JP6588331B2 - Temporary hair dye composition - Google Patents

Description

  The present invention relates to a temporary hair dye composition.

  Hair dyes are permanent hair dyes (hair color, etc.) that are colored by coloring in the hair using an oxidative dye, and semi-permanent hair dyes (hair manicure, etc.) that are colored by penetrating the dye directly into the hair. And a temporary hair dye (hair mascara, etc.) that is colored by forming a colored film containing a colorant (mainly pigment) on the hair. Of these, temporary hair dyes are preferred as being able to enjoy hair dyeing casually because they have little damage to the hair, can be easily removed by shampooing, and can be easily used. As a conventional temporary hair dye, it contains a film-forming polymer in order to fix the colorant on the hair as a colored film, impart water resistance to the colored film, and prevent color transfer to the skin and clothing. Known compositions and the like are known.

  Patent Document 1 discloses a temporary hair dye containing a specific range of poly (N-acylalkylenimine) -modified organopolysiloxane. This temporary hair dye is excellent not only in colorability and difficulty in color transfer, but also in water resistance of the colored film, soft touch of the hair after drying, high setability and resistance to breakage.

  Patent Document 2 discloses a temporary hair dye containing a poly (N-acylalkyleneimine) -modified organopolysiloxane having a modification ratio or the like different from that used in Patent Document 1. This product is excellent in colorability, water resistance and difficulty in color transfer, and also has excellent touch of colored hair, non-stickiness, and coatability on the hair.

  On the other hand, in the field of hair styling agents, it is also known to use a mixture of two or more types of poly (N-acylalkylenimine) -modified organopolysiloxanes. A hair cosmetic containing a specific ratio of poly (N-acylalkylenimine) -modified organopolysiloxane is disclosed. This hair cosmetic can give a soft volume to a thin and easily entangled hair and maintain it for a long time, and can give a soft feel and a natural finish to the eye.

JP 2010-163390 A JP 2012-1480 JP 2013-23465 A

  However, when trying to enhance the appearance of the finished product, especially when seeking fashionability, or for the purpose of fashion, not only coloring but also styling action on the colored and dried hair, the hairstyle is changed. Although there is a request to arrange, the temporary hair dyes described in Patent Documents 1 and 2 have insufficient effects for the purpose of arranging after coloring.

  For example, the temporary hair dye described in Patent Document 1 has a high setting property when the hair is set before being applied and dried, but the hair after drying is strongly sticky. In some cases, it was difficult to arrange further.

  In addition, the temporary hair dye described in Patent Document 2 is not sticky and the hair is easy to handle, but if the comb or hand is passed through, the colored film peels off due to friction and may cause discoloration during styling. It was. Furthermore, when changing the color of the original hair greatly, especially when changing to a vivid color such as blue or red, there is a demand to use it only on the weekend or for only one day. It is necessary to wash away, but with the temporary hair dyes described in Patent Documents 1 and 2, as a result of improving the water resistance, a sufficient amount of the temporary hair dye capable of giving a vivid color to black hair is applied to the hair. When applied, the washability with shampoo was insufficient.

  Therefore, the present invention is easy to handle the hair bundle without being sticky after coloring the hair, so that the styling property is not impaired, the combing property is good, the color is not discolored at the time of friction and the color film is not peeled off, and the friction resistance is excellent. The present invention relates to a temporary hair dye composition that is excellent in wash-off properties even when applied in a sufficient amount to impart vivid color to black hair.

  As a result of intensive studies, the present inventors have found that a temporary hair dye composition that satisfies the above requirements by containing two kinds of poly (N-acylalkylenimine) -modified organopolysiloxanes having different modification ratios in a specific ratio. I found out that

That is, the present invention contains the following components (A) to (C), and the mass ratio (B) / (C) of the component (B) to the component (C) is 1 or more and 5 or less. An agent composition is provided.
Component (A): Pigment Component (B): 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);

[Wherein, 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 mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b) is 48/52 or more and 73/27 or less,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is from 15,000 to 80,000,
Organopolysiloxane Component (C): 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 mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is from 82/18 to 98/2,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is from 50,000 to 150,000,
Organopolysiloxane

  The temporary hair dye composition of the present invention has good colorability and can sufficiently conceal the original hair color, has no stickiness after application, has a good hair bundle slip, and has good combing after drying. If you pass the comb, the hair bundle will be easily separated. Further, even if friction is given to the hair bundle after application or the hair once through the comb after application, there is no color fading or peeling of the colored film. Furthermore, it is excellent in wash-off properties, and even when a sufficient amount is applied for strong color development, it can be restored to its original hair color by washing with shampoo.

[Component (A): Pigment]
The component (A) pigment is used in combination with the component (B) and the component (C) to form a film containing the pigment on the hair and color-coat the hair surface. There is no particular limitation as long as it is generally used as a material.

  Any pigment can be used regardless of its shape (spherical, needle, plate, etc.), particle diameter, particle structure (porous, nonporous, etc.), such as inorganic pigments, organic Examples thereof include pigments, pearl pigments, metal powder pigments, and glittering powders.

  Specific examples of inorganic pigments include inorganic black pigments such as carbon black, black iron oxide, and black titanium oxide; inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate; γ-oxidation Inorganic brown pigments such as iron; Inorganic yellow pigments such as yellow iron oxide and ocher; Inorganic blue pigments such as ultramarine and bitumen; Inorganic purple pigments such as manganese violet and cobalt violet; Chromium oxide, chromium hydroxide and titanium Inorganic green pigments such as cobalt oxide; inorganic white pigments such as titanium oxide, zinc oxide and cerium oxide. Of these, carbon black, black iron oxide, black titanium oxide, iron oxide (bengal), yellow iron oxide, ultramarine blue, and bitumen are preferable.

  Organic pigments include red 201, red 202, red 203, red 204, red 205, red 206, red 207, red 208, red 219, red 220, red 221 and red 228, red 404, red 405, orange color 203, orange color 204, orange color 401, yellow 205, yellow 401, blue 404, etc., of which red 202, red 404, Yellow 205, Yellow 401 and Blue 404 are preferred.

  Examples of the pearl pigment include pearl powder, bismuth oxychloride, mica, metal oxide-coated mica (for example, mica titanium, iron oxide-coated mica, iron oxide-coated mica titanium, black iron oxide-coated mica, black iron oxide-coated mica titanium, yellow Iron oxide coated mica, iron oxide / black iron oxide coated mica titanium, bitumen coated mica titanium, iron oxide / bitumen coated mica titanium, carmine coated mica titanium, barium sulfate coated mica titanium, etc.), metal oxide coated alumina flakes, metal oxide Product-coated silica flakes, multilayer coated pearl pigments (for example, TiO2-SiO2-TiO2-Mica, etc.) and the like.

Examples of the metal powder pigment include gold powder, silver powder, copper powder, aluminum powder, and brass powder.
Examples of the glitter powder include polyethylene terephthalate / aluminum / epoxy laminate, polyethylene terephthalate / polyolefin laminate film, and the like.

  The pigment of component (A) can be used alone or in combination of two or more. The content of component (A) in the temporary hair dye composition is such that red or blue is completely different from the original hair color, regardless of the original hair color, whether it is black hair or blonde hair. From the point of developing a vivid color, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass or more. Further, the amount is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less from the viewpoint that the hair feel is not impaired and the hair is easily handled during styling.

[Component (B): First organopolysiloxane]
The organopolysiloxane of component (B) is the following poly (N-acylalkylenimine) -modified organopolysiloxane (hereinafter also simply referred to as “first organopolysiloxane”).

  Component (B) is represented by the following general formula (1) via an alkylene group containing a hetero atom in at least two silicon atoms of the organopolysiloxane segment constituting the main chain:

[Wherein, 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 mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b) is 48/52 or more and 73/27 or less,
An organopolysiloxane in which the weight average molecular weight of the organopolysiloxane segment constituting the main chain is from 15,000 to 80,000.

  In component (B), at least two poly (N-acylalkylenimine) segments can be bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom. In addition, it is preferably bonded to one or more silicon atoms excluding both ends via the alkylene group, and more preferably bonded to two or more silicon atoms excluding both ends via the alkylene group.

  The alkylene group containing a hetero atom intervening in the bond between an organopolysiloxane segment and poly (N-acylalkyleneimine) has 2 to 20 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms. An alkylene group is mentioned. Specific examples thereof include the following.

The N-acylalkyleneimine unit constituting the poly (N-acylalkylenimine) segment is represented by the general formula (1). In the general formula (1), R ¹ has 1 to 22 carbon atoms. Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 22 carbon atoms, and specifically include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group, nonadecyl group, eicosyl group, docosyl group, etc. Is done. Among these, an alkyl group having 1 to 10 carbon atoms, and more preferably 1 to 6 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, preferably an alkyl group having 1 to 6 carbon atoms.

  The mass ratio (a / b) of the organopolysiloxane segment (a) to the poly (N-acylalkyleneimine) segment (b) in the component (B) is 48/52 or more, and 50/50 or more is Moreover, it is 73/27 or less and 71/29 or less is preferable.

In this specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of component (B) or component (C) in deuterated chloroform, and analyzing by nuclear magnetic resonance ( ¹ H-NMR). The value obtained from the integral ratio of the alkyl group or phenyl group in the organopolysiloxane segment and the methylene group in the poly (N-acylalkylenimine) segment.

  In addition, in the component (B), the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is preferably 1,500 from the viewpoint that it is not sticky after coloring and the hair bundle is easy to handle. More preferably, it is 1,800 or more, more preferably 2,000 or more, preferably 3,500 or less, more preferably 3,200 or less, still more preferably 3,000 or less.

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 to the segment (bonding point A) to a bonding point (bonding point B) of the 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 —Z—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 R ⁷ represents a residue of a polymerization initiator. -Z-R ⁷ represents a poly (N-acylalkylenimine) segment, 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. When the functional group of the modified organopolysiloxane, which is a raw material compound, is 100% substituted with poly (N-acylalkyleneimine), it matches the functional group equivalent (g / mol) of the modified organopolysiloxane.

  Also, when the functional group equivalent (g / mol) of the modified organopolysiloxane that is the raw material compound is known, MWg is the case where the functional group is not 100% substituted with poly (N-acylalkyleneimine) Even so, it can be calculated by the following equation.

  MWg = [functional group equivalent of modified organopolysiloxane (g / mol)] ÷ [substitution rate (%) / 100 (%)]

  When the functional group equivalent of the modified organopolysiloxane is not known, MWg uses the content of organopolysiloxane segment (Csi) constituting the main chain and the molecular weight (MWox) of the poly (N-acylalkyleneimine) segment. Thus, it can be obtained by the following formula.

  The molecular weight (MWox) of the poly (N-acylalkylenimine) segment can be measured by a method of calculating from the molecular weight of N-acylalkyleneimine units and the degree of polymerization, or by a gel permeation chromatography (GPC) measurement method described later. Although possible, in the present invention, the number average molecular weight measured by the GPC measurement method shall be used. The component (B) MWox is preferably 800 or more, more preferably 850 or more, still more preferably 900 or more, and preferably from the viewpoint of excellent friction resistance without causing discoloration or peeling of the colored film during friction. Is 3,500 or less, more preferably 3,200 or less, and still more preferably 3,000 or less.

  In the component (B), the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is 15,000 or more from the viewpoint of excellent friction resistance without color fading or peeling of the colored film during friction. , Preferably 20,000 or more, more preferably 25,000 or more, and 80,000 or less, preferably 70,000 or less, from the viewpoint of excellent washability even when applied in a sufficient amount for vivid color development on black hair, More preferably, it is 60,000 or less. Since the organopolysiloxane segment constituting the main chain has a skeleton common to 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. In addition, the weight average molecular weight of the modified organopolysiloxane which 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: 50μL

  The weight average molecular weight (MWt) of the component (B) organopolysiloxane is preferably 18,000 or more, more preferably 24,000 or more, more preferably 37,000 or more, and preferably 200,000 or less, more preferably 150,000 or less, Preferably it is 120,000 or less, more preferably 92,000 or less, more preferably 80,000 or less, and further preferably 75,000 or less. Thereby, it has sufficient film | membrane intensity | strength and can fix a pigment on hair, without peeling off at the time of friction. Further, while having sufficient water resistance, it dissolves in an activator and the like, and has excellent wash-off properties. In the present specification, MWt can be determined from the weight average molecular weight of the modified organopolysiloxane that is a raw material compound and the aforementioned mass ratio (a / b).

  The organopolysiloxane of component (B) can be produced by a known production method such as the method disclosed in Japanese Patent Application Laid-Open No. 2009-024114 or International Publication 2011/062210.

  Examples of the component (B) organopolysiloxane include poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, and poly (N-propionylethyleneimine) organosiloxane.

  The organopolysiloxane of component (B) can be used alone or in combination of two or more. When two or more components (B) are combined, it is preferable to contain at least two of the following components (B-1) and (B-2).

Component (B-1): Among the components (B), the mass ratio (a / b) between the organopolysiloxane segment (a) and the poly (N-acylalkyleneimine) segment (b) is 48/58 or more 55 / 45 or less organopolysiloxane

Component (B-2): Among the components (B), the mass ratio (a / b) of the organopolysiloxane segment (a) to the poly (N-acylalkylenimine) segment (b) is 65/35 or more 73 / Organopolysiloxane less than 27

  Furthermore, the component (B-1) preferably has a weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments of 2,000 or more and 3,000 or less. The molecular weight (MWox) of the (N-acylalkylenimine) segment is preferably from 1,600 to 3,500.

  Furthermore, in the component (B-2), the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is preferably 2,000 or more and 3,000 or less. The molecular weight (MWox) of the (N-acylalkylenimine) segment is preferably from 800 to 1,600.

  The content of the component (B) in the temporary hair dye composition of the present invention is preferably from the viewpoint of fixing the pigment on the hair and preventing the pigment from peeling off even during friction, and having sufficient water resistance. It is 5% by mass or more, more preferably 7% by mass or more, further preferably 9% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 18% by mass or less.

[Component (C): Second organopolysiloxane]
The organopolysiloxane of component (C) is similar to the organopolysiloxane of component (B) in that the poly (N-acylalkylenimine) segment comprising the repeating unit represented by the general formula (1) has a main chain. A poly (N-acylalkyleneimine) -modified organopolysiloxane (hereinafter simply referred to as “second organopolysiloxane”) bonded to at least two silicon atoms of the organopolysiloxane segment constituting it via an alkylene group containing a hetero atom. Also called).

  Therefore, the component (B) and the component (C) 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 (B) in the following points.

i) The mass ratio (a / b) between the organopolysiloxane segment (A) and the poly (N-acylalkylenimine) segment (B) is from 82/18 to 98/2.
The a / b of the component (C) is non-sticky and excellent in smooth feel, and is preferably 84/16 or more, more preferably 85/15 or more, from the viewpoint of improving combing and finger sliding. More preferably, it is 86/14, more preferably 97/3 or less, and still more preferably 95/5 or less.

ii) The weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is from 50,000 to 150,000.
Ingredient (C) 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 combing and finger slipping. From the viewpoint that the treated temporary hair dye is excellent in water resistance and can be washed away by shampoo, it is preferably 70,000 or more, more preferably 90,000 or more, and 130,000 or less, more preferably 110,000 or less.

iii) The weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is preferably 10,000 or more and 40,000 or less.
The MWg of component (C) is non-sticky and excellent in smooth feel, and is preferably 15,000 or more, more preferably 18,000 or more, from the viewpoint of improving combing and finger sliding. More preferably, it is 35,000 or less, and further preferably 32,000 or less.

iv) The number average molecular weight (MWox) of the poly (N-acylalkylenimine) segment is preferably 500 or more and 4,000 or less.
Component (C) MWox is more preferable from the viewpoint of forming a moderate continuous film on the hair surface, making it non-sticky and having a smooth feel, and improving combing and finger slipping. It is 800 or more, more preferably 1,000 or more, more preferably 3,500 or less, and still more preferably 3,000 or less.

  Further, the weight average molecular weight (MWt) of the organopolysiloxane of component (C) is preferably 60,000 or more, more preferably 80,000 or more, further preferably 9,0000 or more, further preferably 100,000 or more, and preferably 160,000 or less, more preferably 140,000 or less, and still more preferably 120,000 or less. As a result, the non-sticky and smooth feel is further improved, and in addition, the temporary hair dye treated on the hair is excellent in water resistance and at the same time can be washed away by shampoo.

  The organopolysiloxane of component (C) can be used alone or in combination of two or more. The content of the component (C) in the temporary hair dye composition of the present invention is non-sticky and has an excellent smooth feel, and is preferably 0.5 mass from the viewpoint of excellent combability and finger sliding. % Or more, more preferably 1% by weight or more, still more preferably 1.5% by weight or more, and 10% by weight or less, more preferably 8% by weight or less, and further preferably 6% by weight or less.

  The mass ratio (B) / (C) of the component (B) and the component (C) in the temporary hair dye composition of the present invention is difficult to peel off when the hair is rubbed or passed through a comb after hair dyeing, It is 1 or more, preferably 2 or more, more preferably 2.5 or more from the point of no color transfer after combing and excellent wash-off property. Comb is excellent in styling by suppressing clinging to fingers. From the viewpoint of excellent passability, it is 5 or less, preferably 4.5 or less, more preferably 4 or less.

  In addition, the total amount of component (B) and component (C) in the temporary hair dye composition of the present invention is sufficient to fix a sufficient amount of pigment on the hair to coat the hair, From the viewpoint of making it difficult to occur, it is preferably 5.5% by mass or more, more preferably 7% by mass or more, and still more preferably 12% by mass or more. Further, from the viewpoint of suppressing clinging to the finger without impairing the natural feel of the hair and being excellent in washability, it is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. .

  Furthermore, the mass ratio [(B) + (C)] / (A) of the sum of component (B) and component (C) and component (A) in the temporary hair dye composition of the present invention is the hair dye From the viewpoint of preventing the color from peeling off when the hair is subsequently rubbed or passed through a comb, and the color transfer after the comb is suppressed, it is preferably 0.5 or more, more preferably 2 or more, and still more preferably 3 or more. Moreover, from the point which suppresses clinging to a finger | toe and the viewpoint which is excellent in the wash-off property, Preferably it is 20 or less, More preferably, it is 10 or less, More preferably, it is 6 or less.

〔solvent〕
The temporary hair dye composition of the present invention preferably uses a mixture of water and a lower alcohol or a lower alcohol as a solvent from the viewpoint of preventing color transfer to clothing and the like after application and improving the feel. Examples of the lower alcohol include monohydric alcohols having 2 to 4 carbon atoms such as ethanol, 1-propanol and 2-propanol. Among them, ethanol and 2-propanol are preferable, and ethanol is more preferable.

  The content of the lower alcohol in the temporary hair dye composition of the present invention is preferably 30% by mass or more, more preferably 40%, from the viewpoint of promoting solubility during preparation, pigment dispersibility, quick drying after application, and the like. It is at least mass%, more preferably at least 50 mass%, preferably at most 99 mass%, more preferably at most 98 mass%, still more preferably at most 97 mass%.

  Further, when a mixture of water and a lower alcohol is used as a solvent, the content of water in the temporary hair dye composition of the present invention is that the drying time is fast and the color does not transfer to other than the desired part. 35% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[Optional ingredients]
In the temporary hair dye composition of the present invention, in addition to the above components, in order to increase the commercial value within the limits that do not interfere with the effects of the present invention, in order to prevent the deterioration of the composition over time Preservatives and antioxidants can be added to the surfactant, and if necessary, surfactants, curing agents, antistatic agents, antifoaming agents, dispersants, thickeners, UV absorbers, antioxidants Agents, preservatives, colored dyes, dye fixing agents, propellants and the like can also be added.

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

Synthesis Example 1: Organopolysiloxane A
Dissolve 6.17 g (0.04 mol) of diethyl sulfate and 93.8 g (0.947 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 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 an 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. 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: Organopolysiloxane B
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 1000. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 50,000, 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 (138 g, yield 98%). The content of the organopolysiloxane segment in the final product was 71% by mass, and the weight average molecular weight was 70,000. 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 3 Organopolysiloxane C
In the same manner as in Synthesis Example 1, 19.0 g (0.12 mol) of diethyl sulfate and 81.0 g (0.82 mol) of 2-ethyl-2-oxazoline were dissolved in 203 g of dehydrated ethyl acetate and heated under reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethyleneimine) was synthesized. The number average molecular weight measured by GPC was 800. A 33% ethyl acetate solution of 300 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 50,000, 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 rubbery solid (390 g, yield 97%). The content of the silicone segment in the final product was 75% by mass, and the weight average molecular weight was 67,000. 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 4 Organopolysiloxane D
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 100,000, amine equivalent 20,000) 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 colorless solid (108 g, yield 95%). The final product had an organopolysiloxane segment content of 88 mass% and a weight average molecular weight of 114,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

[Examples 1-7, Comparative Examples 1-5]
Temporary hair dye compositions shown in Table 1 were prepared by a conventional method, and 0.4 g of each composition was spread over the hair bundle for evaluation shown below from the root of the hair bundle to the hair tip. The hair bundle was dried at room temperature for 1 minute. Thereafter, performance evaluation was performed according to the following methods and standards.

<Evaluation hair bundle>
A hair bundle with a length of 25 cm and a weight of 1 g was made from Japanese straight hair with no chemical treatment history. This hair bundle was washed with a model shampoo shown below. After towel drying, the hair bundle after drying for 1 minute with a dryer (Soris dryer 315, manufactured by Solis) was used for evaluation.

Model shampoo composition
(mass%)
Polyoxyethylene (2.5) sodium lauryl ether sulfate 15.50
Lauric acid diethanolamide 2.28
Edetate disodium 0.10
Sodium benzoate 0.50
Oxybenzone 0.03
Phosphoric acid 0.075
Dibutylhydroxytoluene 0.01
Sodium chloride 0.80
Red No. 106 0.00012
Fragrance 0.26
Purified water balance

<Colorability to black hair>
The four-stage visual evaluation by five panelists was performed on the colorability of each colored hair bundle.
4 points: The hair color is concealed and fully colored 3 points: The hair color is slightly concealed and colored 2 points: The hair color is not concealed and colored too much No 1 point: Not colored at all

<Combination after drying>
The panel was evaluated by five panelists when combs (HK0103 B's set comb L, manufactured by Kaiinsha Co., Ltd.) were passed through the dried colored hair bundle once every second for a total of 10 passes.
4 points: easy combing to break the hair bundle 3 points: slightly combing to comb the hair bundle 2 points: Slightly bad combing and difficult to break the hair bundle 1 point : The comb does not pass and the hair bundle cannot be broken.

<Peeling resistance after combing>
While the 5 cm square black drawing paper was folded in half, the root of the hair bundle evaluated for combability after drying was sandwiched and a 200 g weight was placed. With the weight placed, the hair bundle was pulled out in 3 seconds, the black drawing paper after the test was observed, and the pigment of the colored hair bundle remaining on the paper was visually observed to evaluate the peel resistance under a 200 g load environment. . Observation was performed by four-stage visual evaluation by five panelists.
4 points: No color transfer 3 points: Some peeling film fragments adhere slightly, but almost no color transfer 2 Points: The peeling film adheres in a streak shape and slightly transfers 1 point: Color transfer

<No clinging to fingers>
The hair bundles that were evaluated for combability after drying were touched with a finger, and the absence of clinging to the finger was evaluated according to the following criteria. Evaluation was performed by four-level evaluation by five panelists.
4 points: no stickiness and good slipping 3 points: little stickiness and easy slipping 2 points: slightly sticky feeling and slightly slipping 1 point: sticky feeling and poor slipping

<Washability>
After wetting the hair bundle evaluated for combability after drying for 10 seconds with tap water at 40 ° C, apply 0.5g of the model shampoo listed above, lather for 30 seconds, and then rinse with tap water at 40 ° C for 15 seconds. Was performed twice. Thereafter, towel drying was performed, and then the color of the hair bundle was observed after drying with a dryer (Soris Dryer 315) for 1 minute. Observation was performed by four-stage visual evaluation by five panelists.
4 points: Can be completely washed out and has no colored portion 3 points: Can be almost completely washed out and has almost no colored portion 2 points: Almost completely washed out, but there are few colored portions 1 Point: It cannot be washed off, and there are noticeable colored parts

Claims (6)

A temporary hair dye composition comprising the following components (A) to (C), wherein the mass ratio (B) / (C) of the component (B) to the component (C) is from 1 to 5.
Component (A): Pigment Component (B): 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);

[Wherein, 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 mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b) is 48/52 or more and 73/27 or less,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is from 15,000 to 80,000,
Organopolysiloxane Component (C): 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 mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is from 82/18 to 98/2,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is from 50,000 to 150,000,
Organopolysiloxane   Temporary hair dyeing according to claim 1, wherein the mass ratio [(B) + (C)] / (A) of the sum of component (B) and component (C) to component (A) is 0.5 or more and 20 or less. Agent composition.   The temporary hair dye composition according to claim 1 or 2, wherein the content of the component (A) is 0.5 mass% or more and 20 mass% or less.   The temporary hair dye composition according to any one of claims 1 to 3, wherein the total content of the component (B) and the component (C) is 5.5% by mass or more and 30% by mass or less.   The temporary hair dye composition according to any one of claims 1 to 4, wherein the number average molecular weight of the poly (N-acylalkylenimine) segment bonded to the organopolysiloxane of component (B) is 800 or more and 3,500 or less. object.   Temporary hair dye composition given in any 1 paragraph of Claims 1-5 whose content of water is 10 mass% or less.