A composition, use and product for hair damage repair and color lock

Abstract

The application provides a composition, application and product for hair damage repair and color fixation, and belongs to the technical field of hair repair and care. The hair damage repair composition is composed of the following components in parts by weight: a fixing agent 0.10-20.29, a disulfide bond compound 0.05-8.56; wherein the fixing agent is a compound containing greater than or equal to 1 alpha, beta-alkene carbonyl structure group or a compound containing greater than or equal to 1 benzoyl structure group; the disulfide bond compound is selected from one or more of dioctanoyl cystine, diacetyl cystine dimethyl ester, dipalmitoyl cystine and cystine bis-PG-propyl silane triol. The fixing agent in the composition component can react with the mercapto group in the hair, the disulfide bond compound assists in repairing the damaged area of the hair scale, synergistically enhances the effect of damage repair and hair color fixation, and significantly improves the effect of damage repair and hair color fixation.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of hair repair care, and relates to a composition for hair damage repair and color fixation, application and product. BACKGROUND

[0002] Hair damage refers to damage to the microstructure of hair caused by external factors, mainly manifested as reduced hair hydrophobicity, loss of luster, dryness and brittleness, reduced elasticity, discoloration, increased bifurcation, reduced tensile strength, and easy breakage. External factors causing hair damage include natural factors and human factors. Natural factors include temperature, humidity, ultraviolet rays, and fine particles such as smog in the atmosphere, which can all damage the microstructure of hair to some extent. Human factors include improper hair washing and post-washing care methods (including improper dry hair methods), excessive force when combing hair, external pulling, hair dyeing, and hair perming. In particular, during the hair dyeing process, on the one hand, the purpose of dyeing hair is to color and fix the color of hair, and on the other hand, the chemical reactions occurring during the dyeing process are complex, and the damage to the microstructure of hair caused by the chemicals contained in the hair dye is difficult to completely recover, so the dyed hair is damaged and becomes rough and frizzy. Therefore, timely repair of hair damage and reinforcement of the color of dyed hair are important technical problems for improving hair quality and enhancing people's sense of consumption.

[0003] Chinese patent CN106074252A provides a shampoo, which comprises the following components in parts by mass: water 50-60 parts, phase A hair conditioner 0.5-1.0 parts, citric acid 0.1-0.2 parts, phase B surfactant 14-18 parts, chelating agent 0.1-0.2 parts, emollient 0.1-1.0 parts, phase B hair conditioner 1-5 parts, phase C surfactant 5-15 parts, antidandruff agent 0.1-0.5 parts, phase D surfactant 2-5 parts, phase E hair conditioner 2-5 parts, skin conditioner 3-8 parts, humectant 1-4 parts, pearl agent 0.5-1 part, emulsion stabilizer 0.1-0.5 parts, fragrance 0.2-0.4 parts, preservative 0.2-0.4 parts, and sodium chloride 0.8-2 parts. The skin conditioner is a complex of hydrolyzed sericin, olive oil PEG-7 ester, panthenol, and plant extract. The plant extract is selected from one or more of saffron extract, apple extract, grape fruit extract, strawberry fruit extract, litchi fruit extract, Chinese kiwi fruit extract, calendula extract, and yam seed extract.

[0004] Chinese invention patent CN118806863A provides a hair growth and black hair preparation and its preparation method, which is made of Lycium ruthenicum, blackberry, cranberry, mulberry, hops, flaxseed, milfoil, oyster extract, turmeric, sea buckthorn, ligustrum lucidum, safflower, soapstick, honeysuckle and borneol. The preparation can consider black hair, hair loss prevention and care effects, reduce and delay melanin loss, improve hair follicle state, promote new hair growth, improve scalp state and have good affinity.

[0005] Chinese invention patent CN118902919A provides a composition for slowing down hair dyeing damage and caring for scalp and its preparation method and application. The composition of the technology is composed of squalane, sea buckthorn fruit oil and camellia seed oil. The three components cooperate with each other, have the effects of slowing down the damage and itching of the scalp caused by hair dyeing, caring for the scalp, reducing hair damage, giving hair good combing property and toughness, and making hair healthy.

[0006] However, most of the components mentioned in the prior art play a role by means of intermolecular forces, and how to play a role is not mentioned. There is no better hair damage repair composition technical solution that repairs damaged hair scales by repairing exposed sulfhydryl bonds, repairing disulfide bond breakage or enhancing hair dyeing fixation effect. SUMMARY

[0007] Terms and statements of the present invention:

[0008] 1. The articles "a", "an", and "the": unless otherwise expressly specified to one (kind) of object, include plural objects.

[0009] 2. Numerical ranges: unless otherwise expressly indicated, all ranges or ratios disclosed herein are to be understood to be inclusive of any and all sub-ranges or sub-ratios subsumed therein. For example, a stated range or ratio of 1 to 30 should be considered to include any and all sub-ranges or sub-ratios between the minimum value of 1 and the maximum value of 30, including endpoints and any integer, decimal, or sub-range or sub-ratio consisting of an integer or decimal.

[0010] Unless otherwise specified, the term "alkyl" used herein includes branched and straight chain saturated aliphatic hydrocarbon groups having a specified number of carbon atoms, including all isomers. Common abbreviations for alkyl groups, such as methyl, can be represented by "Me" or CH3, ethyl by "Et" or CH2CH3, propyl by "Pr" or CH2CH2CH3, butyl by "Bu" or CH2CH2CH2CH3, and the like. For example, "C 1-4 "alkyl" (or "C1-C4 alkyl") refers to straight chain or branched chain alkyl groups having a specified number of carbon atoms, including all isomers. C 1-4Alkyl includes n-, iso-, sec- and t-butyl, n- and iso-propyl, ethyl and methyl. The term "C 1-10 "Alkyl" and the like have similar meanings. In addition, common abbreviations of alkyl include: isopropyl can be represented by "i-Pr", n-propyl can be represented by "n-Pr", n-butyl can be represented by "n-Bu", tert-butyl can be represented by "t-Bu", etc.

[0011] The term "alkoxy" represents straight and branched chain alkyl groups having the indicated number of carbon atoms attached through an oxygen bridge.

[0012] The term "halogen" (or "halo") refers to fluorine, chlorine, bromine, and iodine (alternatively referred to as fluoro (F), chloro (Cl), bromo (Br), and iodo (I)).

[0013] The term "aryl" refers to aromatic mono- and polycyclic carbocyclic ring systems wherein the individual carbon rings in the polycyclic ring system are fused or linked to each other by single bonds. Typical aryl groups include phenyl, naphthyl and biphenylene.

[0014] The term "heterocycle" refers to a cyclic structure composed of carbon atoms and non-carbon atoms such as nitrogen, oxygen, and sulfur. Typical heterocyclic groups include pyridine, quinoline, tropane, phenothiazine, benzodiazepine, furan, pyrazolone, and pyrimidine.

[0015] The term "aromatic heterocycle" refers to a 5- or 6-membered monocyclic aromatic ring or a 7- to 12-membered bicyclic ring composed of carbon atoms and one or more heteroatoms selected from N, O and S. Examples of aromatic heterocycles include pyridyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl (or thiophenyl), thiazolyl, furanyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, diazolyl, thiazolyl, isothiazolyl and thiadiazolyl, benzotriazolyl, indolyl, isoindolyl, indazolyl, indolinyl, isoindolinyl, quinoxalinyl, quinazolinyl, cinnolinyl, chromanyl, isochromanyl, tetrahydroquinolinyl, quinolinyl, tetrahydroisoquinolinyl, isoquinolinyl, 2,3-dihydrobenzofuranyl, 2,3-dihydrobenzo-1,4-dienyl, imidazo(2,1-b)(1,3)thiazole and benzo-1,3-dioxolyl.

[0016] The aryl group in the term "substituted aryl" is as defined above. When the substituent of the substituted aryl group is not specified, the substituent group may be selected from the following groups, including but not limited to: halogen, C1-C 20 Alkyl, CF3, NH2, N(C1-C6 alkyl)2, NO2, oxo, CN, N3, -OH, -O(C1-C6 alkyl), C3-C 10 Cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, (C0-C6 alkyl)S(O) 0-2 -, aryl-S(O)0-2 -, (C0-C6 alkyl)S(O) 0-2 (C0-C6 alkyl)-, (C0-C6 alkyl)C(O)NH-, H2N-C(NH)-, -O(C1-C6 alkyl)CF3, (C0-C6 alkyl)C(O)-, (C0-C6 alkyl)OC(O)-, (C0-C6 alkyl)2NC(O)-(C0-C6 alkyl)O(C1-C6 alkyl)-, (C0-C6 alkyl)C(O) 1-2 (C0-C6 alkyl)-, (C0-C6 alkyl)OC(O)NH-, aryl, aralkyl, heteroaryl, heterocyclylalkyl, halogen-aryl, halogen-aralkyl, halogen-heterocycle, halogen-heterocyclylalkyl, cyano-aryl, cyano-aralkyl, cyano-heterocycle and cyano-heterocyclylalkyl. The term "substituted phenyl" has a similar definition.

[0017] Unless otherwise specified, all ranges listed herein are inclusive. For example, "n is an integer between 0 and 2" means that n can be 0, 1 or 2.

[0018] In view of the above problems existing in the prior art, the object of the present invention is to provide a composition and its application and related products for repairing damaged hair by means of exposed thiol bonds of damaged hair, rebuilding the hydrophobic layer of hair and locking color.

[0019] To achieve the above-mentioned object of the invention, on the one hand, the present invention provides a composition for repairing damaged hair and locking color, which is composed of the following components in parts by weight:

[0020] 0.10-20.29 parts of a fixative and 0.05-8.56 parts of a disulfide bond compound;

[0021] Wherein, the fixing agent is a compound containing greater than or equal to one α,β-olefinic carbonyl structural group or a compound containing greater than or equal to one benzoyl structural group; the disulfide bond compound is selected from one or more of dioctanoylcystine, diacetylcystine dimethyl ester, dipalmitoylcystine, cystine, and cystine bis-PG-propylsilanetriol.

[0022] The above-mentioned "disulfide bond compound" includes itself, salts, solvates and optical isomers.

[0023] The above-mentioned “α,β-olefin carbonyl structure” refers to a structure in which a carbon-carbon double bond is connected to a carbonyl group through a chemical bond.

[0024] The above-mentioned "benzoyl structure" refers to a structure in which a benzene ring and a carbonyl group are connected by a chemical bond.

[0025] The carbonyl group includes but is not limited to an aldehyde carbonyl group, a ketone carbonyl group, a carboxyl group, an ester group, and an amide group.

[0026] Preferably, the fixing agent is selected from the following structures:

[0027] ;

[0028] ; or

[0029] ;

[0030] wherein, is independently selected from the following structures:

[0031] , , , , , , , p-coumaric acid, kojic acid, kaempferol, coumarin, furanone, curcumin, cinnamate, anemonin, protoanemonin, or chlorogenic acid missing one hydrogen atom;

[0032] R, R A , R B is independently selected from the following structures:

[0033] substituted or unsubstituted hydrocarbyl, hydrocarboxy, aminyl, ammonium salt group, siloxane group, polyphenol group, peptide group, polyesters group, polyoxyethylene group, polyethyleneimine group, polystyrene group, polytetrafluoroethylene group, polyacrylic acid group, polyacrylate group, polyvinyl acetate group, polymethacrylate group, polyacrylonitrile group, polyphenylene sulfide group, polynorbornene group, or mixed copolymer group of one or more of the following monomers: ethylene, propylene, acetylene, butadiene, isoprene, vinyl chloride, styrene, tetrafluoroethylene, acrylonitrile, acrylic acid, acrylate, methacrylate, epoxy ethylene, ethyleneimine, or vinyl acetate;

[0034] the substituents are independently selected from at least one of C 1-30 alkyl, C 1-30 cycloalkyl, C 1-30 alkoxy, C 1-30 alkynyl, C 1-30 alkenyl, C 1-30 halogenated alkyl, amino, aminyl, hydroxyl, thiol, halogen, cyano, aromatic ring group, oxygen- and / or nitrogen-containing 5-6-membered aromatic heterocyclic group, oxygen- and / or nitrogen-containing 5-6-membered heterocyclic group.

[0035] Preferably, the substituents are independently selected from at least one of C 1-30 alkyl, hydroxyl, thiol, halogen, or cyano.

[0036] More preferably, the substituents are independently selected from methyl, ethyl, propyl, or hydroxyl.

[0037] the structure of , which is missing one hydrogen atom , , , , , , which is missing two hydrogen atoms, p-coumaric acid, kojic acid, cinamaldehyde, coumarin, furanone, curcumin, cinnamate, anemonin, protoanemonin, or chlorogenic acid.

[0038] a is an integer greater than or equal to 1.

[0039] Preferably, a is 1, 2, or 3.

[0040] More preferably, and as an example of the present application, a is 1 or 2.

[0041] Preferably, R, R A , R B have the following structure:

[0042] ;

[0043] wherein each B is independently selected from the following structures:

[0044] , , , , a chemical bond;

[0045] R1is selected from the following structures: a substituted or unsubstituted hydrocarbyl, hydrocarboxy, amine, ammonium salt, siloxane, polyphenol, peptide, polyesters, polyoxyethylene, polyethyleneimine, polystyrene, polytetrafluoroethylene, polyacrylic acid, polyacrylate, polyvinyl acetate, polymethacrylate, polyacrylonitrile, polyphenylene sulfide, polynorbornene, or a mixed polymer of one or more of the following monomers: ethylene, propylene, acetylene, butadiene, isoprene, vinyl chloride, styrene, tetrafluoroethylene, acrylonitrile, acrylic acid, acrylate, methacrylate, epoxy ethylene, ethyleneimine, vinyl acetate;

[0046] said substituents are independently selected from at least one of C 1-30 alkyl, C 1-30 cycloalkyl, C 1-30 alkoxy, C 1-30 alkynyl, C 1-30 alkenyl, C 1-30 halogenated alkyl, amino, amine, hydroxyl, thiol, halogen, cyano, aromatic ring group, oxygen- and / or nitrogen-containing 5-6-membered aromatic heterocyclic group, oxygen- and / or nitrogen-containing 5-6-membered heterocyclic group.

[0047] Preferably, R1 is selected from one of substituted or unsubstituted hydrocarbyl, siloxanyl, polyphenolyl, hydrophobic peptidyl.

[0048] The hydrocarbyl group includes, but is not limited to, C1-C 30 alkyl, C1-C 30 alkenyl, C1-C 30 alkynyl.

[0049] The siloxanyl group includes, but is not limited to, C1-C 30 alkyl, in which one or more methylene groups are replaced by a chain of one or more Si-O-Si, Si-O-Si-O-Si, or Si-(O-Si-) x O-Si siloxane chain groups (x takes an integer greater than or equal to 2, preferably x takes an integer from 2 to 15).

[0050] The polyphenolyl group includes, but is not limited to, groups in which aryl groups are alternately connected by oxygen atoms. The aryl group refers to aromatic mono- and polycarbocyclic ring systems in which the individual carbocyclic rings are fused or connected to one another by single bonds in polycyclic ring systems. Typical aryl groups include phenyl, naphthyl, and biphenylene.

[0051] The hydrophobic peptidyl group refers to a polypeptide group composed of amino acids containing hydrophobic side chains, including, but not limited to, α-amino acids, β-amino acids, γ-amino acids, and the like.

[0052] Preferably, the amino acids containing hydrophobic side chains include, but are not limited to, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, methionine, proline.

[0053] Preferably, R is independently selected from the following structures:

[0054] , , , , , , ; n, n1, n2 take an integer greater than or equal to 1.

[0055] Preferably, n, n1, n2 can each take an integer from 1 to 20.

[0056] More preferably, n can take an integer from 1 to 10.

[0057] In the structure of the above fixing agent, Structure is also called unit point fixative. The unit point fixative has the function of repairing damaged hair. The principle is that after a single site interacts with the hair, the unit point fixative is fixed on the damaged area of the hair, and the hydrophobic tail of the unit point fixative is also fixed on the damaged area of the hair, thereby achieving the purpose of repairing the damaged area of the hair. Therefore, the unit point fixative can also be called "repairing and protecting hair unit point fixative".

[0058] In structure, the number of connection positions can be one or two, which is determined by the number of connection positions. For example, when , , , , the number of is one; when , the number of is two.

[0059] Preferably, the comprises the following structure:

[0060] ; ; ; ; ; ; ; ; ; ;

[0061] ;

[0062] ; ; , ;

[0063] ;

[0064] ; ;

[0065] ;

[0066] ;

[0067] ;

[0068] ;

[0069] ; In the above compound, n is an integer greater than or equal to 1, preferably, n is an integer in the range of 8-25.

[0070] for 、 , two structures, respectively called dual-site fixatives and multi-site fixatives. Dual-site and multi-site fixatives lock and fix color. Their principle is that two or more sites can interact with hair simultaneously, forming a ring-like space that locks pigment molecules and creates a color-locking, color-fixing effect. Therefore, these fixatives are also called "color-locking, color-fixing multi-site fixatives."

[0071] For the structure , in the structure, The number can be 1 or 2, and the number is determined by The number of connection positions is determined by Independently selected from 、 、 、 hour, The number is 1; when two Both hour, The number is two.

[0072] Preferably, the Includes the following structures:

[0073] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、

[0074] .

[0075] In the above compounds, n is an integer greater than or equal to 1, and preferably, n is an integer within the range of 8-25.

[0076] Preferably, In the formula (a), a is an integer greater than or equal to 1. When a is 1, the fixing agent is a three-site fixing agent, including the following structure:

[0077] 、 、 、 、 、

[0078] 、 、 .

[0079] Preferably, when a is taken as 2, the fixative is a tetra-site fixative comprising the following structure:

[0080] 、

[0081] 、 、

[0082] 、

[0083] .

[0084] In the above compounds, n is taken as an integer in the range of 1-25, specifically, n is taken as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25.

[0085] Preferably, n is taken as an integer in the range of 8-25.

[0086] Preferably, the fixative is selected from the group consisting of bis-maleoyl oxal diamide, bis-pyrus acid bis(amino propyl) polydimethyl siloxane ammonium salt, bis-maleoyl bis(amino propyl) polydimethyl siloxane ammonium salt, dodecanoyl maleamide, octyloxymethyl maltol, decanoic acid p-hydroxystyrene ester, isooctadecyl pyrus acid ester, ascorbic acid eicosyl ester, bis(hydroxycoumarin decane) maleic diamide, bis(ferulic acid) poly(maleic acid-octanediol) ester, poly-maleic acid octyl ester, poly-maleic acid octyl ammonium salt, poly-maleic acid siloxane ammonium salt, 4-octyl curcumin, bis-ascorbic acid bis-amino propyl polydimethyl siloxane ammonium salt, bis(curcumin methoxy diphenyl ether) maleic diamide, or bis(decyl cinnamate) maleic diamide; and the disulfide bond compound is selected from the group consisting of dipalmitoyl cystine or cystine bis-PG-propyl silane triol.

[0087] More preferably, the composition consists of, by weight parts: fixative 0.1-20.29 parts and disulfide bond compound 0.05-8.56 parts; more preferably, the composition consists of, by weight parts: fixative 6.31-17.04 parts and disulfide bond compound 2.04-6.21 parts; further preferably, the composition consists of, by weight parts: fixative 11.3 parts and disulfide bond compound 4.8 parts.

[0088] In another aspect, the present application provides a repair and color fixing composition, comprising the following ingredients:

[0089] The above-mentioned composition and Asian white birch bark extract.

[0090] Preferably, the repair and color fixing composition comprises the following ingredients, by weight parts:

[0091] Fixative 0.10-20.29 parts, disulfide bond compound 0.05-8.56 parts, and Asian white birch bark extract 1.05-9.05 parts.

[0092] More preferably, the repair and color fixing composition comprises the following ingredients, by weight parts:

[0093] Fixative 6.31-17.04 parts, disulfide bond compound 2.04-6.21 parts, and Asian white birch bark extract 3.81-8.45 parts.

[0094] More preferably, the repair and color fixing composition comprises the following ingredients, by weight parts:

[0095] Fixative 11.3 parts, disulfide bond compound 4.8 parts, and Asian white birch bark extract 6.3 parts.

[0096] Preferably, the content of betulinol in the Asian white birch bark extract is ≥300 ppm.

[0097] More preferably, the content of betulinol in the Asian white birch bark extract is ≥500 ppm.

[0098] In another aspect, the present application provides the use of the above-mentioned composition and repair and color fixing composition in hair care products.

[0099] The hair care products include but are not limited to hair dyeing products, hair perming products, post-dyeing care products, etc. The use objects of the hair care products include but are not limited to the hair of human and other kinds of mammals. The dosage forms of the hair care products include but are not limited to shampoo, hair wash, hair wash, hair conditioner, hair conditioner, hair oil, hair mask, hair oil, essence, etc.

[0100] In addition to the above-mentioned composition, the above-mentioned product can further contain a suitable base, which is a base for hair products known to those skilled in the art.

[0101] In particular, the base of the hair oil includes, but is not limited to: PPG-12-PEG50 lanolin, acetamide MEA, hydroxyethyl cellulose, propylene glycol, bis(hydroxymethyl)imidazole alkyl urea, oleyl polyether-20, benzyl acetate, hydroxyphenyl propyl ester, oleyl benzyl dimethyl ammonium chloride, etc. The base of the hair oil includes, but is not limited to: vegetable oil, mineral oil, ester compound, polydimethylsiloxane, antioxidant, colorant, etc. The base of the hair conditioner includes, but is not limited to: oil, silicone oil, protein, etc.

[0102] In a last aspect, the present application provides a hair care product comprising the above-mentioned composition or the above-mentioned repair and color-fixing composition.

[0103] Compared with the prior art, the present application has the following beneficial effects:

[0104] (1) The present application provides a composition for repairing hair damage and fixing color, which significantly improves the smoothness of hair combing and the color fixing effect on dyed and permed hair by repairing the disulfide bond breaking site through strong interaction through the effective combination of the two components of the fixing agent, disulfide bond compound or its derivative, and enhances the wash resistance and color persistence.

[0105] (2) On the basis of the two components of the fixing agent, disulfide bond compound or its derivative, the present application provides a repair and color-fixing composition. By adding Asian white birch bark extract in combination with the two components of the fixing agent, disulfide bond compound or its derivative, the reasonable combination of the three components is realized and the hair repair effect is synergistically enhanced, especially the effect of hair hydrophobicity reconstruction, combing power reduction (smoothness), etc. Experiments show that the repair and color-fixing composition can further improve the smoothness of hair combing and the color fixing effect on dyed and permed hair, and has a better persistent color fixing effect. DETAILED DESCRIPTION

[0106] Terms and statements of the present application:

[0107] 1. The articles "a", "an", and "the": include plural objects unless otherwise expressly limited to one (singular) object.

[0108] 2. Numerical ranges: Unless otherwise expressly specified, all ranges or ratios disclosed herein are to be understood to be inclusive of any and all sub-ranges or sub-ratios subsumed therein. For example, a stated range or ratio of 1 to 30 should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 30; that is, all subranges or sub-ratios beginning with a minimum value of 1 or more and ending with a maximum value of 30 or less, as well as every number or integer, fraction, or range of numbers or integers, within that range.

[0109] The following non-limiting examples can more fully illustrate the application to one of ordinary skill in the art, but are not to be construed as limiting the application in any way. The following examples merely represent exemplary embodiments of the application and are not intended to limit the scope of the application, which is defined by the claims. Various changes and modifications to the application can be suggested to one skilled in the art, and it is intended that the application encompass such changes and modifications as fall within the scope of the appended claims.

[0110] The application is further described in the following non-limiting examples. The various chemical reagents used in the examples are either commercially available or are prepared by conventional methods known to those skilled in the art unless otherwise specified. The amounts recited in the following examples are amounts by weight unless otherwise specified. It is to be understood that the processes are conducted at room temperature unless otherwise specified.

[0111] Examples 1-5 provide a composition for hair damage repair and color lock. The ingredients are shown in Table 1 (in parts by weight):

[0112] Table 1

[0113]

[0114] In the above examples, the fixative is bis-maleic acid bis(amino propyl) polydimethylsiloxane ammonium salt, and the disulfide compound is dipalmitoyl cystine.

[0115] Example 6

[0116] Comparing with Example 1, the difference is that the disulfide compound is cystine bis-PG-propyl silane triol, and the rest is the same.

[0117] Example 7

[0118] Comparing with Example 1, the difference is that the fixative is bis-maleic acid bis(amino propyl) polydimethylsiloxane ammonium salt, and the rest is the same.

[0119] Example 8

[0120] Comparing with Example 1, the difference is that the fixative is bis-maleic acid ethylenediamide, and the rest is the same.

[0121] Example 9

[0122] Comparing with Example 1, the difference is that the fixative is maleic acid dodecanamide, and the rest is the same.

[0123] Comparative Examples 1 to 7 provide a substance that can be used for repairing damaged hair and locking color. The composition thereof is shown in Table 2 below (unit: parts by weight):

[0124] Table 2

[0125]

[0126] In Comparative Examples 1 and 3, the fixative used was bis(aminopropyl)polydimethylsiloxane ammonium salt of bisshikimic acid, and in Comparative Example 2, the disulfide bond compound used was dipalmitoylcystine. In Comparative Example 4, the disulfide bond compound was cystine bis-PG-propylsilanetriol. In Comparative Examples 5, 6, and 7, the fixatives were bis(aminopropyl)polydimethylsiloxane ammonium salt of bismaleic acid, bismaleic acid oxalylamide, and maleic acid laurylamide, respectively.

[0127] Examples 10 to 14 provide a color-repairing and color-fixing composition, the ingredients of which are shown in Table 3 below (unit: parts by weight):

[0128] Table 3

[0129]

[0130] Among them, the fixative is bismaleic acid ethylenediamine, the disulfide bond compound is dipalmitoylcysteine, and the mass content of betulin in the Asian birch bark extract is 98% (trade name betulin, brand Adamas, grade RG, specification 98%+).

[0131] Comparative Example 8

[0132] Compared with Example 10, the difference is that the Asian birch bark extract is replaced by ursolic acid in equal parts by weight, and the rest are the same.

[0133] Among them, the chemical structural formula of betulin is:

[0134] .

[0135] The chemical structure of ursolic acid is:

[0136] .

[0137] Examples 15-17 provide shampoo formulations, which are composed of the following ingredients by weight. Specific information is shown in Table 4 below (weight percentage (%)):

[0138] Table 4

[0139]

[0140] In Examples 15-17, the hair damage repair composition is the repair and color-locking composition provided in Example 10.

[0141] Examples 18-30 provide a shampoo, which differs from Example 15 in that the hair damage repair composition used is successively the composition for hair damage repair and color-locking provided in Examples 1-9, the repair and color-locking composition provided in Examples 11-14, respectively.

[0142] Comparative Examples 9-16 provide a shampoo, which differs from Example 15 in that the hair damage repair composition used is successively the composition provided in Comparative Examples 1-7, the repair and color-locking composition provided in Comparative Example 8, respectively.

[0143] Comparative Example 17 provides a shampoo, which differs from Example 15 only in that no hair damage repair composition is used, and is otherwise identical.

[0144] The shampoo is prepared by mixing the raw materials according to the formula, and is obtained.

[0145] Effect Evaluation 1

[0146] Comb performance test of hair strands.

[0147] Referring to the prior art “Establishment and Evaluation of a New Moisturizing Repair Shampoo System” (Liu Peihua et al., Guangzhou Chemical Industry, Vol. 38, No. 5, 2010, 176-178), the comb performance of hair strands using the shampoo provided in Examples 15-30, Comparative Examples 9-17, and a blank control group (water) is tested.

[0148] Test procedure

[0149] (1) Determine the dry comb combing force (F1) of the blank hair strands.

[0150] (2) The instrument automatically flushes the hair strands with water, and determines the wet comb combing force (F2) of the blank hair strands.

[0151] (3) Take 1 mL of the shampoo to wash the hair strands, repeat twice, and determine the wet comb combing force (F3) of the hair strands. The blank control group does not use the shampoo, but only uses water to wash the hair.

[0152] (4) Dry the hair strands, and determine the dry comb combing force (F4) of the hair strands.

[0153] Wet comb combing force improvement rate = (F2-F3) ÷ F2 x 100%.

[0154] Dry comb combing force improvement rate = (F1-F4) ÷ F1 x 100%.

[0155] Each group of parallel experiments 5 times, the average value and standard deviation.

[0156] The results of the hair combing force test are summarized in Table 5 (average ± standard deviation) below.

[0157] Table 5

[0158]

[0159] Among them, indicates that there is a significant difference in the same column of data compared with Example 15 and p < 0.05; indicates that there is a significant difference in the same column of data compared with Example 15 and p < 0.01; indicates that there is a significant difference in the same column of data compared with Example 15 and p < 0.001.

[0160] The hair bundle combing test is to dynamically simulate the process of using a hair comb to comb hair in people's daily life when the hair bundle is in a wet and dry state, respectively. This test measures and characterizes the degree of smoothness of the hair bundle after using the shampoo samples provided in Examples 15-30 and Comparative Examples 9-17 by accurately recording the change of frictional resistance during combing and calculating the combing force.

[0161] The results show that the combing force improvement of the blank control group using water instead of shampoo is negatively correlated under dry and wet hair conditions, indicating that water cannot improve the combing performance and the hair bundle is easy to tangle. Compared with Comparative Examples 9-17, the shampoo samples provided in Examples 15-30 all improve the wet combing and dry combing combing force improvement rate of wet hair, improving the dry and wet combing performance of the hair bundle, i.e. the samples provided in Examples 15-30 reduce the resistance of the hair bundle when passing through the comb, making the hair softer and smoother, and the combing effect better. Among them, the wet combing and dry combing combing force improvement of Example 15 is the largest, and the smoothing effect is better. It can be seen that the shampoo containing the composition for hair damage repair and color fixation provided by the present application exhibits better dry and wet combing, can effectively avoid the tangling of hair in dry and wet states, and greatly reduces the dry and rough feeling and the problem of difficult combing of hair. Therefore, the composition for hair damage repair and color fixation provided by the present application applied to shampoo and hair care products will have significant advantages in hair conditioning and maintenance, and can better meet the urgent needs of consumers for hair smoothness and easy to manage.

[0162] Effect evaluation 2

[0163] Combing performance test of hair bundle after perm and straightening.

[0164] After the curling and straightening operation, the baseline and the frictional resistance of the hair strands after the test of the shampoo samples provided by Examples 15-30, Comparative Examples 9-17, and the blank control group (water instead of the shampoo to be tested) are recorded according to the test method in Effect Evaluation 1, and the combing force and the improvement rate of the hair strands in wet and dry combing states are calculated according to the data.

[0165] The operation method of the hair strands after the curling and straightening operation is as follows:

[0166] After the hair strands without curling and dyeing are rinsed with clean water, the softener is applied until it is fully soaked, and the softening is performed at room temperature for 30 min. After the softening is completed, the setting agent is applied to the hair strands, each hair strand is coated with the setting agent, and then the curling rod is used to curl the hair strands. After the curling is completed, the hair strands are placed for 10 min, and then the curling is performed (110°C constant temperature for 10 min). After the completion, the hair strands are naturally cooled to room temperature, the agents are removed by rinsing with clean water, and the hair strands are dried with a hair dryer to obtain the curled hair strands.

[0167] The curled hair strands are straightened. The specific method is to soak the curled hair strands after the curling with the softener, and then the straightening is performed using the straightening board. After the straightening of the hair strands, the agents are removed by rinsing with clean water, and the hair strands are dried with a hair dryer to obtain the curled and straightened hair strands.

[0168] The results of the combing force test of the curled and straightened hair strands are summarized in Table 6 (average value ± standard deviation).

[0169] Table 6

[0170]

[0171] Among them, represents that there is a significant difference compared with Example 15 in the same column, and p<0.05; represents that there is a significant difference compared with Example 15 in the same column, and p<0.01; represents that there is a significant difference compared with Example 15 in the same column, and p<0.001.

[0172] In the dry and wet hair states, the hair strands after the curling are damaged due to the chemical reagents and high temperature treatment, and are more prone to frizz, dry touch, and greater frictional resistance when combing, indicating that the hair quality is damaged. This test is used to evaluate the improvement degree of the damaged hair quality after the curling and straightening treatment of the shampoo samples provided by Examples 15-30, Comparative Examples 9-17, and the blank control group (clean water).

[0173] The results showed that the combing force probability rates for both dry and wet damaged hair bundles tested in the blank control group were negative, indicating no improvement in dry and wet combing force, resulting in a negative correlation. Damaged hair bundles exhibited poor combing performance and were more fragile when wet, generating greater frictional resistance during combing and making combing difficult. This indicates that water failed to improve the combing performance of damaged hair bundles. Compared to Comparative Examples 9-17, the shampoo samples provided in Examples 15-30 significantly reduced frictional resistance in both dry and wet combing tests, resulting in smoother sliding between hair strands and a smoother combing experience for the combed hair bundles. Example 15 showed the greatest improvement in combing force for both wet and dry combing, resulting in a smoother combing experience. This indicates that shampoos containing the composition for hair damage repair and color-fixing provided by the present invention can effectively repair both dry and wet hair that has undergone perming and straightening, demonstrating significant repair effects. This not only significantly improves the combing performance of the hair, but also restores the health of the hair, making it soft and smooth again, improves the quality of damaged hair and successfully solves the problem of dry and frizzy hair that is difficult to repair after perming.

[0174] Effect evaluation 3

[0175] Evaluation of hair color care efficacy after hair tresses were dyed.

[0176] Originally black real hair was faded to a lighter shade using a bleaching agent. The faded hair was then dyed red using a semi-permanent red hair dye. The red-dyed hair was then placed in a 45°C hot air oven for 48 hours to simulate the effects of dry heat on hair. The dry heat-treated hair was divided into tresses, and the baseline chromaticity values ​​L1, a1, and b1 of the hair tresses after the same dyeing and dry heat treatment were measured and recorded using a hair color tester. L represents the lightness of the color, and a and b represent the chromaticity index of the color. The dyed hair tresses were washed with 1 mL of the shampoo samples provided in Examples 15-30, Comparative Examples 9-17, and a blank control (water). The dyed hair tresses were then hung to dry. After washing three and ten times, the chromaticity values ​​L2, a2, and b2 of the hair tresses were measured, respectively.

[0177] calculate The values ​​were averaged ± standard deviation (n=7) and recorded as the color difference, ΔE, between the hair tresses before and after washing. A smaller color difference indicates a better color-locking and color-fixing effect of the shampoo; conversely, a larger color difference indicates a more pronounced color change in the dyed hair, indicating more severe hair fading.

[0178] The color locking and color fixing effects of each group of shampoo samples are summarized in Table 7 below.

[0179] Table 7

[0180]

[0181] Among them, a means that the data in the same column are significantly different from those in the blank control group and p < 0.05; aa means that the data in the same column are significantly different from those in the blank control group and p < 0.01; aaa means that the data in the same column are significantly different from those in the blank control group and p < 0.001.

[0182] The chemical ingredients in dyes alter the hair's natural pigments and protein structure to achieve the desired coloring effect, but they also cause damage to the hair, such as damage to the hair cuticle and surface, loss of cortical protein, loss of moisture and lipids, a gradual loss of the hair's self-repair ability, and decreased color durability. Studies have found that the surfactants in shampoos dissolve and remove lipids and proteins from the hair, a significant factor in hair damage and color fading after dyeing. Therefore, people hope that shampoos and hair care products can effectively slow color fading and help hair maintain its color better.

[0183] The results showed that, based on hair color testing, the shampoo samples provided by Comparative Examples 9-17 had the highest color difference values, followed by the blank control group (water), followed by Examples 16-30, and the lowest value for Example 15. This indicates that compared to Comparative Examples 9-17, the shampoo samples provided by Examples 15-30 had the least impact on dyed hair tresses, effectively preventing pigment loss and providing hair color care. Furthermore, with increasing wash cycles, the color difference ΔE values ​​of the dyed hair tresses from Comparative Examples 9-17 and the blank control group increased, and the hair tresses gradually faded. The color difference values ​​of the hair tresses from Examples 16-30 showed a smaller change, with Example 15 showing the smallest change. Example 15 demonstrated the best performance in locking pigment ions and prolonging the durability of the dyeing effect. This indicates that shampoos containing the composition for hair damage repair and color-locking provided by the present invention help maintain stable hair color after dyeing, preventing fading and providing enhanced color-locking and color-fixing effects.

[0184] Example 31

[0185] Synthesis of bismaleic acid oxalamide.

[0186] The chemical structure of bismaleic acid oxalamide is:

[0187] .

[0188] Weigh 11.7200 g (0.1 mol) of maleic acid solid powder into a 100 mL three-necked round bottom flask, and add 55 mL of anhydrous ether. Install a constant pressure dropping funnel on the left side of the three-necked flask, mechanical stirring in the middle, and a water separator on the right side. Install a coiled condenser on the water separator, and then install a low-temperature circulation pipeline. Set the circulation liquid temperature to 5°C and start the circulation. Apply vaseline or vacuum silicone grease to the interface to ensure system sealing. Accurately weigh 3.0400 g (0.05 mol) of ethylenediamine into a 5 mL constant pressure dropping funnel, install a nitrogen balloon above the dropping funnel, replace the air in the reaction system three times, and maintain a slight aeration to maintain an inert gas environment. Turn on the heating mantle and stirring, control the heating temperature to 40°C, open the dropping funnel, and control the dropping speed to complete the addition within 10 min.

[0189] After completion, take 5 mL of anhydrous ether and inject it from the rubber interface above the constant pressure funnel in two portions to ensure that the wall adhered ethylenediamine is completely added to the reaction flask. During the addition of ethylenediamine, the reaction occurs. Since ether and water are not miscible and form azeotrope, they will gradually evaporate and condense into the water separator at a heating temperature of 40°C. Observe the layered liquid in the water separator, with water at the bottom. When no water is separated (about 4 h), the reaction is considered complete. The water in the water separator is weighed as 1.7545 g (theoretical value: 1.8015 g).

[0190] Due to the poor solubility of the target substance in ether, the solution gradually becomes turbid during the reaction. After the reaction is completed, disassemble the device, open the vacuum pump, and transfer the reaction liquid in the three-necked flask to a filter funnel. Use about 5 mL of anhydrous ether to clean the three-necked flask three times each time to obtain 12.4852 g of white solid. Use a 50% acetic acid solution to heat and recrystallize the obtained crude product. After filtration, washing, and drying, 11.3687 g of white powder is obtained as the target substance. The yield of bis-maleic acid ethylenediamide is 88.7% (theoretical value: 12.8105 g, liquid chromatography characterization purity is 98.1%).

[0191] The nuclear magnetic resonance hydrogen spectrum and carbon spectrum data of bis-maleic acid ethylenediamide are as follows.

[0192] 1 H NMR (DMSO-d6): δ (ppm) = 3.53 (s, 4H, CH2), 6.51 (m, 2H, =CH), 6.75 (m, 2H, =CH), 9.13 (s, 2H, NH), 11.53 (s, 2H, OH);

[0193] 13C NMR(DMSO-d6): δ(ppm) = 38.6(CH2), 133.8(=CH), 137.6(=CH), 166.5(CO), 169.6(CO).

[0194] Example 32

[0195] Synthesis of bis(aminopropyl)polydimethylsiloxane dihydrate ammonium salt.

[0196] The chemical structure of bis(aminopropyl)polydimethylsiloxane ammonium salt of bisshikimic acid is:

[0197] .

[0198] Weigh 17.7704 g (approximately 0.1 mol) of shikimic acid and 16.4628 g (approximately 0.05 mol) of bis(aminopropyl)polydimethylsiloxane into a 250 mL three-necked round-bottom flask. Add 150 mL of pure water to the reaction flask. Assemble the experimental apparatus: install a thermometer on the left side of the three-necked flask, a mechanical stirrer in the middle, and a spherical condenser (cooled with tap water) on the right side. Stirring was initiated, and the temperature was raised to 60°C for 3 h. Turn off the heat, remove the heating mantle, and cool to room temperature. Dismantle the apparatus, transfer the reaction solution to a separatory funnel, and extract three times with equal volumes of 150 mL of ethyl acetate. Separate the aqueous phase and collect it in a 250 mL beaker. Transfer the aqueous phase to the reservoir of a rotary evaporator. Start the rotary evaporator and apply vacuum to evaporate the water (do not allow complete evaporation). Transfer the remaining liquid to an evaporating dish and place it in a vacuum drying oven set at 45°C for evaporation. After complete drying, the product was removed to yield 32.5638 g of a white to light yellow powder. The solid was dissolved in 50% acetone and recrystallized overnight. The filter cake was rinsed with acetone, filtered, and dried to yield 31.3684 g of a white to light yellow powder, the target substance (theoretical value: 33.5490 g). The yield of bis(aminopropyl)polydimethylsiloxane dishikimate ammonium salt was 93.5%. The liquid chromatography purity was 98.5%.

[0199] The H NMR and C NMR data of bis(aminopropyl)polydimethylsiloxane ammonium salt of bisshikimic acid are as follows.

[0200] 1H NMR (DMSO-d6): δ (ppm) = 0.18 (s, 6H, Si-CH3), 0.23 (s, 12H, Si-CH3), 0.67 (t, 4H, CH2), 1.93 (dd, 4H, CH2), 2.03 (m, 4H, CH2), 3.45 (t, 4H, CH2), 3.78 (m, 4H, CH), 4.08 (2H, CH), 4.39 (s, 2H, OH), 5.23 (s, 2H, OH), 5.78 (s, 2H, OH), 6.69 (2H, =CH), 8.32 (s, 6H, + NH3);

[0201] 13 C NMR (DMSO-d6): δ (ppm) = 4.9 (CH3), 6.3 (CH3), 21.3 (CH2), 21.9 (CH2), 30.3 (CH2), 42.6 (CH2), 68.7 (CH), 70.3 (CH), 145.7 (=CH), 150.2 (=C), 170.9 (CO).

[0202] Example 33

[0203] Synthesis of Bis(maleato)bis(ammoniopropyl)polydimethylsiloxane ammonium salt.

[0204] The chemical structure of Bis(maleato)bis(ammoniopropyl)polydimethylsiloxane ammonium salt is:

[0205] n = 2.

[0206] Maleic acid 11.7163 g (about 0.1 mol) and Bis(ammoniopropyl)polydimethylsiloxane 16.4628 g (about 0.05 mol) were weighed in a 250 mL three-necked round bottom flask, 150 mL pure water was measured and added into the flask. The experimental device was set up, a thermometer was installed on the left port of the three-necked flask, a mechanical stirrer was installed in the middle, and a spherical condenser was installed on the right port (using tap water for cooling). The stirring was started, and the reaction temperature was maintained at 30°C for 5 h. The heating was turned off, the device was removed, and the reaction solution was transferred to a separatory funnel for three times of extraction operation using equal amount of 150 mL ethyl acetate. The aqueous phase was collected in a 250 mL beaker. The aqueous phase was transferred to the storage bottle of a rotary evaporator, the rotary evaporator was started, and vacuum was applied to evaporate the water (the liquid could not be completely evaporated). The remaining liquid was transferred to an evaporating dish and placed in a vacuum drying oven set at 45°C for evaporation. After complete drying, it was taken out to obtain 26.8654 g of white powder. The solid was dissolved in 50% acetone aqueous solution for recrystallization operation. Filtration was performed, the filter cake was washed with acetone, and the white powder was obtained after drying to obtain 26.3569 g (theoretical value: 27.7410 g) of bis(ammoniopropyl)polydimethylsiloxane ammonium bis-maleate. The yield of bis(ammoniopropyl)polydimethylsiloxane ammonium bis-maleate was 95.0%. The liquid chromatography purity was 99.2%.

[0207] The nuclear magnetic resonance hydrogen spectrum and carbon spectrum data of bis(ammoniopropyl)polydimethylsiloxane ammonium bis-maleate are as follows:

[0208] 1 H NMR (DMSO-d6): δ (ppm) = 0.19 (s, 6H, Si-CH3), 0.26 (s, 12H, Si-CH3), 0.63 (t, 4H, CH2), 1.99 (m, 4H, CH2), 3.36 (t, 4H, CH2), 6.63 (2H, =CH), 6.82 (2H, =CH), 8.46 (s, 6H, NH3), 11.96 (s, 2H, OH);

[0209] 13 C NMR (DMSO-d6): δ (ppm) = 5.8 (Si-CH3), 6.5 (Si-CH3), 22.6 (CH2), 23.5 (CH2), 44.6 (CH2), 135.2 (=CH), 139.6 (=CH), 167.5 (CO), 170.4 (CO).

[0210] Example 34

[0211] Synthesis of dodecanamide maleate.

[0212] The chemical structure of dodecylamide maleate is as follows:

[0213] n = 10.

[0214] Weigh 5.8534 g (about 0.05 mol) of maleic acid solid powder into a 100 mL three-necked round-bottom flask, and add 35 mL of anhydrous ether. Install the experimental device. Install a constant-pressure dropping funnel on the left side of the three-necked flask, mechanical stirring in the middle, and a water separator on the right side. After the installation and fixation are completed, install the low-temperature circulation pipeline, set the circulating liquid temperature to 5°C, and start the circulation. Apply vaseline or vacuum silicone grease to the interface to ensure the system is sealed.

[0215] Weigh 9.4566 g (0.05 mol) of dodecylamine accurately on an analytical balance, quickly add it to a 50 mL beaker, and dissolve it in 15 mL of anhydrous ether added to the beaker. Transfer it to a 30 mL constant-pressure dropping funnel, and use about 5 mL of anhydrous ether to wash the beaker and add it to the dropping funnel. Install a nitrogen balloon above the dropping funnel, replace the air in the reaction system three times, and maintain a slight aeration to maintain an inert gas environment in the system. Turn on the heating mantle and stirring, control the heating temperature to 40°C, open the dropping funnel, control the dropping speed, and complete the addition in 10-20 min. After completion, use a syringe to add 5 mL of anhydrous ether from the rubber interface above the constant-pressure funnel in two portions to rinse and ensure that the wall adheres to the dodecylamine completely enters the reaction flask. During the addition of the dodecylamine solution, the reaction occurs. Since ether and water are not miscible and form azeotrope, they will gradually evaporate and condense into the water separator at a heating temperature of 40°C. Observe that the liquid in the water separator is layered, with water at the bottom. When no water is separated out (about 4 h), it can be judged that the reaction is complete. Weigh the water in the water separator as 0.8863 g (theoretical value: 0.9008 g).

[0216] Due to the poor solubility of the target substance in ether, the solution gradually became turbid during the reaction. After the reaction is completed, disassemble the device, turn on the vacuum pump, and transfer the reaction liquid in the three-necked flask to a filter funnel, washing it with about 5 mL of anhydrous ether three times each time to obtain a light yellow block-shaped solid 13.9963 g. The obtained crude product is subjected to a recrystallization operation by heating and condensing acetone. After filtration, washing, and drying, 13.3305 g of light yellow powder is obtained, which is the target substance dodecylamide maleate. The yield of dodecylamide maleate is 94.1% (theoretical value: 14.1705 g). The sample is prepared for liquid chromatography purity analysis and nuclear magnetic structure characterization. The liquid chromatography purity of dodecylamide maleate is 99.3%.

[0217] The nuclear magnetic resonance hydrogen spectrum and carbon spectrum data of dodecylamide maleate are as follows.

[0218] 1 H NMR (DMSO-d6): δ (ppm) = 1.01 (t, 3H, CH3), 1.27 - 1.31 (m, 18H, CH2), 1.53 (m, 2H, CH2), 3.35 (t, 2H, CH2), 6.48 (m, 1H, =CH), 6.86 (m, 1H, =CH), 9.26 (s, 1H, NH), 11.76 (s, 1H, OH);

[0219] 13 C NMR (DMSO-d6): δ (ppm) = 14.2 (CH3), 22.9 (CH2), 26.8 (CH2), 29.6 - 29.9 (CH2), 30.6 (CH2), 31.8 (CH2), 41.3 (CH2), 132.6 (=CH), 136.5 (=CH), 165.2 (CO), 167.6 (CO).

[0220] Example 35

[0221] Synthesis of bis (curcumin methoxy diphenyl ether) male diamide

[0222] The structure is as follows:

[0223] .

[0224] The synthesis method is as follows:

[0225] Under argon protection, curcumin (10.0 g, 27.2 mmol) was dissolved in anhydrous pyridine (100 mL) in a 250 mL three-necked flask, the left side was connected with a constant pressure dropping funnel, the middle was installed with mechanical stirring, and the right side was connected with a thermometer. After cooling to 0°C in an ice bath, acetyl chloride (7.8 mL, 108.8 mmol) was slowly added through the dropping funnel, and stirred at room temperature for 12 hours. After quenching the reaction, it was extracted with ethyl acetate, and dried to obtain tetraacetyl curcumin (14.1 g, 95%).

[0226] Bis (4-methoxy diphenyl ether) (15.0 g, 42.5 mmol) was dissolved in 150 mL of anhydrous DCM (dichloromethane) in a 500 mL three-necked flask, and triethylamine (17.7 mL, 127.5 mmol) was added in turn. After adding trifluoromethanesulfonic anhydride (14.3 mL, 85.0 mmol) through a constant pressure dropping funnel under ice bath, stirring at room temperature for 6 hours, bis-trifluoromethanesulfonate intermediate (21.4 g, 94%) was obtained after purification.

[0227] Tetraacetylcurcumin (12.0 g, 21.9 mmol) and the bistrifluoromethanesulfonate intermediate (20.0 g, 37.4 mmol) were dissolved in 200 mL of anhydrous DMF in a 500 mL three-necked flask. Cs2CO3 (35.7 g, 109.5 mmol) was added. After argon replacement three times, the mixture was heated in an oil bath to 80°C and reacted for 24 hours. Column chromatography (PE / EA gradient elution) yielded the tetraacetyl-bisether bridged intermediate (14.8 g, 65%).

[0228] The intermediate (10.0 g, 9.6 mmol) was dissolved in 200 mL of MeOH / THF (1:1) in a 500 mL three-necked flask. 2M NaOH (50 mL) was added and stirred at 60°C for 8 hours. The pH was adjusted to neutral and the mixture was concentrated to obtain the free phenolic hydroxyl intermediate (7.2 g, 89%).

[0229] Maleic acid (3.5 g, 30.1 mmol) and SOCl2 (10 mL) were refluxed in a 100 mL round-bottom flask for 2 h and distilled under reduced pressure to obtain maleic acid chloride (4.1 g, 95%).

[0230] The deprotected intermediate (7.0 g, 8.4 mmol) was dissolved in 150 mL of anhydrous DCM in a 500 mL three-necked flask. After cooling in an ice bath, maleoyl chloride (4.1 g, 33.6 mmol), DMAP (0.5 g, 4.2 mmol), and DIPEA (8.4 mL, 48.0 mmol) were added sequentially. Stir at room temperature for 36 hours. The product was filtered, purified by preparative HPLC (acetonitrile / water = 70:30), and lyophilized to obtain the final product (3.8 g, 28%).

[0231] The H NMR and C NMR data of bis(curcumin methoxydiphenyl ether)maleimide amide are as follows:

[0232] 1H NMR(DMSO-d6): δ(ppm) = 3.71(s, 6H, CH3), 3.85(s, 6H, CH3), 5.13-5.14(m, 8H), 6.72(m, 2H), 6.80-6.85(m, 4H, CH), 6.88-6.91(m, 4H, CH), 6.92-6.94(m, 2H, CH2), 6.97-7.07(m, 12H, CH), 7.12(m, 4H, CH),7.28-7.29(m, 8H,CH), 7.45(m,4H) 7.48(m, 4H) 8.36(br, 2H, OH);

[0233] 13 C NMR(DMSO-d6): δ(ppm) = 55.31, 56.05, 56.25, 68.93, 71.29, 111.96,112.71, 114.89, 116.39, 116.82, 117.26, 120.28, 124.60-124.85, 126.97,127.53-127.56, 128.89, 129.41, 130.79, 132.08, 143.57-143.96, 149.34, 149.46,149.58, 150.91-150.86, 152.41, 157.20, 165.89, 194.62.

[0234] Example 36

[0235] Synthesis of Bis(Decylcinnamate)Maleic Diamine Amide

[0236] The structural formula is as follows:

[0237] .

[0238] The synthesis method is as follows:

[0239] Maleic acid (14.8 g, 0.1 mol) was accurately weighed and dissolved in 100 mL of tetrahydrofuran in a 250 mL three-necked round bottom flask. The flask was equipped with a mechanical stirrer, a spherical condenser, and was protected by nitrogen. Decamethylenediamine (17.2 g, 0.11 mol) and DMAP (1.2 g) were added to the flask successively, and the flask was cooled to 0 °C in an ice bath. DCC (24.6 g) was dissolved in 50 mL of tetrahydrofuran and was transferred to a constant pressure dropping funnel, and the dropping speed was controlled to be completed within 10-15 min. The ice bath was removed, and the reaction was stirred at room temperature for 12 h. The DCU precipitate was removed by filtration, and the solvent was removed by rotary evaporation under reduced pressure. The crude product was recrystallized with a mixture of ethanol / water (3:1), and was dried under vacuum to obtain maleic acid bis-decamethylenediamide as a white solid (23.5 g, yield 85%).

[0240] A 250 mL three-necked flask was charged with maleic acid bis-amide (15.6 g, 0.05 mol), which was dissolved in 120 mL of dichloromethane. Sodium borohydride (7.6 g, 0.2 mol) was added in batches under ice bath conditions, and methanol (30 mL) was added dropwise. After 1 h of reaction at 0 °C, the reaction was continued at room temperature for 4 h. The reaction was quenched by slowly adding 50 mL of water, and the organic phase was collected by liquid separation, dried over anhydrous magnesium sulfate, filtered, and rotary evaporated to obtain the crude hydroxylated intermediate (14.8 g).

[0241] A 250 mL three-necked flask was equipped with a mechanical stirrer, a water separator (connected to a serpentine condenser), and was protected by nitrogen. The crude hydroxylated intermediate (14.8 g), methyl cinnamate (19.2 g, 0.12 mol), p-toluenesulfonic acid (1.2 g), and toluene (100 mL) were added. The reaction was heated to reflux, and water was continuously removed through the water separator for 8 h. After the reaction solution was cooled, it was washed with saturated sodium carbonate solution (50 mL x 2), and the organic phase was collected by liquid separation, dried over anhydrous sodium sulfate, filtered, and rotary evaporated. Column chromatography separation (petroleum ether: ethyl acetate = 5:1) yielded the target product as a white solid (22.3 g, total yield of two steps 70%).

[0242] The results of the nuclear magnetic resonance hydrogen spectrum and carbon spectrum of bis (methyl cinnamate decyl) maleic diamide amide are as follows.

[0243] 1H NMR (DMSO-d6): δ (ppm) = 1.26-1.34 (m, 16H, CH2), 1.35-1.41 (m, 8H, CH2), 1.50-1.54 (m, 4H, CH2), 1.63-1.69 (m, 4H, CH2), 3.16-3.19 (t, 4H, CH2), 4.13-4.15 (t, 2H, CH2), 6.40-6.44 (d, 2H, =CH), 6.61 (s, 2H, =CH), 7.31-7.37 (m, 10H), 7.45-7.47 (m, 2H, NH), 7.57-7.59 (m, 2H, =CH), 7.62-7.66 (m, 2H, =CH);

[0244] 13 C NMR (DMSO-d6): δ (ppm) = 23.88, 25.92, 28.39, 28.68, 29.68, 20.02, 30.12, 30.17, 4.64, 64.06, 116.86, 128.57, 129.10, 130.70, 131.11, 134.35, 145.27, 166.94, 167.62.

[0245] Example 37

[0246] Synthesis of bis(hydroxycoumarin decane) maleic diamide

[0247] The structure is as follows:

[0248] .

[0249] The synthesis method is as follows:

[0250] An analytical balance was used to weigh 7-hydroxycoumarin (16.2 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol), which were placed in a 250 mL three-necked round-bottom flask and dissolved in 200 mL DMF. A mechanical stirrer, spherical condenser, and nitrogen protection were installed on the three-necked flask. 1,10-dibromodecane (37.6 g, 0.12 mol) was measured and transferred to a constant-pressure dropping funnel, and the dropping rate was controlled at 80°C. The addition was completed within 15-20 min. The reaction was refluxed at 80°C for 12 hours. The reaction solution was cooled, quenched with 100 mL of water, extracted with 50 mL of ethyl acetate three times, the organic phases were combined, and concentrated by rotary evaporation. Column chromatography (petroleum ether: ethyl acetate = 8:1) was used for separation, and bis-7-coumarin oxydecane intermediate (28.5 g, yield 75%) was obtained.

[0251] To a 250 mL round-bottom flask, add maleic acid (11.6 g, 0.1 mol) and 100 mL of anhydrous ethanol and stir to dissolve. Slowly add a 20 mL solution of decanediamine (17.2 g, 0.11 mol) in anhydrous ethanol to the solution dropwise. Maintain stirring during the addition and control the rate of addition to avoid excessive reaction. After the addition is complete, stir the reaction mixture at room temperature for 8 hours. After the reaction is complete, remove the ethanol under reduced pressure to obtain a crude product. Dissolve the crude product in 100 mL of distilled water and adjust the pH of the solution to neutral with dilute hydrochloric acid. Solids will precipitate. Filter the solution and wash the solid with distilled water three times (30 mL each time). Then, dry the solid in a vacuum drying oven at 60°C to constant weight to obtain maleic bisdecanediamine amide diacid.

[0252] A 250 mL three-necked flask equipped with a mechanical stirrer and a spherical condenser was purged with nitrogen. The bis-7-coumarinoxydecane intermediate (20.0 g, 0.035 mol) and maleic bisamide diacid (18.0 g, 0.035 mol) were added and dissolved in 200 mL of dichloromethane. DCC (8.6 g, 0.042 mol) and DMAP (0.4 g) were added and stirred at room temperature for 24 hours. Byproducts were removed by filtration, and the mixture was concentrated by rotary evaporation. Recrystallization from ethanol and vacuum drying gave the desired product (22.1 g, 78% yield).

[0253] The H NMR and C NMR data of bis(hydroxycoumarindecane)maleic acid diamine amide are shown below.

[0254] 1 H NMR(DMSO-d6): δ(ppm) = 1.26-1.43 (m, 16H, CH2), 1.50-1.54(m, 4H,CH2), 1.60-1.62(m, 4H, CH2), 1.68-1.70(m, 4H, CH2), 2.84-3.14(m, 4H, CH2),3.16-3.19(m, 4H, CH2), 3.46-3.58(m, 4H, CH2), 4.09-4.11(m, 2H, NH), 5.76(s,2H, CH), 7.08-7.10(m, 2H, CH), 7.17-7.18(m, 2H, CH), 7.30-7.32(m, 2H, CH),7.36-7.38(m, 2H, CH), 7.45-7.64(m, 2H, CH).

[0255] 13C NMR(DMSO-d6): δ(ppm) =23.88, 25.91, 27.37, 28.68, 28.79, 29.42,29.66, 20.02, 30.07, 30.10, 30.12, 30.15, 30.61, 36.60, 40.64, 68.55, 69.40,75.48, 93.17, 116.38, 116.95, 119.29, 124.39, 124.55, 124.62, 124.64, 127.83,130.11, 131.11, 133.52, 150.66, 155.61, 163.49, 165.34, 166.94, 167.77.

[0256] Example 38

[0257] Synthesis of N-(2,3-dimethylmaleimido)-L-phenylalanyl-L-phenylalanine furan-2-carboxylate

[0258] The structural formula is as follows:

[0259]

[0260] The synthesis method is as follows:

[0261] Weigh maleic acid (116.1 mg) and phenylalanine dipeptide (312.3 mg) into a dry 100 mL round-bottom flask. Add 20 mL of anhydrous DMF and stir until completely dissolved. Cool to 0°C in an ice bath. Add DCC (247.3 mg) and DMAP (12.2 mg). Remove the ice bath and stir at room temperature (25°C) for 12 hours. Filter to remove the white precipitate (DCU), and concentrate the filtrate to dryness under reduced pressure.

[0262] The crude product was dissolved in 10 mL of ethyl acetate and washed with water (3 × 10 mL). The organic phase was dried over anhydrous Na₂SO₄. After concentration, it was purified by column chromatography (eluent: CH₂Cl₂ / MeOH = 15:1) to obtain maleic acid-Phe-Phe as a white solid.

[0263] Dissolve maleic acid-Phe-Phe (340 mg, 0.85 mmol) in 15 mL of anhydrous CH2Cl2, add EDC·HCl (230.7 mg) and DMAP (12.2 mg). Add furanone (98.1 mg dissolved in 5 mL of CH2Cl2) dropwise, and stir at room temperature for 6 hours. Quench with 10 mL of ice-cold water, and separate the organic phase using a separatory funnel. Wash the organic phase with saturated NaHCO3 (2 × 10 mL) and water (2 × 10 mL), then dry over anhydrous Na2SO4. Concentrate to obtain furanone-maleic acid-Phe-Phe ester as a light yellow oil.

[0264] Dissolve the crude product from the previous step (380 mg) in 20 mL of anhydrous toluene, add acetic anhydride (1.5 mL) and pyridine (0.5 mL). Heat in an oil bath to 110°C (reflux) and stir for 4 hours. Cool to room temperature, wash off excess acetic anhydride with 1 M HCl (10 mL), and then wash with saturated aqueous NaHCO₃ (2 × 10 mL). The organic phase is dried, concentrated, and purified by column chromatography (eluent: EtOAc / hexane = 1:3) to afford white crystals. Yield: 75% (approximately 280 mg).

[0265] The H NMR and C NMR data of N-(2,3-dimethylmaleimido)-L-phenylalanyl-L-phenylalanine furan-2-carboxylate are shown below.

[0266] 1 H NMR(DMSO-d6): δ(ppm) = 1.45-1.48(m, 12H, CH3), 2.67-2.71(m, 4H,CH2), 2.79-2.83(m, 4H, CH2), 3.76-3.81(m, 6H, CH), 4.75-5.04(m, 4H),6.46-6.47(m, 2H, =CH), 7.62-7.77(m, 20H,Ph-H);

[0267] 13 C NMR(DMSO-d6): δ(ppm) =14.48 (CH3), 16.73 (CH3), 37.37 (CH2), 57.54( CH), 68.26( CH), 127.64( Ph-C), 129.60( Ph-C), 129.91( Ph-C), 132.12( C=C), 134.57( C=C), 137.30( Ph-C), 138.09( C=C), 165.78( C=O), 169.30( C=O), 172.48( C=O), 195.38( C=O).

[0268] Example 39

[0269] Synthesis of Poly(octanediol-maleate) Bis(ferulic acid)

[0270] The structural formula is as follows:

[0271] .

[0272] The synthesis method is as follows:

[0273] Mount a 250 mL round-bottom flask on a magnetic stirrer and add a stirrer. Connect a water separator (pre-filled with toluene to the branch outlet) and a condenser (top port connected to condensed water, bottom inlet, top outlet). Seal all other ports with a nitrogen balloon or rubber stopper to ensure leak-proof operation. Add ferulic acid (7.28 g), octanediol (5.92 g), and toluene (100 mL) to the flask. Finally, add p-toluenesulfonic acid (0.23 g) to prevent premature exposure of the catalyst to water vapor. Heat to reflux: Raise the bath temperature to 120-140°C and start magnetic stirring (300-500 rpm). Flow water through the condenser until toluene begins to reflux in the water separator. Observe for accumulation of aqueous phase (a sign of reaction progress). Continue the reaction for 6 hours, until no more water droplets form in the water separator. Cool the mixture to 80°C and slowly add maleic acid (2.32 g) via an addition funnel. Add additional toluene (50 mL) to maintain the solvent volume. Reflux again, raise the temperature to 130°C, and continue the reaction for 5 hours. Collect the generated water again in a water trap. Terminate the reaction, cool to room temperature, and transfer the reaction mixture to a separatory funnel. Wash with saturated NaHCO₃ solution (3 × 50 mL) until neutral to remove residual acid catalyst. Combine the organic phases, dry over anhydrous Na₂SO₄, and concentrate to dryness on a rotary evaporator under reduced pressure. Purify by column chromatography on a silica gel column (200-300 mesh) using a gradient of petroleum ether → ethyl acetate / petroleum ether (1:1) as the eluent. Rotary evaporation yields the product as a white solid.

[0274] The H NMR and C NMR data of poly(octanediol maleate) bis(ferulic acid) ester are as follows.

[0275] 1 H NMR(DMSO-d6): δ(ppm) = 1.20-1.33(br, 36H, CH2), 4.27-4.32(t, 12H,CH2), 6.39-6.42 (d, 4H), 6.81-6.83(d, 4H), 7.23-7.25(d, 4H), 7.36-7.39(d,4H), 9.64(2H, OH).

[0276] 13C NMR(DMSO-d6): δ(ppm) =22.35, 22.59, 22.70, 23.34, 25.16, 25.56,25.64, 28.20, 28.43, 64.63, 64.81, 64.90,120.40, 126.09, 130.88, 133.27,134.40, 135.47, 136.92, 153.36, 168.68, 171.10, 171.89.

[0277] Example 40

[0278] Synthesis of Octyloxymethyl Maltol

[0279] The structural formula is as follows:

[0280] .

[0281] The synthesis method is as follows:

[0282] Accurately weigh 7.407 g (0.05 mol) of ethyl maltol on an analytical balance and add it to a 250 mL three-necked round-bottom flask. Dissolve 50 mL of anhydrous pyridine in the flask. Install a constant-pressure dropping funnel at the left end of the three-necked flask, with a mechanical stirrer in the middle. Connect the right end to a water separator, with a serpentine condenser above the separator. Once assembled and secured, seal the interfaces with vacuum silicone grease to ensure a tight seal. Weigh 4.16 g (0.052 mol) of acetyl chloride on an analytical balance and transfer it to the constant-pressure dropping funnel. Stirring was initiated, and acetyl chloride was slowly added dropwise to the flask at room temperature. Stirring was continued for 3 h. Upon completion of the reaction, the system was poured into an ice-water mixture, filtered, the solid washed with distilled water, and dried to obtain the acetyl-protected intermediate.

[0283] Transfer the acetyl-protected intermediate to a 250 mL round-bottom flask and dissolve it in 120 mL of carbon tetrachloride. Install a reflux condenser and light irradiation device. Slowly add 8 g (0.05 mol) of bromine dropwise while stirring in the dark. After the addition is complete, turn on the light and reflux for 5 hours. After cooling, wash the organic phase with 5% NaCO solution, dry over anhydrous sodium sulfate, and remove the solvent by rotary evaporation to obtain the bromoethyl intermediate.

[0284] Weigh 7.41 g (0.05 mol) of octanol on an analytical balance and add it to a dry 100 mL round-bottom flask. Dissolve it in 40 mL of anhydrous ether. Add 1.15 g (0.05 mol) of metallic sodium in batches and stir at room temperature until the sodium reacts completely to obtain a sodium octanol solution.

[0285] The bromoethyl intermediate was transferred into a 250 mL three-necked flask with sodium octanol solution, THF 80 mL was used as solvent, heated to reflux for 10 h (TLC monitoring, developing agent: petroleum ether: ethyl acetate = 5:1). After the reaction was completed, it was cooled and filtered, and the solvent was removed by rotary evaporation. The crude product was recrystallized with petroleum ether-ethyl acetate to obtain the octyloxy intermediate.

[0286] The octyloxy intermediate was transferred into a 250 mL round-bottom flask, 120 mL of methanol and 10 mL of 1 M dilute hydrochloric acid were added, and heated to reflux for 3 h (TLC monitoring, developing agent: petroleum ether: ethyl acetate = 2:1). Concentrated by rotary evaporation, adjust pH to neutral with ice water, suction filtration, recrystallize the solid with ethanol-water mixture, dry to obtain the target compound 14.21 g. Yield 94.7%.

[0287] The nuclear magnetic resonance hydrogen spectrum and carbon spectrum data of octyloxy methyl maltol are as follows.

[0288] 1 H NMR(DMSO-d6): δ(ppm) = 0.89(t, 3H, CH3), 1.26-1.34(m, 10H, CH2),1.54-1.60(m, 2H, CH2), 3.47(t, 2H, CH2), 4.34(2H, CH2), 6.21(1H, CH),8.08(1H,OH) 9.43(s, 1H, CH).

[0289] 13 C NMR(DMSO-d6): δ(ppm) = 14.08, 22.70, 26.28, 29.31, 29.36, 29.81,31.85, 68.79, 71.74, 112.42, 139.81, 146.22, 164.77, 175.74 。

[0290] Finally, it should be pointed out that the above content is only used to illustrate the technical solutions of the present application, and is not a limitation on the protection scope of the present application. Simple modifications or equivalent replacements of the technical solutions of the present application made by those skilled in the art do not deviate from the essence and scope of the technical solutions of the present application.

Claims

1. A color-fixing and repairing composition, characterized in that: The following ingredients are included by weight: 6.31-17.04 parts of a fixative, 2.04-6.21 parts of a disulfide compound, and 3.81-8.45 parts of an Asian birch bark extract; The content of betulin in the Asian birch bark extract is 98%; the fixative is a compound containing one or more α,β-olefinic carbonyl groups or a compound containing one or more benzoyl groups; The chemical structure of the fixative is: 、 n=2, or n=10; The disulfide bond compound is selected from dipalmitoylcystine or cystine bis-PG-propylsilanetriol.

2. The color-repairing and color-fixing composition according to claim 1, characterized in that: The composition comprises the following ingredients by weight: 11.3 parts of a fixing agent, 4.8 parts of a disulfide bond compound and 6.3 parts of an Asian birch bark extract.

3. Use of the color-repairing and color-fixing composition according to any one of claims 1 to 2 in the preparation of hair care products.

4. A hair care product, characterized in that The color-repairing and color-fixing composition comprises the color-repairing and color-fixing composition according to any one of claims 1 to 2; The hair care products include shampoo and hair care products.

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