Resin for hair cosmetic and hair cosmetic

Abstract

Provided are: a resin for hair cosmetics, which is not sticky and has both high adhesiveness and combability without impairing properties such as water resistance, coloring properties, and easy-to-clean properties; and a hair cosmetic. The resin for hair cosmetics is characterized in that: the resin for hair cosmetics is obtained by bonding a poly (N-acyl alkyl imine) segment (b) containing a repeating unit represented by formula (1) to at least two silicon atoms of an organopolysiloxane segment (a) constituting the main chain via a heteroatom-containing alkylene group; the heteroatom-containing alkylene group is an arbitrary group represented by formula (i) or (ii), the mass-average molecular weight of the segment (a) is 10,000-100,000, the number-average molecular weight of the segment (b) is less than 800, and the mass ratio ((a) / (b)) of (a) and (b) is 58 / 42-90 / 10. # imgabs0 # [In formula (1), R1 represents a hydrogen atom, an alkyl group having 1-22 carbon atoms, an aralkyl group, or an aryl group, and n represents 2 or 3. ] (i) # imgabs1 # (ii) # imgabs2 #

Description

Technical Field

[0001] This specification relates to a hair cosmetic resin and a hair cosmetic having both high adhesion and combing properties. Background Art

[0002] Conventionally, hair cosmetics for eyelashes, hair, etc. have been known to have various formulations and have been used in various forms.

[0003] Generally, hair cosmetics applied using an applicator such as a brush or a comb are required to have good combing properties, non-stickiness, adhesion, water resistance, colorability, easy cleaning, and the like.

[0004] As conventional hair cosmetics, for example, the following cosmetics are known: 1) A resin emulsion for eyelash cosmetics and an eyelash cosmetic containing the acrylic resin emulsion for eyelash cosmetics, characterized in that when used as a mascara, the resin emulsion for eyelash cosmetics has excellent water resistance, curl retention under high humidity, and easy washing with water, and contains a polyvinyl alcohol resin I and a vinyl resin A, and the weight ratio of the polyvinyl alcohol resin I to the vinyl resin A in the emulsion is 55:45 to 99:1 (see, for example, Patent Document 1).

[0005] 2) An organopolysiloxane and a hair cosmetic containing the organopolysiloxane, wherein the organopolysiloxane is excellent in spreadability and has excellent solubility and dispersibility in water and lower alcohols, wherein a poly(N-acylalkyleneimine) segment comprising a repeating unit represented by a specific formula is bonded to at least two silicon atoms of an organopolysiloxane segment constituting a main chain via an alkylene group containing a heteroatom, wherein the number average molecular weight of the poly(N-acylalkyleneimine) segment is 800 to 1600, the mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly(N-acylalkyleneimine) segment (b) is 65 / 35 to 82 / 18, and the weight average molecular weight of the organopolysiloxane segment constituting the main chain is 10,000 to 100,000 (see, for example, Patent Document 2).

[0006] 3) A temporary hair dye composition, in order to provide a temporary hair dye having excellent colorability, water resistance, color transfer resistance, good touch of colored hair, non-stickiness, and easy application to hair, the composition contains an organopolysiloxane as component (A) and a pigment and / or direct dye as component (B), wherein the content of component (A) is 3 to 20% by mass, and the organopolysiloxane is a poly(N-acylalkyleneimine) segment having a number average molecular weight of 800 to 1600, which comprises a repeating unit represented by a specific formula and is bonded to at least two silicon atoms of an organopolysiloxane segment having a weight average molecular weight of 10,000 to 200,000 constituting the main chain, via an alkylene group containing a heteroatom, the mass ratio of the organopolysiloxane segment to the poly(N-acylalkyleneimine) segment is 83 / 17 to 98 / 2, and the molecular weight between the grafting points is 12,000 to 30,000 (see, for example, Patent Document 3).

[0007] However, although the hair cosmetic resins and hair cosmetics containing these resins described in Patent Documents 1 to 3 are not sticky and have good water resistance, coloring properties, and easy cleaning properties, when the colorant (coloring material) contained therein is applied to the hair, the hair cosmetic resins (adhesive resins) become hard, resulting in a different texture from the surrounding hair. To solve this problem, the hair is combed with a comb after the application is dried, but if the hair is hard after the application, the comb may get stuck when combing the hair, which puts a great burden on the hair, making it difficult to achieve both adhesion and combing properties.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2019-85366 (claims, examples, etc.)

[0011] Patent Document 2: Japanese Patent Application Publication No. 2009-24114 (claims, examples, etc.)

[0012] Patent Document 3: Japanese Patent Application Publication No. 2012-1480 (claims, examples, etc.) Summary of the invention

[0013] Problem that the invention aims to solve

[0014] The present invention attempts to solve the above-mentioned conventional problems and aims to provide a hair cosmetic resin and a hair cosmetic which are non-sticky and have both high adhesion and combing properties without impairing performance such as water resistance, coloring properties and easy cleaning.

[0015] Solutions for solving problems

[0016] The present inventors have conducted intensive studies on the above-mentioned conventional technical problems and the like, and as a result, have found that in an organopolysiloxane in which a poly(N-acylalkyleneimine) segment (b) comprising a repeating unit represented by a specific formula is bonded to at least two silicon atoms of an organopolysiloxane segment (a) constituting the main chain via an alkylene group containing a heteroatom, by controlling the number average molecular weight of the poly(N-acylalkyleneimine) segment (b) in the side chain to be below a prescribed value, etc., thereby achieving the present invention.

[0017] That is, the hair cosmetic resin of the present invention is characterized in that a poly(N-acylalkylimide) segment (b) comprising a repeating unit represented by the following formula (1) is bonded to at least two silicon atoms of an organopolysiloxane segment (a) constituting a main chain via an alkylene group containing a hetero atom, wherein the alkylene group containing a hetero atom is any group represented by the following formulae (i) to (vii), the mass average molecular weight of the segment (a) is 10,000 to 100,000, the number average molecular weight of the segment (b) is less than 800, and the mass ratio of (a) to (b) [(a) / (b)] is 58 / 42 to 90 / 10.

[0018]

[0019] [R1 in the above formula (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].

[0020] (i)

[0021]

[0022] (ii)

[0023]

[0024] (iii)

[0025]

[0026] (iV)

[0027]

[0028] (V)

[0029]

[0030] (Vi)

[0031]

[0032] (vii)

[0033]

[0034] The heteroatom-containing alkylene group of the hair cosmetic resin is preferably a group represented by the above formula (i) or (ii).

[0035] The hair cosmetic resin is preferably polyethyloxazoline amodimethicone or polysilicone-9.

[0036] The hair cosmetic of the present invention is characterized by containing the resin for hair cosmetic having the above-mentioned structure.

[0037] Effects of the Invention

[0038] According to the present invention, there are provided a hair cosmetic resin and a hair cosmetic which are non-sticky and have both high adhesion and combing properties without impairing properties such as water resistance, coloring properties, and easy cleansing. DETAILED DESCRIPTION

[0039] The embodiments of the present invention are described in detail below.

[0040] The hair cosmetic resin of the present invention is characterized in that a poly(N-acylalkylimide) segment (b) comprising a repeating unit represented by the following formula (1) is bonded to at least two silicon atoms of an organopolysiloxane segment (a) constituting a main chain via an alkylene group containing a hetero atom, wherein the alkylene group containing a hetero atom is any group represented by the following formulae (i) to (vii), the mass average molecular weight of the segment (a) is 10,000 to 100,000, the number average molecular weight of the segment (b) is less than 800, and the mass ratio of (a) to (b) [(a) / (b)] is 58 / 42 to 90 / 10.

[0041]

[0042] [In the above formula (1), R1 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.]

[0043] (i)

[0044]

[0045] (ii)

[0046]

[0047] (iii)

[0048]

[0049] (iV)

[0050]

[0051] (v)

[0052]

[0053] (Vi)

[0054]

[0055] (vii)

[0056]

[0057] In the present invention, the poly(N-acylalkyleneimine) segment may have at least two groups bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a heteroatom, but preferably the groups are bonded to one or more silicon atoms other than the two terminals via the alkylene group containing a heteroatom, and more preferably the groups are bonded to two or more silicon atoms other than the two terminals via the alkylene group containing a heteroatom.

[0058] The heteroatom-containing alkylene group functions as a linking group of the poly(N-acylalkylimine) segment (b). The heteroatom-containing alkylene group is composed of any group represented by the above formulas (i) to (vii), preferably a group represented by the above formula (i) or (ii), and more preferably a group represented by the above formula (i).

[0059] The N-acylalkyleneimine unit constituting the poly(N-acylalkyleneimine) segment (b) is represented by the general formula (1) above. In the general formula (1), the alkyl group having 1 to 22 carbon atoms as R1 may be, for example, a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a docosyl group, etc. Among them, an alkyl group having 1 to 10 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms, is more preferred.

[0060] Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, and specific examples include benzyl, phenethyl, trityl, naphthylmethyl, anthrylmethyl, etc. Among them, aralkyl groups having 7 to 14 carbon atoms are preferred, and aralkyl groups having 7 to 10 carbon atoms are more preferred.

[0061] Examples of the aryl group include aryl groups having 6 to 14 carbon atoms, and specific examples include phenyl, tolyl, xylyl, naphthyl, biphenylyl, anthracenyl, and phenanthryl. Among them, aryl groups having 6 to 12 carbon atoms are preferred, and aryl groups having 6 to 9 carbon atoms are more preferred.

[0062] Among these, R1 is particularly preferably an alkyl group having 1 to 6 carbon atoms.

[0063] The mass ratio (a / b) of the organopolysiloxane segment (a) to the poly(N-acylalkyleneimine) segment (b) is 58 / 42 to 90 / 10, but is preferably 61 / 39 to 88 / 12, more preferably 64 / 36 to 86 / 14, from the viewpoint of achieving both coloring properties, which are the basic performances of a hair cosmetic, and water resistance, soft touch, non-stickiness, and good combing properties of the colored film.

[0064] In the present specification, the above (a) / (b) is a value obtained by dissolving the organopolysiloxane of component (A) in deuterated chloroform at 5 mass %, and analyzing it by nuclear magnetic resonance (1H-NMR), and by the integrated ratio of the alkyl group or phenyl group in the organopolysiloxane segment to the methylene group in the poly(N-acylalkyleneimine) segment.

[0065] The mass average molecular weight (molecular weight between grafting points; MWg) of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments is 1000 to 3500, but is preferably 1100 to 3200, more preferably 1200 to 3000, from the viewpoint of achieving both coloring properties, which are the basic performances of a hair cosmetic, and water resistance, soft touch, non-stickiness, and good combing properties of the colored film.

[0066] In the present specification, the “organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments” refers to the portion surrounded by a dotted line between two points from the bonding point of the poly(N-acylalkyleneimine) segment to the organopolysiloxane segment (bonding point A) and the bonding point of the adjacent poly(N-acylalkyleneimine) segment (bonding point B), as shown in the following formula (2), which is composed of one R 2 SiO unit, 1 R 6 and y+1 R 2 3SiO units. In addition, the "poly (N-acyl alkylene imine) segment" refers to the above R 6 Bonded Z.

[0067]

[0068] In the above general formula (2), R 2 Each independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, and R 6 represents an alkylene group containing a heteroatom, Z represents a poly(N-acylalkyleneimine), R 7 represents the residue of a polymerization initiator, and y represents a positive number.

[0069] MWg is the molecular weight of the portion surrounded by the dotted line in the above general formula (2), which can be understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly(N-acylalkyleneimine) segment. When the functional group of the modified organopolysiloxane as a raw material compound is 100% replaced by the poly(N-acylalkyleneimine), it is consistent with the functional group equivalent (g / mol) of the modified organopolysiloxane.

[0070] The molecular weight (MWox) of the poly(N-acylalkyleneimine) segment can be measured by a method of calculation from the molecular weight and polymerization degree of the N-acylalkyleneimine unit or by the gel permeation chromatography (GPC) measurement method described later. However, in the present invention, it refers to the number average molecular weight measured by the GPC measurement method, which is preferably less than 800, preferably 100 or more and less than 800, and more preferably 200 or more and less than 800.

[0071] By setting the number average molecular weight to less than 800, good combing properties can be achieved. By setting the mass average molecular weight of the segment (a) to a predetermined range and setting the mass ratio of (a) to (b) to a predetermined range, a hair cosmetic resin of the present invention having both high adhesion and combing properties can be obtained. If the number average molecular weight exceeds 800, the effects of the present invention cannot be achieved (this point will be described in more detail in the preparation examples etc. described later).

[0072] The mass average molecular weight (MWg) of the organopolysiloxane segment can be determined by the following formula using the content (Csi) of the organopolysiloxane segment constituting the main chain.

[0073] MWg=(Csi×MWox) / (100-Csi)

[0074] The mass average molecular weight (MWsi) of the organopolysiloxane segment (a) constituting the main chain is 10,000 to 100,000, but is more preferably 12,000 to 80,000, particularly preferably 14,000 to 60,000, from the viewpoint of achieving a balance between solubility in lower alcohols such as ethanol and easy handling after dissolution, colorability which is a basic performance of a hair cosmetic, and water resistance of the colored film, soft touch, non-stickiness, and good combing properties.

[0075] For MWsi, since it has a common skeleton with the modified organopolysiloxane as a raw material compound, MWsi is approximately the same as the mass average molecular weight of the modified organopolysiloxane as a raw material compound. It should be noted that the mass average molecular weight of the modified organopolysiloxane as a raw material compound is measured by GPC based on the following measurement conditions and converted into the mass average molecular weight of polystyrene.

[0076] Column: Two TSKgel SupreMultiporeHZ-M (manufactured by Tosoh Corporation) connected in series

[0077] Eluent: 1 mM triethylamine / THF

[0078] Flow rate: 0.35mL / min

[0079] Column temperature: 40°C

[0080] Detector: RI

[0081] Sample: 50 μL

[0082] The weight average molecular weight (MWt) of the organopolysiloxane in the present invention is preferably 11,000 to 170,000, more preferably 14,000 to 140,000, and even more preferably 17,000 to 95,000. This allows the coloring properties of the hair cosmetic to be combined with water resistance, soft touch, non-stickiness, and good combing properties of the colored film, and also allows excellent solubility in lower alcohols such as ethanol. In the present specification, MWt can be determined from the weight average molecular weight of the modified organopolysiloxane as a raw material compound and the aforementioned mass ratio (a / b).

[0083] The organopolysiloxane can be produced, for example, by reacting a modified organopolysiloxane represented by the following general formula (3) with a terminally reactive poly(N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic imino ether represented by the following general formula (4).

[0084]

[0085] In formula (3), R 2 Synonymous with above, R 3 , R 4 Respectively represent and R 2 The same group or a monovalent group represented by any one of the following formulae (viii) to (xiii), R 5 represents a monovalent group represented by the following formula, p represents an integer of 135 to 1350, and q represents an integer of 3 to 57.]

[0086] (viii)

[0087]

[0088] (ix)

[0089]

[0090] lr3

[0091]

[0092] (xi)

[0093]

[0094] (xii)

[0095]

[0096] (xiii)

[0097]

[0098] The modified organopolysiloxane shown and the following formula (4)

[0099]

[0100] [In formula (4), R 1 and n have the same meaning as above. ]

[0101] The functional group equivalent of the modified organopolysiloxane is preferably 1000 to 3500, more preferably 1100 to 3200, particularly preferably 1200 to 3000. The mass average molecular weight of the modified organopolysiloxane is substantially the same as the mass average molecular weight (MWsi) of the organopolysiloxane segment (a) constituting the main chain.

[0102] A polymerization initiator can be used in the ring-opening polymerization of the cyclic imino ether (4). As the polymerization initiator, a compound with strong electrophilic reactivity can be used, for example, alkyl benzenesulfonate, alkyl p-toluenesulfonate, alkyl trifluoromethanesulfonate, alkyl trifluoroacetate, alkyl sulfate and other strong acid alkyl esters, among which dialkyl sulfate is preferably used. The amount of the polymerization initiator used is usually 2 to 100 mol per 1 mol of the polymerization initiator relative to the cyclic imino ether (4).

[0103] As the polymerization solvent, for example, 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 dichloromethane; nitrile solvents such as acetonitrile and benzonitrile; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide can be used, and acetates are preferably used. The amount of the solvent used is usually 20 to 2000 parts by mass relative to 100 parts by mass of the cyclic imino ether (4).

[0104] The polymerization temperature is usually 30 to 170°C, preferably 40 to 150°C. The polymerization time varies depending on the polymerization temperature and the like, but is usually 1 to 60 hours.

[0105] As the cyclic imino ether (4), for example, if 2-substituted-2-oxazoline is used, a poly(N-acylethyleneimine) in which n=2 in the general formula (1) can be obtained, and if 2-substituted-dihydro-2-oxazine is used, a poly(N-acylpropyleneimine) in which n=3 in the general formula (1) can be obtained.

[0106] As a method for connecting the poly(N-acylalkyleneimine) and the organopolysiloxane segment, for example, the following method can be mentioned.

[0107] 1) A method of reacting a modified organopolysiloxane represented by the general formula (3) with a terminally reactive poly(N-acylalkylene imine) obtained by active polymerization of a cyclic imino ether

[0108] 2) The reaction of carboxyl and hydroxyl groups condensing to form esters

[0109] 3) The reaction of carboxyl group and amino group condensing to form amide

[0110] 4) Reaction of haloalkyl with primary, secondary or tertiary amino groups to form secondary, tertiary or quaternary ammonium

[0111] 5) Addition reaction of vinyl groups with organopolysiloxanes having Si-H groups

[0112] 6) Reaction of epoxy group and amino group to form β-hydroxyamine

[0113] Among these, as shown in the theoretical formula shown below [MWi is the molecular weight of the poly(N-acylalkyleneimine)], the method 1) above is the most preferred from the viewpoint that the degree of polymerization can be easily controlled by the amount of the cyclic amino ether (4) and the polymerization initiator used, and a substantially monodisperse poly(N-acylalkyleneimine) having a narrow molecular weight distribution can be obtained compared with conventional free radical polymerization.

[0114] MWi = [number of moles of cyclic imino ether / number of moles of polymerization initiator] × molecular weight of cyclic imino ether + molecular weight of polymerization initiator (theoretical formula)

[0115] Examples of the organopolysiloxane include poly(N-formylethyleneimine)organosiloxane, poly(N-acetylethyleneimine)organosiloxane, poly(N-propionylethyleneimine)organosiloxane, polysilicone-9, and polyethyloxazoline aminodimethylsiloxane.

[0116] It is particularly preferred that the heteroatom-containing alkylene group of the hair cosmetic resin is the above-mentioned formula (i) or (ii).

[0117] More preferably, the hair cosmetic resin is polyethyloxazoline amodimethicone or polysilicone-9.

[0118] The hair cosmetic resin of the present invention of such a constitution is a hair cosmetic resin in which a poly(N-acylalkylimide) segment (b) comprising a repeating unit represented by the above formula (1) is bonded to at least two silicon atoms of an organopolysiloxane segment (a) constituting the main chain via an alkylene group containing a heteroatom, the alkylene group containing a heteroatom being any group represented by the above formulae (i) to (vii), the mass average molecular weight of the segment (a) being 10,000 to 100,000, the number average molecular weight of the segment (b) being less than 800, and the mass ratio of (a) to (b) [(a) / (b)] being 58 / 42 to 90 / 10. Thus, a water-resistant resin having an appropriate hardness can be prepared, and thus a hair cosmetic resin having a non-sticky feel and having both high adhesion and combing properties without impairing properties such as water resistance, coloring properties and easy cleansing can be obtained.

[0119] 〔Hair cosmetics〕

[0120] The hair cosmetic of the present invention is characterized by containing the above-mentioned resin for hair cosmetics, and preferably contains at least a pigment and a solvent in addition to the above-mentioned resin for hair cosmetics.

[0121] The pigment that can be used is not particularly limited as long as it is a pigment used for hair cosmetics, and examples thereof include at least one of inorganic pigments, organic pigments, pearlescent pigments, metal powder pigments, and glitter pigments (each alone or as a mixture of two or more, the same below).

[0122] Examples of inorganic pigments include black pigments such as carbon black, black iron oxide, and black titanium oxide; red pigments such as iron oxide (ferric oxide), iron hydroxide, and iron titanate; brown pigments such as γ-iron oxide; yellow pigments such as iron oxide yellow and loess; blue pigments such as ultramarine and navy blue; purple pigments such as manganese violet and cobalt violet; green pigments such as chromium oxide, chromium hydroxide, and cobalt titanate; and white pigments such as titanium oxide, zinc oxide, and cerium oxide. Among these, carbon black, black iron oxide, black titanium oxide, iron oxide (ferric oxide), iron oxide yellow, ultramarine, and navy blue are preferred.

[0123] Examples of the organic pigment include at least one of legal coloring matter such as Red No. 201, Red No. 202, Red No. 203, Red No. 204, Red No. 205, Red No. 206, Red No. 207, Red No. 208, Red No. 219, Red No. 220, Red No. 221, Red No. 228, Red No. 404, Red No. 405, Orange No. 203, Orange No. 204, Orange No. 401, Yellow No. 205, Yellow No. 401, and Blue No. 404. Among these, Red No. 202, Red No. 404, Yellow No. 205, Yellow No. 401, and Blue No. 404 are preferred.

[0124] Examples of pearlescent pigments include pearlescent powder, bismuth oxychloride, mica, metal oxide-coated mica (e.g., titanium mica, iron oxide-coated mica, iron oxide-coated titanium mica, black iron oxide-coated mica, black iron oxide-coated titanium mica, yellow iron oxide-coated mica, iron oxide / black iron oxide-coated titanium mica, navy blue-coated titanium mica, iron oxide / navy blue-coated titanium mica, carmine-coated titanium mica, barium sulfate-coated titanium mica, etc.), metal oxide-coated aluminum oxide flakes, metal oxide-coated silicon dioxide flakes, multilayer-coated pearlescent pigments, and dark blue.

[0125] Examples of the metal powder pigment include at least one of gold powder, silver powder, copper powder, aluminum powder, and brass powder.

[0126] Examples of the glittering pigment include at least one of polyethylene terephthalate / aluminum / epoxy laminates and polyethylene terephthalate / polyolefin laminate films.

[0127] The total content of these pigments varies depending on the use of the hair cosmetic (temporary hair dye, mascara cosmetic, hair wax, color spray) from the viewpoints of coloring properties, color transfer resistance, touch after application, and ease of application, but is 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 15% by mass, based on the total amount of the hair cosmetic.

[0128] In addition to the above-mentioned pigments, surfactants, thickeners, oils, polyols, fragrances, pearlescent agents, pigments, ultraviolet absorbers, antioxidants, various medicinal agents (bactericides such as triclosan and triclocarban, anti-inflammatory agents such as dipotassium glycyrrhizinate and tocopherol acetate, anti-dandruff agents such as zinc pyrithione and octopirox), preservatives such as methylparaben and butylparaben, pH adjusters such as malic acid, lactic acid, and citric acid, etc. may be appropriately contained as needed.

[0129] The content of the resin for hair cosmetics of the above-mentioned constitution varies depending on the use of the hair cosmetics (temporary hair dye, mascara cosmetics, hair wax, color spray), application form, etc., from the viewpoint of achieving both coloring properties, which are basic properties of the hair cosmetics, and water resistance of the colored film, soft touch, non-stickiness, and good combing properties, but is 5 to 30% by mass, more preferably 7 to 28% by mass, and particularly preferably 10 to 25% by mass, based on the total amount of the hair cosmetics.

[0130] If the content of the hair cosmetic resin is less than 5%, the adhesion and water resistance are insufficient, which is not preferred. On the other hand, if it exceeds 30%, it cannot be dissolved in a solvent, or the texture after application to the hair is deteriorated and the combing property is poor, which is not preferred. It should be noted that in the case of the aerosol type described below, it refers to the "content" relative to the entire composition of the stock solution excluding the spray. The same applies below.

[0131] As the solvent that can be used, lower alcohol, water, or a mixture of water and lower alcohol can be used as the solvent. As the lower alcohol, for example, ethanol, 1-propanol, 2-propanol, tert-butanol, etc. can be listed, among which ethanol and 2-propanol are preferred, and ethanol is particularly preferred.

[0132] The content of these solvents is preferably 0.1 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 80% by mass based on the total amount of the hair cosmetic from the viewpoint of pigment dispersibility and quick drying after application.

[0133] In addition to the above-mentioned components, the hair cosmetic of the present invention may contain components generally used in hair cosmetics within a range that does not impair the effects of the present invention. For example, it may appropriately contain polyols, surfactants, fats and oils, oily components such as low-volatile hydrocarbons and silicone oils, thickeners such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxyvinyl polymers, sprays such as LPG (liquefied petroleum gas), pentane, dimethyl ether and diethyl ether, fragrances, preservatives, ultraviolet absorbers, chelating agents, antioxidants, plant extracts and the like.

[0134] As the polyol, for example, it is preferred to contain an appropriate amount of glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, isoprene glycol, 1,3-butylene glycol, etc., for example, 5% by mass or less relative to the total amount of the hair cosmetic, and glycerols such as glycerol, diglycerol, polyglycerol, etc. It should be noted that the amount can be appropriately increased or decreased depending on the use of the hair cosmetic. For example, in the case of a mascara type, a foam type, a spray type, etc., it is preferred to reduce the amount.

[0135] The hair cosmetic of the present invention can be prepared by a conventional method, and can be produced by blending the above-mentioned hair cosmetic resin, pigment, lower alcohol, water and other components within the above-mentioned content range and uniformly stirring and mixing.

[0136] For example, the hair cosmetic resin, alcohol such as a lower alcohol, pigment, and water are stirred uniformly by a general-purpose dispersing machine, etc., and then optional components such as a pH adjuster and a thickener are added, stirred uniformly by a dispersing machine, etc., and then stirred by a homomixer, etc. The preparation form of the hair cosmetic according to the present invention, such as foam, hair dye, gel, spray, cream, wax, etc., can be prepared by appropriately containing each preferred component.

[0137] When the hair cosmetic of the present invention having such a configuration is used, it can be used according to the above-mentioned dosage form, and when using a hair applicator, for example, an applicator with a tap valve device, a mascara-type applicator, a tube-type applicator, an applicator with a piston pressing mechanism, etc. can be used.

[0138] The hair cosmetic composition of the present invention thus constituted contains the hair cosmetic resin of the above-mentioned constitution, and therefore can provide a hair cosmetic composition which is not sticky and has both high adhesion and combing properties without impairing properties such as water resistance, coloring properties, and easy cleansing.

[0139] Example

[0140] Hereinafter, the present invention will be described in detail with reference to preparation examples, examples, comparative examples, etc. It should be noted that the present invention is not limited to the following examples, etc.

[0141] In the following production examples, the content of the organopolysiloxane segment in the hair cosmetic resin is a value determined by nuclear magnetic resonance (1H-NMR), and the mass average molecular weight of the final product is a calculated value. The molecular weight of poly(N-propionylethyleneimine) is a number average molecular weight determined by gel permeation chromatography (GPC).

[0142] Column: Two K-804L columns (manufactured by Tosoh Corporation) were used in series.

[0143] Eluent: 1mmol / dimethyldodecylamine / chloroform

[0144] Flow rate: 1.0mL / min

[0145] Column temperature: 40°C

[0146] Detector: RI

[0147] Sample volume: 50 μL

[0148] Polystyrene Conversion

[0149] (Production Example 1: Resin A for Hair Cosmetics)

[0150] 8.5g (0.055 mol) of diethyl sulfate and 42.1g (0.43 mol) of 2-ethyl-2-oxazoline were dissolved in 101g of dehydrated ethyl acetate, and heated at 70°C for 8 hours under a nitrogen atmosphere to synthesize terminal reactive poly (N-propionylethyleneimine). The number average molecular weight was measured by GPC, and the result was 770. Thereto, 49.4g of amino-terminated polydimethylsiloxane (mass average molecular weight: 20000, amine equivalent: 1700) was made into a 33% ethyl acetate solution, then added at one time, and heated to reflux for 8 hours. The reaction mixture was concentrated under reduced pressure to obtain polyethyloxazoline amino-terminated polydimethylsiloxane as a light yellow rubbery solid (92g, yield 92%). Neutralization titration was performed using hydrochloric acid with methanol as solvent, and it was found that there were no residual amino groups.

[0151] (Production Example 2: Resin B for hair cosmetics)

[0152] By the same method as in the above-mentioned Preparation Example 1, 10.6 g (0.069 mol) of diethyl sulfate, 25.0 g (0.25 mol) of 2-ethyl-2-oxazoline, and 71 g of dehydrated ethyl acetate were used to obtain poly(N-propionylethyleneimine) having a number average molecular weight of 370. Furthermore, 64.5 g of amino-terminated polydimethylsiloxane (weight average molecular weight 20,000, amine equivalent 1,700) was used to obtain polyethyloxazoline amino-terminated polydimethylsiloxane as a light yellow rubber solid (94 g, yield 94%). Neutralization titration was performed using hydrochloric acid using methanol as a solvent, and it was found that no amino group remained.

[0153] (Production Example 3: Resin C for Hair Cosmetics)

[0154] By the same method as in the above-mentioned Preparation Example 1, 5.1 g (0.033 mole) of diethyl sulfate, 66.1 g (0.67 mole) of 2-ethyl-2-oxazoline, and 142 g of dehydrated ethyl acetate were used to obtain poly(N-propionylethyleneimine) with a number average molecular weight of 2000. Furthermore, 28.8 g of amino-terminated polydimethylsiloxane (weight average molecular weight 20000, amine equivalent 1700) was used to obtain polyethyloxazoline amino-terminated polydimethylsiloxane (95 g, yield 95%) as a pale yellow rubbery solid. Neutralization titration was performed using hydrochloric acid using methanol as a solvent, and it was found that no amino group remained.

[0155] (Production Example 4: Resin D for Hair Cosmetics)

[0156] By the same method as in the above-mentioned Preparation Example 1, 2.1 g (0.014 mole) of diethyl sulfate, 44.1 g (0.45 mole) of 2-ethyl-2-oxazoline, and 92 g of dehydrated ethyl acetate were used to obtain poly(N-propionylethyleneimine) with a number average molecular weight of 3100. Furthermore, 53.8 g of aminopropyl polydimethylsiloxane (weight average molecular weight 8800, amine equivalent 8000) was used to obtain polysiloxane-9 (93 g, yield 93%) as a light yellow rubber solid. Neutralization titration was performed using hydrochloric acid using methanol as a solvent, and it was found that no amino group remained.

[0157] The physical properties of the hair cosmetic resins obtained in Production Examples 1 to 4 are shown in Table 1 below, and their solubility in ethanol was evaluated by the following evaluation method. The results are shown in Table 1 below.

[0158] (Solubility test in ethanol)

[0159] 20 g of each of the hair cosmetic resins obtained in Production Examples 1 to 4 were mixed and stirred in a container containing 100 ml of ethanol, and the mixture was evaluated according to the following evaluation criteria.

[0160] These results are shown in Table 1 below.

[0161] Evaluation criteria:

[0162] ◎: Transparent

[0163] ○: Generally transparent, but slightly turbid

[0164] △: White turbidity occurs

[0165] ×: The resin is not dissolved and exists in a solid state

[0166] [Table 1]

[0167]

[0168] a / b, MWsi, MWox, MWg, and MWt in the above Table 1 are as follows.

[0169] a / b: mass ratio of organopolysiloxane segment (a) to poly(N-acylalkyleneimine) segment (b)

[0170] MWsi: the mass average molecular weight of the organopolysiloxane segment (a) constituting the main chain

[0171] MWox: number average molecular weight of the poly(N-acylalkyleneimine) segment (b)

[0172] MWg: the mass average molecular weight of the organopolysiloxane segments between adjacent poly(N-acylalkyleneimine) segments

[0173] MWt: mass average molecular weight of organopolysiloxane

[0174] [Examples 1 to 9 and Comparative Examples 1 to 3: Preparation of Hair Cosmetics]

[0175] Using the hair cosmetic resins obtained in the above-mentioned Production Examples 1 to 4, hair cosmetics of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared by a conventional method according to the formulations shown in Table 2 below.

[0176] The obtained hair cosmetics of Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated for hand coloring inhibition, combing properties, adhesion, stickiness, water resistance, coloring properties, and cleansing properties according to the following evaluation methods.

[0177] These results are shown in Table 2 below.

[0178] (Evaluation method of adhesion)

[0179] 0.2 g of each of the obtained hair cosmetics was applied to 1 g of human gray hair and dried at room temperature for 120 minutes (hereinafter referred to as "after application to human gray hair and drying"), then rubbed with hands and the degree of color transfer to hands was visually confirmed and evaluated according to the following evaluation criteria.

[0180] Evaluation criteria:

[0181] ◎: No color transfer at all

[0182] ○: Slight transfer but no problem

[0183] △: Slightly darker color shift

[0184] ×: Darker color transfer

[0185] (Comprehensive evaluation method)

[0186] Each of the obtained hair cosmetics was applied to human white hair and dried, and then 10 panelists performed a sensory evaluation on a 5-level scale to determine which hand exerted a greater load when combing the hair using a comb, using Comparative Example 1 as a standard. Evaluation was performed based on the total score of the 10 panelists according to the following criteria.

[0187] Evaluation criteria:

[0188] 5 points: Less than Comparative Example 1

[0189] 4 points: Slightly less than Comparative Example 1

[0190] 3 points: Same as Comparative Example 1

[0191] 2 points: Slightly larger than Comparative Example 1

[0192] 1 point: Greater than Comparative Example 1

[0193] ◎: 46 points or more

[0194] ○: 40 points or more and less than 46 points

[0195] △: 31 points or more and less than 40 points

[0196] ×: Less than 31 points

[0197] (Evaluation method of stickiness)

[0198] Each of the obtained hair cosmetics was applied to human gray hair and dried, and then 10 panelists performed a sensory evaluation on a 5-level scale to determine which of the cosmetics had a sticky feeling when touching the hair, using Comparative Example 1 as a standard.

[0199] Evaluation criteria:

[0200] 5 points: Less sticky than Comparative Example 1

[0201] 4 points: Less sticky than Comparative Example 1

[0202] 3 points: Same as Comparative Example 1

[0203] 2 points: Slightly stickier than Comparative Example 1

[0204] 1 point: Stickier than Comparative Example 1

[0205] ◎: 40 points or more

[0206] ○: 20 points or more and less than 40 points

[0207] △: 15 points or more and less than 20 points

[0208] ×: Less than 15 points

[0209] (Evaluation method of water resistance)

[0210] Each of the obtained hair cosmetics was applied to human gray hair and dried, and then a filter paper moistened with water was pressed thereon, and the degree of coloration on the filter paper was evaluated according to the following evaluation criteria.

[0211] Evaluation criteria:

[0212] ◎: Does not adhere to filter paper at all

[0213] ○: Some adhesion on the filter paper, but no problem

[0214] △: Slightly heavier adhesion on filter paper

[0215] ×: Heavy adhesion on filter paper

[0216] (Evaluation method of colorability)

[0217] Each of the obtained hair cosmetics was applied to human gray hair and dried, followed by visual observation and evaluation based on the following evaluation criteria.

[0218] Evaluation criteria:

[0219] ◎: The color has changed significantly compared to the original white hair color.

[0220] ○: slightly lighter than ◎

[0221] △: The color of the gray hair has not changed much.

[0222] ×: The color of the white hair has hardly changed

[0223] (Evaluation method of cleanliness)

[0224] Each of the obtained hair cosmetics was applied to human gray hair and dried, and then washed with a commercially available shampoo, and then evaluated for fading and sticking according to the following evaluation criteria.

[0225] Evaluation criteria:

[0226] ◎: No color residue and no stickiness

[0227] ○: There is slight color residue or sticking, but there is no problem in actual use.

[0228] △: Some color remains or sticks

[0229] ×: Color residue or sticking

[0230] [Table 2]

[0231]

[0232] As shown in Table 2, the hair cosmetic resins and hair cosmetics of Examples 1 to 9 within the scope of the present invention are not sticky, and have high adhesion and combing properties without impairing performance such as water resistance, coloring properties, and easy cleaning, as compared to Comparative Examples 1 to 3 which are not within the scope of the present invention.

[0233] Industrial Applicability

[0234] The hair cosmetic resin and hair cosmetic suitable for hair cosmetics such as mascara, hair dye, temporary hair dye, etc. can be obtained.

Claims

1. A resin for hair cosmetics, characterized in that: The hair cosmetic resin comprises a poly(N-acylalkylimide) segment (b) comprising a repeating unit represented by the following formula (1) bonded to at least two silicon atoms of an organopolysiloxane segment (a) constituting a main chain via an alkylene group containing a heteroatom, wherein the alkylene group containing a heteroatom is any group represented by the following formulae (i) to (vii), the mass average molecular weight of the segment (a) is 10,000 to 100,000, the number average molecular weight of the segment (b) is less than 800, and the mass ratio of (a) to (b) [(a) / (b)] is 58 / 42 to 90 / 10. In the above formula (1), R1 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. (i) (ii) (iii) (iv) (v) (vi) (vii) 2. The resin for hair cosmetics according to claim 1, wherein The heteroatom-containing alkylene group of the hair cosmetic resin is represented by a group represented by the above formula (i) or (ii).

3. The resin for hair cosmetics according to claim 1 or 2, characterized in that The resin used in hair cosmetics is polyethyloxazoline amino-terminated polydimethylsiloxane or polysilicone-9.

4. A hair cosmetic, characterized in that: The hair cosmetic composition comprises the resin for hair cosmetics according to claim 1 or 2.

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