JP5808183B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic containing an organopolysiloxane having a specific structure in a specific ratio.

  Since organopolysiloxane has many excellent characteristics, various forms are frequently used as a touch improver in shampoos, hair conditioners and the like. For example, Patent Document 1 discloses a hair setting agent composition containing a poly (N-acylalkylenimine) -modified organopolysiloxane that does not break or plastically deform within a certain range of elongation. Compared to conventional hair setting compositions that use film-forming resins, this hair setting agent is superior in hair setting ability and retention, and gives a soft and soft feel to hair after it has been trimmed. In addition, it has excellent performance that it can be easily washed away by washing the hair. However, with this hair set composition, the effect of setting a soft, voluminous hairstyle on the thin, entangled hair that is difficult to produce a voluminous feel, and maintaining the voluminous feel when a finger is passed through the hair. Not enough.

  Patent Document 2 discloses that poly (N-acylalkylenimine) -modified organopolysiloxane having a different modification ratio from that used in Document 1 has excellent extensibility and is soluble in water and lower alcohols. It is disclosed as having excellent properties and dispersibility. Hair cosmetics containing this organopolysiloxane have a good feel for the set purpose of maintaining curl shape and keeping the hair aligned and flowing, and external factors (passing fingers through hair, wind, vibration Etc.) for the purpose of giving and maintaining a soft and voluminous feel for thin, tangled hair that is difficult to produce a voluminous feel. It was insufficient.

Japanese Unexamined Patent Publication No. 07-133352 JP 2009-24114

  The present invention provides a hair cosmetic capable of giving a soft volume and maintaining for a long time with respect to thin and easily entangled hair that does not give a sense of volume, and can give a soft feel and a natural finish to the eye. This is the issue.

  The inventors of the present invention can solve the above-mentioned problems by preparing a hair cosmetic in which two poly (N-acylalkylenimine) -modified organopolysiloxanes having a specific structure are blended at a specific ratio. I found it.

The present invention provides a hair cosmetic containing the following components (A) and (B) in a mass ratio of (A) / (B) = 1.6 or more.
Component (A): At least two silicon atoms of the organopolysiloxane segment 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-acylalkyleneimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 800 to 1,600,
The mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly (N-acylalkylenimine) segment (b) is 73/27 to 80/20,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1,500-3,500,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 10,000 to 100,000,
Organopolysiloxane Component (B): It consists of a repeating unit represented by the above general formula (1) via an alkylene group containing a hetero atom on at least two silicon atoms of the organopolysiloxane segment constituting the main chain. An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments,
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4,000,
The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 82/18 to 99/1,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 10,000 to 40,000;
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 50,000 to 150,000,
Organopolysiloxane

  Furthermore, the present invention provides a hair treatment method in which after applying the above-described hair cosmetic composition to hair, air drying or natural drying is performed without washing away.

  The hair cosmetic composition of the present invention can give a soft and voluminous feel to a thin and easily entangled hair that does not give a voluminous feel and can maintain a soft feel and a natural finish.

[Component (A): First organopolysiloxane]
In the organopolysiloxane of component (A), poly (N-acylalkyleneimine) segments are spaced at predetermined intervals via an alkylene group containing a hetero atom on at least two silicon atoms of the organopolysiloxane segment constituting the main chain. And a specific structure coupled at a predetermined ratio. 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 N-acylalkyleneimine unit constituting the poly (N-acylalkylenimine) segment, in the general formula (1), the alkyl group having 1 to 22 carbon atoms in R ¹ is, for example, a straight chain having 1 to 22 carbon atoms. Examples include chain, branched or cyclic alkyl groups, and specifically include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, and cyclohexyl groups. Examples include xyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, nonadecyl, eicosyl, docosyl 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) of the organopolysiloxane segment (a) to the poly (N-acylalkyleneimine) segment (b) in component (A) is 73/27 to 80/20, but the hair surface From the viewpoint of making it particularly suitable for expressing the effects of the present invention by forming an appropriate continuous film on the hair and ensuring appropriate elasticity and adhesiveness on the hair, preferably 73/27 It is -79/21, More preferably, it is 73 / 27-78 / 22.

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 calculated | required from the integral ratio of the alkyl group of this, or a phenyl group, and the methylene group in a poly (N-acyl alkylene imine) segment.

  The weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is 1,500 to 3,500, preferably 1,600 to 3,200, more preferably 1,700 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.

  MWg is the molecular weight of the portion surrounded by the broken line in the above general formula (2), but is understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkylenimine) segment. Can do. When the functional group of the modified organopolysiloxane, which is a raw material compound, is 100% substituted with poly (N-acylalkylenimine), it matches the functional group equivalent (g / mol) of the modified organopolysiloxane.

  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. However, in the present invention, it means the number average molecular weight measured by the GPC measurement method. The MWox of component (A) is from 800 to 1,600, preferably from 850 to 1,500, more preferably from 900 to 1,400. Thereby, a soft volume can be given to the hair, and sufficient hardness and good feel can be imparted to maintain the hairstyle.

  MWg 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 10,000 to 100,000. From the viewpoint of solubility in polar solvents such as water and ease of handling after dissolution, preferably 20,000 to 80,000, More preferably, it is 30,000-60,000. 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 (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 (A) is preferably from 12,000 to 150,000, more preferably from 24,000 to 120,000, and even more preferably from 37,000 to 92,000. Thereby, the good touch to hair can be provided, and also the solubility with respect to polar solvents, such as water, becomes excellent. Moreover, the sustainability of the soft and voluminous volume 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 (A) will be described.
The organopolysiloxane of component (A) is, for example, the following general formula (3)

[Wherein, R ² has the same meaning as R ^{2 in the} general formula (2), 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 the above formulas (ix) to (xiv), a represents an integer of 135 to 1,350, and b represents 3 Represents an integer of ~ 57. ]
Modified organopolysiloxane represented by the following general formula (4)

Wherein, R ¹ and n are respectively R ¹ and n in the general formula (1) synonymous. ]
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 (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 the weight average molecular weight is preferably 10,000 to 100,000, more preferably. It is desirable to use 20,000-80,000, more preferably 30,000-60,000. 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 800 to 1,600, preferably 850 to 1,500, more preferably 900 to 1,400. 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 20 to 2,000 parts by mass with respect to 100 parts by mass of the cyclic iminoether (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.

  In the organopolysiloxane of component (A), at least two silicon atoms of the organopolysiloxane segment having a predetermined molecular weight have poly (N-acylalkyleneimine) segments at predetermined intervals via an alkylene group containing a hetero atom, In addition, it has a unique structure combined at a predetermined ratio. Thereby, the finger passage to the hair is made good, and a soft and voluminous and high sustainability is obtained. Moreover, it can be dissolved in polar solvents such as water and lower alcohols.

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

  The component (A) organopolysiloxane can be used alone or in combination of two or more thereof, and its content improves the slipperiness of the finger and maintains the soft and voluminous feel for a long time. From 0.01 to 30% by mass, more preferably from 0.05 to 20% by mass, still more preferably from 0.1 to 10% by mass, and even more preferably from 0.5 to 5% by mass, based on the total mass of the hair cosmetic. In addition, by using such a content, when used in combination with the component (B) described below, it improves finger sliding, and has an excellent effect of maintaining a soft and voluminous feeling for a long time. can do.

[Component (B): Second organopolysiloxane]
The component (B) organopolysiloxane is similar to the component (A) in that the poly (N-acylalkyleneimine) segment comprising the repeating unit represented by the general formula (1) constitutes the main chain. The siloxane segment is bonded to at least two silicon atoms via an alkylene group containing a hetero atom. Therefore, the component (A) and the component (B) have structures similar to each other, and both are referred to as “polysilicone-9” by the INCI name. Siloxane is different from the organopolysiloxane of component (A) in the following points.

i) The mass ratio (a / b) between the organopolysiloxane segment (a) and the poly (N-acylalkylenimine) segment (b) is 82/18 to 99/1.
a / b is non-sticky and has an excellent smooth feel, and is preferably 84/16 to 99/1, more preferably 85/15 to 98/2, and more preferably 85/15 to 98/2, from the viewpoint of improving finger sliding. Preferably it is 86 / 14-97 / 3.

ii) The weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 10,000 to 40,000.
The MWg is preferably 15,000 to 35,000, and more preferably 18,000 to 32,000, from the viewpoint that it is non-sticky and has an excellent smooth feel and improves the sliding of the finger.

iii) The number average molecular weight (MWox) of the poly (N-acylalkylenimine) segment is 500 to 4,000.
MWox forms an appropriate continuous film on the hair surface, is non-sticky and has an excellent smooth feel, and is preferably 800 to 3,500, more preferably 1,000 to 100% from the viewpoint of improving finger sliding. 3,000.

iv) The weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is 50,000 to 150,000.
MWsi forms a moderate continuous film on the hair surface to satisfy smooth touch and non-stickiness at the same time. In addition, it improves the sliding of the finger and further dissolves in water and other polar solvents. From the viewpoint of ensuring ease of handling after dissolution, it is preferably 70,000 to 130,000, more preferably 90,000 to 110,000.

  Further, the weight average molecular weight (MWt) of the organopolysiloxane of component (B) is preferably 60,000 to 160,000, more preferably 80,000 to 140,000, and still more preferably 100,000 to 120,000. Thereby, it is assumed that the non-sticky and smooth feeling is further improved, and in addition, the solubility in a polar solvent in water or the like becomes excellent.

  The organopolysiloxane of component (B) includes, for example, a modified organopolysiloxane in which a is an integer of 135 to 1,350 and b is an integer of 3 to 57 in the general formula (3), and a cyclic imino ether (4). It can be produced by reacting a terminal-reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization.

  As the modified organopolysiloxane, the functional group equivalent is preferably 10,000 to 40,000, more preferably 15,000 to 35,000, particularly preferably 18,000 to 30,000, and the weight average molecular weight is preferably 50,000 to 150,000, more preferably 70,000 to 130,000. In particular, it is desirable to use those which are 90,000-110,000.

  The terminal reactive poly (N-acylalkylenimine) is preferably adjusted to have a molecular weight of 500 to 4,000, more preferably 800 to 3,500, and still more preferably 1,000 to 3,000.

  Except for these points, the organopolysiloxane of component (B) can be produced in the same manner as in the production of the organopolysiloxane of component (A) described above.

  The component (B) organopolysiloxane can be used alone or in combination of two or more thereof, and its content improves the slipperiness of the finger and maintains the soft and voluminous feel for a long time. Therefore, it is preferably 0.001 to 30% by mass, more preferably 0.005 to 20% by mass, still more preferably 0.01 to 10% by mass, and still more preferably 0.05 to 5% by mass, based on the total mass of the hair cosmetic. Moreover, by setting it as this content, both styling of set property and set sustainability when used in combination with component (A) can be further improved.

  The organopolysiloxanes of component (A) and component (B) have similar structures as described above, but their characteristics are different.The organopolysiloxane of component (A) sets the hairstyle at around room temperature. On the other hand, the organopolysiloxane of component (B) has weak surface tackiness and surface lubricity, and has suitable tackiness and elasticity suitable for holding.

  The mass ratio (A) / (B) of the component (A) to the component (B) in the hair cosmetic composition of the present invention improves the slipping of the finger and maintains a soft and voluminous feeling for a long time. From the viewpoint of improving the above effect, it is 1.6 or more, preferably 1.6 to 10.0, and more preferably 1.9 to 5.0. The above-described effects of the present invention can be obtained by combining the component (A) and the component (B) in the above ratio, and numerically, the organopolysiloxane near the average value when both components are used in combination. Even if siloxane (polysilicone-9) is used alone, such an effect cannot be obtained.

  That is, the present inventors have found that a film formed on the surface of hair has the following characteristics by the combined use of component (A) and component (B).

  When the content ratio (A) / (B) of the two is mixed within the range of 1.6 or more, the surface layer of the organopolysiloxane (B) has weak adhesiveness and surface lubricity, and the continuous layer organopolysiloxane ( Since the surface tackiness and elasticity of A) are moderately compatible, it is particularly excellent in imparting a voluminous hairstyle, suppressing floating hair, and maintaining the finished hairstyle.

[Component (C): Third organopolysiloxane]
The hair cosmetic composition of the present invention can further contain an organopolysiloxane of component (C). The organopolysiloxane of component (C) is similar to component (A) in that the poly (N-acylalkyleneimine) segment comprising the repeating unit represented by the general formula (1) constitutes the main chain. The siloxane segment is bonded to at least two silicon atoms via an alkylene group containing a hetero atom. Therefore, the component (A), the component (B), and the component (C) have structures similar to each other, and both are referred to as `` polysilicone-9 '' under the INCI name. The organopolysiloxane of C) is different from the organopolysiloxane of component (A) and component (B) in the following points.

i) The mass ratio (a / b) of the organopolysiloxane segment (a) to the poly (N-acylalkylenimine) segment (b) is 35/65 to 60/40.
a / b is preferably 42/58 to 58/42, more preferably 45/55 to 55/45, and still more preferably 47/53 to 53/47 from the viewpoint of giving a soft volume to the hair.

ii) The weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is 1300-5500.
MWg is preferably 1600 to 3500, more preferably 1800 to 3200, and still more preferably 2,000 to 3,000, from the viewpoint of giving a soft volume to the hair.

iii) The number average molecular weight (MWox) of the poly (N-acylalkylenimine) segment is from 1,200 to 5,500.
MWox is preferably from 1,600 to 3,500, more preferably from 1,800 to 3,200, more preferably from 2,000 to 3,000, from the viewpoint of giving a soft volume to the hair.

iv) The weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is 7,000 to 100,000.
MWsi is preferably 10,000 to 80,000, more preferably 20,000 to 60,000, from the viewpoint of giving a soft volume to the hair, and further ensuring solubility in a polar solvent in water and the like and ease of handling after dissolution. More preferably, it is 30,000-50,000.

  The weight average molecular weight (MWt) of the organopolysiloxane of component (C) 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 soft volume is given to the hair, and in addition, the solubility in polar solvents in water and the like becomes excellent.

  The organopolysiloxane of component (C) includes, for example, a modified organopolysiloxane in which a is an integer of 89 to 1332 and b is an integer of 2 to 77 in the general formula (3), and a cyclic imino ether (4). It can be produced by reacting a terminal-reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization.

  As the modified organopolysiloxane, the functional group equivalent is preferably 1,700 to 3,500, more preferably 1,800 to 3,200, particularly preferably 2,000 to 3,000, and the weight average molecular weight is preferably 7,000 to 100,000, more preferably 10,000 to 80,000. In particular, it is desirable to use one having a viscosity of 30,000 to 50,000.

  Further, the terminal reactive poly (N-acylalkylenimine) is preferably adjusted to have a molecular weight of 1,200 to 5,500, more preferably 1,600 to 3,500, still more preferably 1,800 to 3,200, still more preferably 2,000 to 3,000.

  Except for these points, the organopolysiloxane of the component (C) can be produced in the same manner as the production of the organopolysiloxane of the components (A) and (B) described above.

  The organopolysiloxane of component (C) can be used singly or in combination of two or more, and the content thereof is from the viewpoint of giving the hair a soft volume and a firm texture. On a mass basis, it is preferably 0.001 to 30% by mass, more preferably 0.005 to 20% by mass, still more preferably 0.01 to 10% by mass, and still more preferably 0.05 to 5% by mass. In addition, by using such a content, when used in combination with the components (A) and (B), it is possible to further improve the effect of giving a soft volume and firm texture and maintaining for a long time. .

  Component (A) and (B) of the present invention, or the total content as organopolysiloxane obtained by further adding component (C) to the hair, from the viewpoint of giving the hair a soft volume and firm texture It is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, still more preferably 0.1 to 10% by mass, and still more preferably 0.5 to 6% by mass, based on the total mass of the cosmetic.

[Lower alcohol]
Furthermore, the hair cosmetic composition of the present invention can contain an aliphatic alcohol having 1 to 6 carbon atoms. The content of the aliphatic alcohol having 1 to 6 carbon atoms is preferably 0.01 to 98% by mass, more preferably 0.1 to 90% by mass, and particularly preferably 0.5 to 75% by mass in the hair cosmetic composition of the present invention. As a result, the conformability of the present hair cosmetic to the hair is improved, and it is possible to more effectively suppress the voluminous hairstyle and the floating hair.

[Cationic surfactant]
The hair cosmetic composition of the present invention preferably further contains a cationic surfactant. Examples of the cationic surfactant include quaternary ammonium salts represented by the following general formula (5).

[In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and simultaneously a hydrogen atom or a benzyl group; Except when it becomes an alkyl group. Z ⁻ represents an anion. ]

Here, one of R ⁸ and R ⁹ is preferably a linear or branched alkyl group having 14 to 24 carbon atoms, particularly a linear alkyl group, and the other is a lower alkyl group having 1 to 3 carbon atoms, A methyl group is particularly preferable. Examples of the anion Z ⁻ include halide ions such as chloride ions and bromide ions; organic anions such as ethyl sulfate ions and methyl carbonate ions, and halide ions, particularly chloride ions are preferable.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Stearyl trimethyl ammonium and behenyl trimethyl ammonium chloride are preferable.

  These cationic surfactants can be used singly or in combination of two or more, and the content thereof is preferably 0.01 to 10% by mass, particularly 0.05 to 5% by mass in the hair cosmetic composition of the present invention. As a result, the adhesion of the film to the hair by the component (A) and the component (B) becomes uniform, thereby improving the suitability of the hair cosmetics to the hair and improving the smoothness of the hair during hair styling. Further, the effect of imparting volume to the hairstyle and the effect of suppressing floating hair are further improved.

[Other surfactants]
The hair cosmetic composition of the present invention can contain a surfactant other than the cationic surfactant from the viewpoint of system stability including solubilization and dispersibility of the solvent. As such a surfactant, any of a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant can be used.

  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 is particularly preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  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-sulfo 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.

  These surfactants other than the cationic surfactant 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 and emulsification of the oil agent, the content thereof is as follows. 0.01 to 10% by mass, particularly 0.05 to 5% by mass in the hair cosmetic composition of the invention is preferred.

[PH]
In the hair cosmetic composition of the present invention, the pH at 25 ° C. when diluted 20 times by mass with water is preferably 2.5 to 7.0, more preferably pH 2.5 to 6.0, and particularly preferably pH 3.0 to 5.0.

  The form of the hair cosmetic composition of the present invention can be appropriately selected from liquid form, gel form, foam form, paste form, emulsion and the like, but a liquid form using water or lower alcohol as a solvent is preferable.

  The hair cosmetic of the present invention is preferably of a type that is used without being washed off after being applied to the hair, and is preferably used as a hair styling agent, hair conditioning agent or the like. Examples of the dosage form include pump spray, aerosol spray, pump foam, aerosol foam, gel, lotion, cream and the like.

[Hair treatment method]
The hair cosmetic composition of the present invention can obtain a desired hair styling effect by applying it to the hair and then finishing it by blowing or natural drying without washing it off. Here, when the hair after application of the hair cosmetic is dried, it may be left as it is, but the hair modifying effect can be obtained by drying by blowing with air. Here, “do not wash away” means that the time from application to the hair until the next shampoo is at least 3 hours, preferably 6 hours or more.

  Furthermore, the effect of this invention can be heightened more by heating hair cosmetics after apply | coating to hair. For heating, a dryer, a heater, a trowel, an iron, or the like can be used. When using a drier, a heater, etc., as temperature, 60 to 150 degreeC, especially 70 to 120 degreeC is preferable. The heating time is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 20 minutes, and particularly preferably 30 seconds to 10 minutes. When using a trowel, iron or the like, the temperature is preferably 80 ° C to 250 ° C, particularly 100 ° C to 200 ° C. The heating time is preferably 0.5 seconds to 3 minutes, more preferably 1 second to 2 minutes, and particularly preferably 2 seconds to 30 seconds. Also, the time from application of the hair cosmetic to heating and heating is preferably within 1 hour, more preferably within 45 minutes, and particularly preferably within 30 minutes.

Synthesis Example 1 Organopolysiloxane A
Dissolve 19.0 g (0.12 mol) of diethyl sulfate and 81.0 g (0.82 mol) of 2-ethyl-2-oxazoline in 203 g of dehydrated ethyl acetate, and heat and 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 1,100. A 33% ethyl acetate solution of 300 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32,000, amine equivalent 2,000) 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 solid (390 g, yield 97%). The final product had an organopolysiloxane segment content of 75 mass% and a weight average molecular weight of 40,000. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, about 20 mol% of amino groups remained.

Synthesis Example 2 Organopolysiloxane B
Dissolve 0.8 g (0.005 mol) of diethyl sulfate and 12.8 g (0.14 mol) of 2-ethyl-2-oxazoline in 29 g of dehydrated ethyl acetate, and heat and 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 pale yellow rubber-like solid (111 g, yield 98%). The final product had an organopolysiloxane segment content of 88 mass% and a weight average molecular weight of 114,000. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, no amino group remained.

Synthesis Example 3 Organopolysiloxane C
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 30,000, amine equivalent 2,000) 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 60,000. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, about 20 mol% of amino groups remained.

Synthesis Example 4 Organopolysiloxane D
6.5 g (0.042 mol) of diethyl sulfate and 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline were dissolved in 87 g of dehydrated ethyl acetate and heated under reflux for 8 hours under a nitrogen atmosphere to react with terminal reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 1300. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) 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 (138 g, yield 98%). The final product had an organopolysiloxane segment content of 71 mass% and a weight average molecular weight of 46000. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, about 22 mol% of amino groups remained.

Examples 1-3 and Comparative Examples 1-5
The hair cosmetics shown in Table 1 were prepared according to a conventional method, and “hair bulk evaluation” and “slip finger evaluation after finishing” were performed according to the following methods.

1. Evaluation of hair bulkiness A wig (average hair diameter of about 50 μm, hair density of 150 hairs / cm ² ) manufactured by Beaulux Co., Ltd. is cut so that the length of the hair becomes medium length. The wig is washed with a plain shampoo (Curel shampoo manufactured by Kao), further treated with rinse (Curel rinse made by Kao), and then dried with hot air from a blow dryer (Ionity EH5305P manufactured by Panasonic). Next, 5 g of water was applied to the wig and combed with a comb, and then the hair treatment agent described in Table 1 (Examples 1 to 3, Comparative Examples 1 to 4) or 2 g of water (Comparative Example 5) was rooted. After the coating, a hand blow finish was performed so as to raise the roots with a blow dryer.

[Immediate evaluation]
The wig subjected to the hand blow finish was allowed to stand for 3 minutes, and then the bulk of the hair was measured with a ruler at 7 cm along the midline from the front root of the wig.

[Evaluation after thirty fingers]
Pass the finger through the front part of the wig after the hand blow finish from the front part to the back of the head for 30 times, leave the wig for 3 minutes, then 7cm along the midline from the front base. The bulk of the hair was measured with a ruler.

2. Evaluation of sliding finger after finishing Cut a wig (average hair diameter of about 50 μm, hair density of 150 pcs / cm ² ) manufactured by Beaulux Co., Ltd. so that the length of the hair becomes medium length. The wig is washed with a plain shampoo (Curel shampoo manufactured by Kao), further treated with rinse (Curel rinse made by Kao), and then dried with hot air from a blow dryer (Ionity EH5305P manufactured by Panasonic). Next, 5g of water was applied to the wig and blended.

・ [Reference product; Comparative Example 5]
2g of water was applied to the base of the wig treated according to the above procedure and hand blow-finished so as to cause the base with a blow dryer, and then left for 3 minutes to obtain a reference product.
[Evaluated product: Examples 1 to 3, Comparative Examples 1 to 4]
2 g of the hair treatment agent shown in Table 1 was applied to the roots of the wig treated according to the above procedure, hand blow-finished so as to cause the roots with a blow dryer, and then left for 3 minutes to obtain an evaluation product.
A sensory evaluation of “good fingering” was performed by five expert panelists.
4 points: fingering is clearly better than the standard 3 points: fingering is better than the standard 2 points: fingering is slightly better than the standard 1 point: fingering is equivalent to the standard or worse than the standard

  Table 1 shows the sum of sensory evaluations of five professional panelists.

Formulation Example 1 (hair mist)
(mass%)
Organopolysiloxane A (Synthesis Example 1) 0.6
Organopolysiloxane B (Synthesis Example 2) 0.3
95 mass% ethanol 11.0
Coatamine 86W (28% by mass, manufactured by Kao Corporation) 0.85
Silicone KF6029 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5
Fragrance 0.05
Purified water remaining

Formulation example 2 (hair lotion)
(mass%)
Organopolysiloxane A (Synthesis Example 1) 0.8
Organopolysiloxane B (Synthesis Example 2) 0.2
95 mass% ethanol 5.0
Coatamine 86W (28% by mass) (manufactured by Kao Corporation) 0.85
Calcoal 6780 (manufactured by Kao Corporation) 1.5
SM8904 COSMETIC EMULSION (40% by mass, Dow Corning Toray) 0.2
Guffcut 734 (50% by mass, ISP) 0.6
Fragrance 0.1
Purified water remaining

Formulation Example 3 (Water)
(mass%)
Organopolysiloxane A (Synthesis Example 1) 0.4
Organopolysiloxane B (Synthesis Example 2) 0.1
Malic acid 1.4
Benzyl alcohol 0.2
Dipropylene glycol 2.0
Coatamine 86W (28% by mass, manufactured by Kao Corporation) 0.85
Ethanol 15.0
Polyoxyethylene hydrogenated castor oil 0.2
Perfume 0.06
Purified water Remaining sodium hydroxide (pH adjuster) Amount adjusted to pH 4.0

Formulation example 4 (hair mist)
(mass%)
Organopolysiloxane A (Synthesis Example 1) 2.0
Organopolysiloxane B (Synthesis Example 2) 1.0
Organopolysiloxane C (Synthesis Example 3) 2.0
95 mass% ethanol 12.0
Coatamine 86W (28% by mass, manufactured by Kao Corporation) 0.85
Fragrance 0.05
Purified water remaining

Claims (8)

A hair cosmetic comprising the following components (A) and (B) in a mass ratio of (A) / (B) = 1.6 to 4.5 .
Component (A): At least two silicon atoms of the organopolysiloxane segment 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-acylalkyleneimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 800 to 1,600,
The mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly (N-acylalkylenimine) segment (b) is 73/27 to 80/20,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1,500-3,500,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 10,000 to 100,000,
Organopolysiloxane Component (B): It consists of a repeating unit represented by the above general formula (1) via an alkylene group containing a hetero atom on at least two silicon atoms of the organopolysiloxane segment constituting the main chain. An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments,
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4,000,
The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 82/18 to 99/1,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 10,000 to 40,000;
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 50,000 to 150,000,
Organopolysiloxane Furthermore, the hair cosmetics of Claim 1 containing a component (C).
Component (C): Poly (N--) comprising a repeating unit represented by the general formula (1) via an alkylene group containing a hetero atom on at least two silicon atoms of the organopolysiloxane segment constituting the main chain An acylpolyalkyleneimine) segment bonded to an organopolysiloxane,
The number average molecular weight of the poly (N-acylalkylenimine) segment is 1,200-5,500,
The mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 35/65 to 60/40,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is 1,300-5,500,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 7,000 to 100,000,
Organopolysiloxane   The hair cosmetic according to claim 1 or 2, further comprising water and / or an aliphatic alcohol having 1 to 6 carbon atoms.   Furthermore, the hair cosmetics in any one of Claims 1-3 containing a cationic surfactant.   The hair cosmetic composition according to any one of claims 1 to 4, wherein the content of the component (A) in the hair cosmetic composition is 0.01 to 30% by mass.   The hair cosmetic composition according to any one of claims 1 to 5, wherein the content of the component (B) in the hair cosmetic composition is 0.001 to 30% by mass.   The hair cosmetic according to any one of claims 1 to 6, which is used without being washed away after being applied to the hair.   A hair treatment method in which after the hair cosmetic composition according to any one of claims 1 to 7 is applied to hair, air drying or natural drying is performed without washing away.