JPH02138110A - Crosslinking agent useful to hair treatment - Google Patents

Abstract

PURPOSE: To set hair permanently without denaturation of keratin by bringing hair into contact with a cross-linking agent bearing a group selectively bonding to a free sulfhydryl group and another group selectively bonding to free amino group in a keratin substance. CONSTITUTION: As a cross-linking agent, is used a compound bearing a part that can selectively bond to free sulfhydryl group and another part that can selectively form a bond with a free amino group in a keratin substance, for example, N-sulfosuccinimidyl [4-(N-maleimidemethyl)] cyclohexanecarboxylate to treat a keratin substance (hair) with the cross-linking agent in such an amount that the cross-linking bonds can be sufficiently formed but the protein of the keratin substance is not substantially modified. This cross-linking agent can make hair wavy or straight, as desired. It can give hair having good curls and strong hair strength and is particularly suitable for curling bleached hair.

Description

[Detailed description of the invention]

The present invention is suitable for permanent hair shaping.
hair shaping compositions and methods for using the compositions. When cold waving hair without using room temperature heat, tresses rolled with appropriate curlers are moistened with waving 1]-shine. The above I-ping

【”−
Cylinders have a reducing effect that chemically destroys the disulfide bonds that are characteristic of keratin and determine the cohesive strength of the protein structure, and this reduction plasticizes the fibers, allowing them to be deformed without stretching or contracting. Vine. In particular, conventional hair shaping involves the use of water-soluble mercaptocarboxylic acids and putrium salts, such as aqueous mercaptocarboxylate, in the form of liquid or thick creams or gels. salt/
This could be done by contacting with a reducing agent such as dibenzene sulfate. The composition is contacted with the hair for a sufficient period of time to reshape the hair by reductively breaking disulfide bonds and forming SH groups. The composition is then rinsed off with water and the hair is treated with a fixing or neutralizing agent (oxidizing agent) that permanently reshapes the treated T by forming disulfide bonds in new locations. If you wish to permanently straighten your hair, apply a reducing lotion in a thick layer, for example as a cream.
Comb through the hair to distribute it evenly. The composition is allowed to act on the hair for a sufficient period of time to avoid cleavage of the disulfide bonds, while the hair is more or less continuously combed to keep it straight, and then the hair is treated with a shaping agent (3 hapi).
ng agent) with water. Next, the hair is fixed or set using a setting composition containing an oxidizing agent in a known manner. Permanent waving cannot be obtained by destroying the ionic bonds or water thread bonds characteristic of hair set. Permanent deformities are obtained by cleaving the cysdine bonds and reforming them in new positions after shaping. When the disulfide bonds are broken during the process of permanent 1-quaving, the hair llff becomes very weak until the disulfide bonds are angulated. Therefore, applying tension to the fibers may pull the individual polypeptide chains apart. This is because the disulfide bonds that normally hold the polypeptide chains together are no longer present, or at least their number is reduced. U.S. Patent No. 2,850,351 and 2.933.3
No. 65 Mei 1 [1tl shows that when a bis-unsaturated crosslinking agent whose unsaturated group is activated by an adjacent carbonyl group is used, it reacts with the SH group to chemically modify keratin, especially wool. It is shown. These specifications also indicate that crosslinking agents are useful for crosslinking between two pendant N1-12 groups. In the case of the compounds described in the above specification, the scope of their use is limited because the unsaturated group must be adjacent to the carbonyl group in order to form a crosslinking bond. The processing of wool is
It can be more extensive than the treatment of live tU due to the free time available for treatment and the lack of toxicity issues. Therefore, a broader range of keratin crosslinking agents is desired. According to the present invention, a crosslinking agent that selectively reacts with the pendant 51-1 group under treatment conditions 1) has a temple portion and a portion that can selectively react with the two groups for pendant N. Forming a cross-link between the pendant amino of the hair and the pendant amino 111 by selectively cross-linking between the S Hl from the disrunoid bond and the pendant N H2 group in the protein molecule. It was discovered that keratin, especially human L hair, can be chemically modified. In a preferred embodiment of the invention, the use of the crosslinking agents of the invention resulted in hair activating good curl formation and often high tensile strength. The invention is particularly suitable for curling treated, eg bleached, hair. Therefore, the present invention [well, a moiety that can selectively bind to a free sulfhydryl group under a condition f1 that is sufficient to form a crosslink but insufficient to actually denature the protein of a keratin material. Disulfide bonds are destroyed by the action of a reducing agent that forms M1 sulfhydryl groups, which consists of contacting the keratin material with a cross-linking agent that can selectively bond with the ``gri-free amino groups of the keratin material. The present invention provides a method for treating keratin materials. The method of the invention processes a wide range of keratin fibers, including animal hair such as camel hair, mohair, wool, horse hair, cow hair, pig bristles, and feathers from animals such as chickens, ducks, and turkeys. However, the invention is particularly suitable for waving hair, live or removed, ie in the form of a wig. The invention is particularly suitable for 1-2]-rudo waving and hair straightening systems, where the hair may be of Caucasian or Black origin. The present invention provides a method for treating hair without permanently deforming it, which method consists in applying any of the compounds specified below as a crosslinking agent to the hair having broken disulfide bonds. The present invention provides a composition for reducing disulfide bonds in hair, a moiety capable of selectively forming a bond with a sulfhydryl group, and a moiety capable of selectively forming a bond with a free amino group in a keratin material. A hair I-ping system is also provided comprising a cross-linking agent as described above. In the following, the present invention and its preferred embodiments will be described in connection with the treatment of human hair to transform it into a desired shape. Before using the crosslinking agent, the disulfide bonds must be broken by the action of a reducing agent. Reducing agents commonly used in cold-waving hair to break cystine bonds are thiols or mercaptans and sulfites and/or bisulfites. Many of the mercaptans are effective only at high pl+, while others with lower p and 1-1 higher ionization constants are effective at lower pH. For example, the ammonium salt of thioglycolic acid is
) When H exceeds 9, a satisfactory waving action (reduction) can be exhibited. Thioglycolamide or glycol thioglycolate, sublime! Other compounds such as salts and/or bisulfites are used with neutral or slightly acidic pl+. - Mercaptans and thiols commonly used in waving lotions are: Boooglycol, DiA lactic acid, Cysdene, Buoglycerol, Buoglycol hydrazide, Thioglycolamide, Glycerol monothiol. mercaptopropionic acid, N-hydroacetamide, N-mercaptopropionic acid, N-mercaptopropionic acid, β-
Mercap l---r thylamine, β-mercapdobu [
] Pionamide, 2-mercapto-ethanesulfonic acid,
A polythiol derivative formed by adding siaamine to a polymer of "dimercaptoadipic acid, Diji A Tray 1 Hel, homocysteine buolactone, cysteine derivative, and maleic anhydride-alkyl vinyl ether." Tipite and/or bisulfite salts that may be used are those commonly used for hair conditioning, such as sodium and ammonium salts. The maximum amount of reducing agent used is, as understood by those skilled in the art, sufficient to break a sufficient number of disulfide bonds to make the hair wavy or straight. By breaking the disulfide bonds and forming free sulfhydryl-31 hairs that hang on the hair []
- You can give your hair the desired shape by wrapping it with a hair curler or a bottle, or combing it if you want it to be straight. - Breaking the disulfide bonds in the usual way, which involves applying a reducing agent to the curled hair within the shell. At this time, it may be heated. The curled or straightened modified hair is then treated with a cross-linking composition containing a cross-linking agent in a carrier or base, such as buffered water or a course or cream. Moisten. The carriers are known and similar to those currently used in waving and "neutralizing" compositions. Preferably, the water or carrier maintains the crosslinking agent in contact with the hair for a sufficient period of time to permanently set the hair. The crosslinking agent is applied at conditions F that promote crosslinking. When using the mulberry agent of the present invention for 1 J, a pl+ of about 6 to 9 times (lower than that which would permanently destroy hair proteins) is effective. The cross-linking agent of the present invention selectively forms chemical bonds with the pendant NH2 on Keraboon under reaction conditions such as pl+, which is substantially neutral to slightly alkaline and not alkaline enough to break the pepbud bonds. The part that can be done,
It can be generally defined as a moiety capable of selectively forming a chemical bond with an SH group bonded by a divalent organic group serving as a bonding means. Preferably rack 8! The binder is water soluble. As used herein, the expression "selectively capable of forming chemical bonds" means that the crosslinking agent forms the majority of bonds between a given group, for example between a pendant sulfhydryl group and a pendant amino group. , and between the pendants S 1-1-38 and between the pendants N 1-12- and N +-12, but the bonds can be formed between the cross-linking agent and the group, e.g.
It means a chemical bond formed between the group and N+-121. The invention is not limited to the actual binding site, as different types of binding may exist at one time. These bonds can be additional bonds, such as between ethylenic unsaturation and an SH group, substituted bonds, where sulfur replaces a halogen and forms a bonding site, for example by hydrolysis. The expression "forming a bond", as is obvious to those skilled in the art, refers to an addition reaction that does not involve substitution of a group; It is meant to include a substitution reaction in which a binding agent is cleaved and a bond is formed via the residue of a crosslinking agent. The crosslinking agent capable of selectively reacting with amino groups and sulfhydryl groups of the present invention has the formula (1); , Z represents any group capable of selectively reacting with the sulfhydryl groups of the hair under the treatment conditions, R represents Y, !: a divalent group that bonds with Z), R represents a group such as It is represented by 2 representing a coupling means for coupling Y and/. The general concept of the invention also includes those in which Y is directly bonded to 7. It is to be understood that the groups represented by Y and 7 can react with S 2 H and NH2 groups, respectively. Such Yli (generally amino reaction + sf) is a) hydroxyl group (-011) b) alkoxy group (-OR2) c) N-succinimide, t:j succinimide) haloacidic group -O-C-( C112) b-X (where b is an integer, i.e. about 1 to 8, preferably 1
~2, X represents haLlgun, preferably b is 1, and X is iodine) t) Phosphonyl group (-0
-P (0)2- R2) g) Phosphoryl group (-0-P (0) -0-R2) h) Sulfonate group (-0-3(0) 2-+<2)i
) sulfate group 10-8 (0) -0-R2) (wherein R2 represents any non-interfering organic substituent such as aryl or alkyl or hydrogen) j) aminobenzoate-N-succinimide group, etc. However, it is not limited to this. Other amine reactive groups may also be used as Y groups. Such z groups (generally sulfhydryl-reactive) are 8[1 acidic groups (-0-C(0)-(CH2), -
X) (in the formula, b is an integer and X represents the same group as in (0) above), and the corresponding examples are sulfonates as in (h) above, and sulfates as in (i) above. , phosphonates such as () above, phosphates and carbonates such as (9) above. Cross-linking with sulfhydryl groups via viscosifying olefinic double bonds may also occur. For this purpose The olefinic double bond can be catalytically activated using catalysts known to those skilled in the art. Preferably, the olefinic double bond is bonded to a carbonyl on the carbon atom adjacent to one of the unsaturated carbon atoms. The unsaturated bonds in compounds having two carbonyl groups adjacent to the unsaturated bonds, such as maleic acid derivatives, are activated more strongly and are particularly preferred.More preferred where zl is an organic group containing an acyl nitrogen group, and the acyl group contains an activated carbon-carbon double bond. Use of these latter compounds eliminates the need for foreign catalysts. Ethylenically unsaturated groups are ethylene, alkenes (C21-12,) such as propylene and butylene, unsaturated carbon atoms such as diacrylic acid, methacrylic acid, methyl methacrylate, niger methacrylate-1-, acrylamide, and methacrylamide. Acids, diesters and amides (RC
=C--C(0) R5, here rR5 is o - or N
H--Q): Formula: %Formula% (wherein R is as defined above and R, R2 and 1 and 3 are independently hydrogen, lower argyl, aryl and generally the i6 substituent is a bridge bond) Another right R group that does not interfere with the reaction, R2 is 1 (1 C(0)-R5 where 5 can be bonded to the amide nitrogen to form a ring, and R3 is 1<5 which can be bonded to the amide nitrogen to form a ring). (C-C(0)-R5 which can form a C ring)
19 from the compound represented by. These compounds include maleic acid, silicanic acid, iteric acid,
1 dermaleic acid, imide group of α-mebruitaconic acid,
Acrylic acid, amide group of angelic acid, imide of unsaturated monocarboxylic acid, T sprue of the above-mentioned unsaturated mono- and dibasic acids, R3=N-C(0) (Ra is maleic acid, itaconic acid, citron) Examples include carbamide derivatives having ethylenic unsaturation, such as di-MA-based unsaturated acid acyl groups such as acids, etc.). Sulfhydryl reactive groups are also described in US Pat. No. 2,850,351, the disclosure of which is hereby incorporated by reference. The <1 base can be, but is not limited to, any divalent hydrocarbon group, aliphatic, cycloaliphatic, or aromatic, or a combination thereof. Aliphatic groups include alkylene (-CoH2o-) where n is 1 to 10, such as medilene, and n is 1 to 10.
alkylidene (C,1HCH=) such as ethylidene; aromatic n-1 group groups include phenylene, cyclohexylphenylene, tolylene, cylylene, naphthylene, aminophenylene; cycloaliphatic groups include cyclohexylene , medylcyclo[J-hexylene, cochylcyclohexylene and)I-nylcyclohexylene. 1 or a substituent having, for example, a carboxylmino group, an amide group, a human 0.1 sil group, etc., as well as ethers (-R-0-Rx-) and xaminecous (dog-N+-1-Rx-). . Many other divalent bonding groups are also included within the scope of R, as will be apparent to those skilled in the art. Among the compounds of formula (1) are compounds of formula (1): (I[) 0 YC (Cl-12) bX (wherein X represents halogen, preferably iodine, and Y
and b t. It also includes halo compounds of L (same school as above). Particularly preferred among these crosslinking compounds are N-succinimidyl compounds, hereinafter represented by formula V. A particularly preferred type of compound of formula 1 is a compound based on a succinimide compound of the formula 2: where R and Z are as defined with respect to formula I. Compounds of formula (1) include maleimide compounds of formula Iv: (wherein R is as defined above). Preferably 1 or phenylene or cyclohexylmethyl (-C6141oCH2
It's hot. Compounds of formula (1) also include formula V: (wherein b is as defined above, most preferably 1
and x is halogen, preferably iodine, and R is as defined above. More preferably, R is aminophenylene (-C6H4-NH-)
The succinimidyl ring is replaced by a water-solubilizing group. Formula 1. n, I[1. Compounds of IV and V are water soluble and generally contain hair (such as those disclosed in U.S. Pat. No. 3,912,808 M:V, the disclosure of which is incorporated herein by reference). Contain moieties that help make the compound water soluble, such as quaternary ammonium groups or sulfonate groups (particularly alkali metal sulfonates), such as those used in waving systems, or succinimidyl rings or sulfonate groups (particularly alkali metal sulfonates), such as those used in waving systems. is preferable. Preferably, water-solubilization
The ing) group is cleaved in the cross-linking reaction to make the z 171 product water-soluble) and is attached to any group that can be washed away from the hair with water, such as the N-succinimidyl group. The water-solubilizing group may be in the form of an alkali metal salt (Na.K), preferably a sodium salt. The cross-linking agent is preferably applied to the hair in a buffered system, especially a one-part system adjusted to maintain I) 11 at about 6-9, preferably about 7-8. Hair treated with a cross-linking composition using any or a combination of alkali metal phosphates, acetates, boric phosphates, etc., which do not react with the cross-linking agent and therefore do not destroy the cross-linking sites. The pH can be maintained within a certain range. To help maintain the pH of the hair within a specified range, it is preferred that the reducing agent does not cause the hair's l)H to fall significantly outside the given range. Any I+ effect caused by the reducing agent can be offset by rinsing the hair before applying the crosslinking composition. The cross-linking agent is used sufficiently to J-ping or straighten the hair as desired. For example, for waving applications, the crosslinking composition may contain from about 0.1% to about 1% by weight of ffi crosslinking agent per buffer volume. Treatment 1 - Unit of crosslinking agent when crosslinking hair 1ffi
The right effect of the hit can be over a wide range. ■ The amount of crosslinking composition applied to the hair is - the amount necessary to wet the hair into the membrane and not be washed away. This can vary depending on the composition used (such as hair straightening gels), the quality of the hair and how the hair is pulled on the rollers. Preferred hangs for curling and straightening hair can be readily determined by those skilled in the art. The crosslinking composition may include a wetting agent or surfactant that is non-reactive with the crosslinker or hair and does not disrupt the crosslinking sites. The surfactant is dodecyl FIAR
Anionic ones such as alkyl sulfates and soaps such as sodium; cationic ones such as quaternary ammonium compounds; They can be non-ionic as well as amphoteric surfactants such as polyoxyalkaline ethers and modified lanolin. One preferred surfactant is sodium doacyl sulfate. The surfactant is used in sufficient quantity to assist in moistening the hair with the cross-linking agent, the effectiveness of which depends on the effectiveness of the surfactant. For example, in the case of doacylptium sulfate, up to 5% ω% of the cloth can be used before application of the crosslinking composition. The type and amount of surfactant used depends on the type of hair and the treatment layer. In preliminary tests, it has been observed that virgin (untreated) hair has a higher sensitivity to surfactants than bleached hair. It is therefore understood that more surface-active agent is used for bleached hair than for virgin hair. As a result of the test, virgin Caucasian hair treated with the cross-linking composition containing 2% w/v dodecyl sulfate of the present invention had good appearance properties such as curlability and gloss. It was also observed that the tensile parameters were abnormal. Caucasian virgin hair crosslinked without 2% dodecyl sulfate had improved tensile parameters. Tensile parameters were also improved in white bleached hair treated with a cross-linking composition containing 2% notrium dodecyl sulfate. Contains 0.2% purium-dodecyl sulfate V
An improvement in tensile parameters was also observed in black virgin hair treated with the 1R: bonding composition. The amount of surfactant used will depend on the type of hair and the treatment layer. The cross-linking agent can be used with the reducing agent if the present waving or oxidizing composition is compatible with the binder. By using a single-step system, The hair can be reduced and directly cross-linked with the sushihydryl groups. The hair is treated for a sufficient time to cross-link to obtain the curl and, in some cases, the desired increase in tensile strength.
JI! Typically, this is 3 minutes or the maximum time that does not actually alter the hair, but a shorter time may be used if it is desired to reduce the effect on the hair. As will be understood by those skilled in the art, the hair may be treated with neutralizing agents and cross-linking agents currently used to oxidize any 'M-SH groups to disulfide bonds. The oxidizing or neutralizing agent used is hydrogen peroxide, alkali gold f
! Any oxidizing agent capable of retaining the disulfide bonds in the keratin of the hair during resetting may be used, such as an aqueous solution such as salts of salts, alkali metal perborates, urea hydrogen peroxide, sodium sesquicarbonate, and the like. Rinsing with water alone may restore the broken bonds, but it will take longer. The permanent waving system of the present invention is designed for use by professionals and individuals. The system and its composition may contain the usual ingredients of such compositions. Fragrance compounds, coloring agents, thickening agents, opacifying agents, sequestering agents, solubilizing agents, gelling agents, conditioning agents, etc., are conventionally used in hair straightening and hair straightening compositions. It may also be added to the composition of the present invention. It is preferred to avoid the addition of compounds that would react with the crosslinking agent to remove or neutralize its reactive sites. These components are DermatologV (M ar
cell) ekker company. Volume 7 of the series entitled (1986), Cha
r-rhe 5science edited by rlGs7y+ak
of Hair Care J, and is incorporated herein by reference. Although the present invention has been discussed above regarding the cross-linking between SHI and N+-12, the present invention is not limited thereto. The present invention uses formulas I, I, I [[
, IV and V, especially compounds of formula ■. This includes the use of the compounds of (1), (2) and (V). Compound N-Sulfosuccinimidyl (4-(N-Maleimide)) Sisifhegysanyl Rupoxylate, N-Sulfosuccinimidyl (3-(N-Maleimide)
]Benzo'-1 and N-sulfosuccinimidyl (4-iodoazedyl) aminobenzoate C(0)0M2CH(H03S)C(0)NOC(0)
In particular, their sodium salts have been found to be effective in treating hair. As used herein in Yamanaka, the expressions "halo" and "halogen" mean chlorine, bromine and iodine, unless otherwise specified. In this specification Yamanaka, the expression "weight % per volume" is 100
mf! It means the number of grams per hit. The following examples further illustrate the invention. For example, commercially available European Caucasian brown hair specimens (0.5 mm; length 20.3 cm) wrapped around a commercially available curling rod with a central diameter of 1.25 to 1.6 cm. Notsu 1
1ill of disulfide bonds were treated for 20 minutes with -Ping [:I-ShiHn (G 1airol■ commercial 1-1a+r PerIII System)]. I broke it. These specimens were then rinsed for 2 minutes under running tap water to a pH of 7.
Approximately 0.45 fnf in 50 mmol sodium phosphate buffer per 1.8 ml of cross-linking solution containing 1% cross-linking agent and 2% sodium doacyl sulfate.
Processed for 0 minutes. The hair strands were rinsed under running tap water for exactly 2 minutes. Some samples were further treated with a neutralizing lotion and a commercially available 11'sH.
The group was oxidized. The rack you tested? ! The binders are N-sulfosuccinimidyl (3-(N-maleimido)) benzoate (sulfo-8MB), N-sulfosuccinimidyl (4-(N-maleimidomedyl)) cyclohexanecarboxylate (sulfo-8MB), 8MCC) and N-sulfosuccinimidyl (4-iodoacetyl)aminobenzoate (sulfo-8lΔB). Immediately after removing the hair specimen from the roll, after gently drying it for 2 hours, apply a few drops of 2.
After soaking in 4 g of tap water containing 9% dodecyl sulfate for 1 hour and drying for an additional 2 hours,
The curl length was analyzed. The lengths were compared during the 5 hour period, ie the final drying stage. A commercially available hair T-ping system (ClairolPa) was used as a control.
rm System), the curl quality was comparable to or better than the 1q curl length.
B, observed in sulfo-8MCC and sulfo-8IAB. Re-oxidation with all three compounds resulted in shorter curl lengths than the complete commercial treatment system (9). Hair specimens treated for 10 minutes with buffer only, i.e. without cross-linking agent, had curls of almost 1. The above treated specimens were analyzed for shine, silkiness and combability. Comparable to commercial lotion treated or untreated hair for all three compounds tested. Or better appearance result 19
It was done. For example, sulfo-8MB and sulfo-8IAB
The treated hair was hair treated with a commercially available product (CIai
Compared to untreated hair specimens, curls were fuller, had more shine, and had a silky feel of 1.7. Sulfo-8MC
G-treated hair was comparable to results obtained using commercially available lotions. The specimens used in Example 1 were tested using another commercially available 1-ping system (Rave Performance).
manccP arm) for 45 minutes to break the disulfide bonds in the hair. These specimens were then rinsed under running tap water for 2 minutes, treated with a buffered crosslinking composition containing 0.5% sulfo-8MB (from Example 1) for 10 minutes, and rinsed again for 2 minutes. is. In order to oxidize all free 51-1 groups, some specimens were treated with neutralization and Raye @ performance perm.
and further treated for 5 minutes. Similar to Example 1, curl l
I [nitered] Risa. Compared to a control using a commercially available 1-pin lotion, shorter curls were obtained using sulfo-8MB as the cross-linking agent after reoxidation. Good shine and flexibility were obtained in the hair specimens treated with the cross-linking agent. Example 3 Split Hair Method for Instron Testing For each experimental sample, 10 strands of hair were each tagged for identification and divided into halves, with one half being treated and the other half serving as an untreated control. . Five of the tufts in each half were from the base to the middle, and the remaining five tufts were from the tip to the middle. One half was placed into a hair 9i specimen (as defined in Example 1) and treated with or without a curler. The other half of the hair tresses remained untreated as a control. For treatment, use commercially available waving lotion (CIai
Disulfide bonds are destroyed by contacting the product for 20 minutes with the Rol Arm System), then rinsed with running tap water for 20 minutes.
rinsing for 5 minutes, neutralizing or reoxidizing for 5 minutes with a neutralizing agent and commercially available waving lotion, and rinsing in two volumes.
I was in v. The second group of hair was treated with commercially available waving lotion (C1airol■)) Crm3 yste.
m) for 20 minutes to break disulfide bonds, and treated with water) for 2 minutes under running water to remove 0.5 wt. treated with 10 d of cross-linking solution of 3lΔB, rinsed with running tap water for 2 minutes, neutralized 5 molecules tjl,
Rinsed for an additional 2 minutes. The third set was treated similarly to the previous procedure, but no crosslinker was used in the buffer. Surbeau 5IABT: Treated split hair tresses,
Tensile parameters including point of break, displacement at break (maximum elongation to break) and total work were then analyzed. Tensile properties were measured on the tagged halves in an In5tron dest apparatus using the following test conditions: Gauge length: 5.08 cm (2 inches) Crosshead speed: 0.99 cm (0.39 in.7)
-)/min i! i1 degree: 50% relative, or 100 in water cell
% Temperature: 22.2°C (72'F) The following results were obtained: 50χ Old 1* +7χ -+1%
+11%100%R11* book --+13X
OX +11% Umbrella R11 - relative humidity. Results were standardized by dividing the results for the treated hair by 1 for the virgin hair in the other half of the tresses. - Relative humidity. No hair technique was used for Subrit 1. The cross-sectional area of the sample hair was standardized by calculation using 1 m and the density. The tensile strength test produced very small increases in break point (approximately 7% increase), tensile bullet mark (approximately 13% increase), and total work (approximately 11% increase) compared to the untreated hair control. Example 4 A specimen of once bleached European Caucasian brown hair (as defined in Example 1) tagged (identified) at 173 of 10 was tagged (identified) as in Example 3 (:, 1airol■l' Crm5
Processed with VStem. Directly apply a buffered sulfo-5 IAB solution containing 5% sulfo-8 IAB and 2% dodecyl raw sodium (as in Example 1) to the rolled hair. and reoxidized as in Example 3. Measure the length of the curl in the same manner as in Example 1. Shorter curls were obtained using Sulfo 5IAB. Hair specimens treated with the above-mentioned cross-linking agent had gloss, feel and combability that were 1.7 times higher than those obtained using the above-mentioned commercially available product. In the tensile strength test, commercially available
Sulfo S compared to control hair treated with the Ping system.
A 1-8% increase in tensile parameters was shown for hair treated with IAB. The percentage range is a range of three separate ast results. Attached tensile properties include point of break (15%), elongation to break (+1%) and
ffi (48%). Example 5 A specimen (same as Example 1) was transferred to C1airO1porm.
3 system treatment. A buffered cross-linking composition containing 0.5% by weight of sulfo-3IAB or sulfo-3MB and 2% of sodium acyl sulfate was applied directly to curly hair and carried out. Reoxidation was carried out in the same manner as in Example 1. This waving procedure was repeated three times over three consecutive times. Curl quality was measured as in Example 1. In each of the 31 songs, C1airol■Pe
Curls equivalent to or shorter than the rm System were obtained. Hair specimens treated with Sulfo-8IAB or Sulfo-8MB showed good shine, feel and combability of 1[1
It was done. Example 6 Contains 10 strands of black hair (identified with a tag)
However, a Caucasian hair specimen (like the one prepared in Example 1) was treated with C1airol Pe in the same manner as in Example 3 (split hair).
rm System. 0.2% sodium dodecyl sulfate and 0.5in%'r% sulfo-8 per serving
Buffer solution containing IAn 10#11! was applied to hair wrapped in rads and reoxidized as in Example 3. About isolated black hair mtta l n5tronR
The test showed that tensile parameters such as break point (114%), elongation to break (11%) and total work fi (-117%) were 11% compared to virgin hair or CIairol treated black hair. It was shown to increase by ~17%. Effective results appear to be obtained on black hair at lower surfactant concentrations, such as 2% to 0.2%, than when used on bleached white hair. The proportion of black fibers that break at a displacement of less than 10% for fibers crosslinked according to the invention is 8 out of 0, whereas in the same displacement range 2 out of 9 waved fibers (22
%), 13 out of 69 (19%) virgin hairs were broken. Procedure Ne1n Seigang (Method) % Formula % 2, Title of Invention Cross-linking agent useful for hair treatment 3
, Relationship to the case of the person making the amendment Name of the patent applicant Name Unilever Namrose Pen Note Sharp 7° Contents of the amendment The clearly written specification is supplemented as shown in the attached sheet. (No change in content)

Claims (18)

[Claims] (1) A method for treating a keratin material whose disulfide bonds have been destroyed by the action of a reducing agent that forms free sulfhydryl groups, comprising a portion that can selectively form a bond with a free sulfhydryl group and a free amino group in the keratin material. contacting the keratin material with a crosslinking agent having a moiety capable of selectively forming a bond, which is sufficient to form a crosslink but not sufficient to substantially denature the proteins of the keratin material. A method characterized in that it is carried out under unsatisfactory conditions. (2) The crosslinking agent has the formula: Y-R-Z (wherein Y represents any group capable of selectively reacting with the amino groups of the keratin material under the processing conditions, and Z represents the reaction with the keratin material under the processing conditions. 2. The method of claim 1, wherein R represents a bond between Y and Z. (3) A claim in which the crosslinking agent is a compound of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y has the same meaning as in claim 2, X represents a halogen, and b is an integer) Method 2. (4) The method of claim 3, wherein b is 1 and X represents iodine. (5) Any of claims 2 to 4, wherein Y is a group selected from the group consisting of hydroxyl, alkoxyl, acyloxyl, haloacidic, N-succinimidyl, phosphonyl, phosphoryl, sulfonate, sulfate, and aminobenzoate-N-succinimidyl. That method. (6) Claim 2, wherein the crosslinking agent is a compound of the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein R and Z have the same meanings as in claim 2, and W is an N-succinimidyl group) the method of. (7) wherein Z represents a group selected from the group consisting of haloacetyl, other haloacidics, phosphonyl, phosphoryl, sulfonate, sulfate, carbonate, iodide, activated olefinic double bond, and mixtures thereof. the method of. 8. The method of claim 7, wherein the activated olefinic double bond is activated by the presence of a carbonyl group on a carbon atom adjacent to one of the unsaturated carbon atoms. (9) The method of claim 8, wherein the group containing an activated olefinic double bond contains an acyl nitrogen. (10) Claim 7 wherein the haloacetyl is iodoacetyl.
the method of. (11) The method according to claim 2, wherein the crosslinking agent is a compound of the formula ▲ has a mathematical formula, chemical formula, table, etc. ▼ (wherein R has the same meaning as in claim 2, and W is an N-succinimidyl group) . (12) is a phenylene group or -C_6H_1_0-CH in which the -C_6H_1_0 moiety is bonded to a carbonyl group
The method according to claim 6 or 11, wherein the _2- group. (13) The crosslinking agent is a compound of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 3. The method of claim 2. (14) The method according to claim 13, wherein R is -C_6H_1_4NH- and X is iodine. (15) The crosslinking agent is N-sulfosuccinimidyl [4
-(N-maleimidomethyl)]cyclohexanecarboxylate, or N-sulfosuccinimidyl (4-iodoacetyl)aminobenzoate, or N-sulfosuccinimidyl[3-(N-maleimido)]benzoate. Method 1. (16) The method according to any one of claims 1 to 15, wherein the crosslinking agent is substituted with a water-solubilizing group. (17) The method according to any one of claims 1 to 16, further comprising the step of reoxidizing the keratin material after crosslink formation. (18) A hair waving system comprising a composition for reducing disulfide bonds in hair and a crosslinking agent as defined in any one of claims 1 to 17.