JPH0460447B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel oxidizing agent-containing neutralizing compositions for use in connection with hair waving and stretching treatments, and to a method for conditioning and conditioning hair subjected to this treatment. In particular, the present invention relates to neutralizing compositions comprising an amino-functional polymeric silicone additive and an oxidizing agent for imparting conditioning properties to hair treated with a reducing agent that reduces keratin bonds in the hair, and the composition. The present invention relates to a hair treatment method using. Hair waving and stretching methods almost always consist of two consecutive steps. In the first step, the hair is softened or loosened with a reducing lotion so that it can be shaped into the desired shape. In a second step, a neutralizing agent is applied to the softened hair to harden and stabilize it in the newly formed form. The main active ingredients of common neutralizing agents are oxidizing agents, among which hydrogen peroxide is the most common nowadays. The action of the oxidizing agent is twofold: (i) it removes any excess reducing agent used in the softening step of the treatment, and (ii) it regenerates disulfide crosslinks in the hair. stabilizes the new hair morphology and restores its strength and elasticity. However, in practice at present, not all of the disulfide bonds cleaved during the softening step of hair waving or stretching methods are regenerated, and increased fiber porosity and deterioration of hair catalytic properties are often caused by this method. It becomes a side effect. Neutralizing compositions often have smooth texture,
Contains modifiers such as quaternary alkyl ammonium compounds to provide plowability and fly-away control. However, the conditioning effect provided by this additive, while convenient, is temporary and disappears after a single hair wash. An example of a permanent "cold" hair waving method using a mercaptan reducing agent is disclosed in Schwartz, US Pat. No. 2,540,494. Schwarz states that the oxidizing agent in the neutralizing solution or fixative used to restore the disulfide bond may be any typical oxidizing compound that is harmless and non-toxic when applied to human hair. hydrogen peroxide and its salts, such as ammonium peroxide sulfate, urea peroxide and pyrophosphate peroxide, sodium and potassium carbonate peroxide and perborate; Metal salt peroxides, persulfates and organic peroxides and substituted peroxides are shown. The fixative "neutralizing" solution from Schwartz may contain at least one acidifying agent such as potassium bromate or iodate or an acid capable of bringing the pH of the neutralizing solution to 2-4. It is also known that Examples of acids in this patent include organic mono- or poly-carboxylic acids such as malonic acid, succinic acid, maleic acid, acetic acid, propionic acid, butyric acid and crotonic acid; organic acids with hydroxy groups such as lactic acid, citric acid, These include tartaric, malic, and glycolic acids; inorganic acids such as sulfuric, hydrochloric, and phosphoric acids; and acid salts such as tartaric, citric, and potassium or sodium phthalates. Additional buffering salts for pH stabilization, e.g. ratio 2: to bring the pH to about 3:
1 sodium acetate and acetic acid can be used. The use of various silicon-containing polymers, such as polysiloxanes, for hair conditioning in permanent waving methods is also known in the art. For example, U.S. Pat. No. 3,248,296 to Schyutainbatzha et al. discloses various epoxyorganosiloxanes that provide an elastic membrane that keeps hair subjected to successive reduction and oxidation treatments from adhering to each other and from water penetration. In this case, an epoxyorganosiloxane is applied after a neutralization step with a hydrogen peroxide oxidizing agent. U.S. Pat. No. 3,687,606 to Schyomier et al. is an improvement on the above-mentioned Schyutteinbach et al. patent in which a functional epoxyorganosiloxane having an epoxy group reacts with the hair material, while the organopolysiloxane moiety provides water repellency. However, conventional compounds are said to have the disadvantage of imparting an oily shine to the hair and are not water soluble. Accordingly, Shyomiel et al. used epoxysilane as a treatment agent for stone treated with a reducing agent, such as thioglycolic acid, before being neutralized using a peroxide oxidizing agent. U.S. Pat. No. 2,944,942 to Chaar uses methylsilylmercaptoacetate in one step in a permanent wave process. This compound dissociates into a mercapto-reducing agent while producing a silanol polymer that protects the hair and makes it easier to comb. This patent does not mention anything about post-treatments such as peroxide fixation, so it is unclear whether this treatment is necessary. Other hot and cold hair waving and stretching compositions may be used with or without reducing agents and/or oxidizing agents.
Such compositions containing various types of siloxane polymers used to individually coat hair are described, for example, in US Pat. Grant, U.S. Pat. No. 3,143,476, uses a neutralizing agent to convert sodium and potassium bromates in the presence of ferrous, ferric, and copper ions, which act as catalysts to increase the reaction rate of the neutralizing agent. It describes the cold wave neutralization composition and method used. There remains a strong need for neutralizing compositions for use in cold permanent waving or stretching hair treatments that are durable, ie, stable to repeated washings. Furthermore, for neutralizing compositions applicable to hair waving or stretching, the drying time is significantly reduced, the porosity of the hair fibers resulting from severe disruption of the hair bonds is significantly reduced, and a smooth texture, easy cardability and There is a need to provide benefits such as fly-away control and reduce drying time. An object of the present invention is to provide a neutralizing composition for hair waving and stretching that has hair styling durability, that is, stability against repeated hair washing. Another object of the present invention is to neutralize the excess reducing agent and regenerate the disulfide cross-links in the hair formed from the hair softening process, dry the hair in a short time and improve the structure of the treated hair. The object of the present invention is to provide a composition that provides curlability and fly-away reduction. Another object of the present invention is to provide a method for simultaneously neutralizing hair on the head that has been treated with a keratin reducing agent such as thioglycolic acid. The present invention achieves these objects, which will become apparent from the detailed description of the preferred embodiments below, by a neutralizing hair composition in which an amino-functional silicone polymer conditioning agent is emulsified in an aqueous oxidizing agent solution. be done.
Amino-functional silicone polymers are the types of silicone polymers with amino functional groups, especially those with the formula () (In the formula, R represents a hydrogen atom or trimethylsilyl, R ₁ represents hydroxy or methyl, R ₂
represents alkyl having 1 to 6 carbon atoms,
R ₃ represents alkyl having 1 to 4 carbon atoms;
x represents a positive number of at least 4, and y represents a positive number of at least 2
and the sum of x and y is such that the silicone polymer has a molecular weight of about 5,000 to about 100,000. The present invention also applies an oxidizing agent aqueous solution emulsified with an amino-functional silicone polymer modifier having a repeating structural unit having the formula () to keratinous fibers such as human hair that has undergone reduction treatment. To provide a neutralizing hair conditioning method that reduces disulfide bonds in the hair. The compositions and methods of the present invention are generally applicable to common reducing agents and reducing compositions as well as common active neutralizing agents. Reducing agents and reducing compositions based generally on thioglycolic acid or thioglycolic acid salts are known in the art and do not form part of this invention per se. In addition to the reducing agent thioglycolic acid, it also gives shape to the hair. Hair treatment agents such as "hair waving mercaptans" (U.S. Pat. No. 2,540,494), alkaline softener compositions, sulfite-based systems, etc. are also effectively neutralized by the neutralizing compositions of the present invention. Ru. Hydrogen peroxide is a preferred neutralizing oxidizing agent in the neutralization adjusting composition of the present invention. However, other neutralizing agents such as inorganic and organic peroxides and peroxide salts, perborate, bromate, etc. can also be used. In addition, neutralization is carried out at an appropriate dilution concentration in the case of alkaline reducing agent compositions.
This can also be done with acidic neutralizing agents such as HCl or other chlorinated acids. The amount of oxidizing agent may be within the range commonly used in neutralizing agent compositions and depends, for example, on the type of oxidizing agent and the amount and type of reducing agent used. Generally, the amount of oxidizing agent is about 0.5 to about
10% by weight, preferably about 1 to about 4% by weight. For optimal results, the pH of the neutralizing composition of the present invention should be acidic, from about 2 to 5, preferably from about 2.5 to 4.5. Schwarz Patent No.
Acids commonly used in hair neutralizing and oxidizing compositions such as those disclosed in US Pat. No. 2,540,494 can be used in the present invention. However, the use of buffered acidifying fluids is most preferred so that, for example, the commonly occurring natural high alkalinity of hair does not substantially increase the PH of the compositions of the present invention. The use of buffering agents is sometimes preferred because it minimizes the degree of hair damage caused by harsh waving chemicals. Desired PH range 2
Any acid and buffer system capable of maintaining a pH of -5 can also be used in the compositions of the present invention. Particularly good results have been obtained using phosphoric acid and a citric acid-citrate ion buffer system as acidifying agents. However, other acids and buffer systems can be used as long as the pH can be maintained between 2-5. Neutralizer,
For example, to prevent a silicone emulsion in peroxide from being destroyed by the high acid capacity created by the buffer during prolonged storage, the buffer is prepared separately from the rest of the composition and mixed with the other ingredients immediately before use. It's good to do that. The oxidizing agent, such as hydrogen peroxide, is the main active ingredient in the composition and serves to remove any residual excess of reducing agent or alkali used during the softening step of the waving or stretching process, while also removing the previous reduction. It also works to restore keratin disulfide bonds that are broken during the process. Another important component of this invention is a silicone polymer modifier. It is an amino-functional silicone polymer with the formula () (In the formula, R represents a hydrogen atom or trimethylsilyl, R ₁ represents hydroxyl or methyl,
R ₂ represents a straight-chain or branched divalent alkyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms;
R ₃ represents a straight-chain or branched divalent alkyl group having 1 to 4 carbon atoms, preferably 2 to 3 carbon atoms;
is a positive number of at least 4, and y is a positive number of at least 2). Such suitable monoamino functional silicone polymers have formula () in which R is hydrogen and R ₁ is -
_CH3 , _R2 is ( _−CH2 ) ₋₃ , and _R3 is ( _−CH2
) _-2 is a cationic polymer commonly called amodimethicone. Amodimethicone is commercially available from the Dow Corning Company in the form of an aqueous emulsion under the names Dow Corning 929 Emulsion and Silicone 929 Cationic Emulsion. The amount of silicone polymer generally ranges from about 0.1 to 10% by weight of the composition, preferably from about 1 to 2%. Although adjustment of the amount below about 0.1% is insufficient,
On the other hand, if it exceeds about 10%, there is no additional profit and it is difficult to produce a stable emulsion. Any emulsifier that is compatible with other components and can maintain a stable emulsion can be used in the neutralization adjusting composition of the present invention.
Cationic emulsifiers may be used with cationic silicone polymers (R=H), and nonionic emulsifiers are preferably used with nonionic silicone polymers (R=trimethylsilyl). Generally, amino-functional silicone polymers are commercially available in the form of emulsions and can be used directly in the compositions of the present invention without the addition of additional emulsifiers. For example, Dow Corning Emulsion 929, an emulsion of the cationic silicone polymer, amodimethicone, contains a mixture of a cationic emulsifier (tallow trimonium chloride) and a nonionic emulsifier (ethoxylated phenol). Dow Corning Emulsion X2-7224 is manufactured by the manufacturer in which R is trimethylsilyl, R ₁ is methyl, and R ₂ is isobutyl.

It is an emulsion containing about 35% by weight of a nonionic silicone polymer having the formula and R ₃ is ethyl (-CH ₂ CH ₂ )-, and the nonionic emulsion is an ethoxylated alcohol. (Triton
X405, a Rohm and Haas product) and ethoxylated phenols (Tergitol)
TMN-6, Union Carbide Products) contains a mixture of approximately 3% by weight. Any common emulsifier typically used in hair treatment compositions can be used in the composition of the present invention. Typical nonionic emulsifiers include, for example, polyethoxylated or polyglycerolated alcohols, linear alkylphenols or fatty acids having 8 to 18 carbon atoms, and generally 2 to 30 moles of ethylene oxide, ethylene oxide-propylene oxide copolymers. , aliphatic alcohols, condensates of ethylene or propylene oxide and aliphatic alcohols, polyethoxylated aliphatic amides, polyethoxylated aliphatic amines, ethanolamides, glycol esters of fatty acids, sorbitol esters of fatty acids and sutucarose esters of fatty acids. be. Representative cationic emulsifiers include, for example, quaternary ammonium, morpholinium and pyridinium compounds. The amount of emulsifier(s) is not particularly important as long as the silicone polymer remains in an emulsified state after being mixed with the oxidizing agent and other components of the composition. Generally, the amount of emulsifier may be from about 2 to about 20%, preferably from about 8 to about 18%, by weight of the silicone polymer. If the silicone polymer is not available in an emulsified state, it is advantageous to emulsify it with one or more emulsifiers before mixing it with the acidic aqueous solution of the oxidizing agent. If necessary, mixing of the emulsifier and the silicone polymer and mixing of the emulsified silicone polymer and the aqueous acidic oxidizing agent solution can be easily accomplished by mixing the components in a conventional mixing apparatus at room temperature or slightly warmed. Of course, the mixing speed, shear rate, etc. must not be such as to destroy the emulsion. Other common additives such as fragrances, thickeners, surfactants, other conditioning agents, bactericides, etc. do not interfere with the activity of the oxidizing agent or silicone polymer or impair the stability of the emulsion. It can be added to the composition in small amounts. Although the buffering agent may be added to the composition at any time, it may be advantageous to package the buffering agent separately from the other components of the composition and provide instructions to mix the two packages immediately before use. Without wishing to be bound by any particular theory as to the mechanism by which silicone polymers exhibit their good properties, it is clear that silicone polymers improve the combing and drying properties of hair and provide a stable film that is mechanically strong and wear-resistant. is estimated to be formed on each hair. The drying properties are due to the low surface tension of the silicone polymer, which creates a thin film of water that evaporates more easily from the treated hair. As noted above, the neutralizing compositions of the present invention can be used with virtually any hair treatment composition that provides waving or stretching effects through the reduction of keratinous disulfide bonds. The following shows a typical emollient composition: Ingredient concentration (wt%) Vaseline 24.00 Soybean oil 16.00 Polawax (non-ionic emulsifying wax)
8.00 Sollan 25 (ethoxylated lanolin alcohol)
3.00 Propylene Glycol 2.50 Sodium Hydroxide 1.75 Cetyl Alcohol 1.25 Fragrance 0.50 Add Water Total Volume 100.00 A typical thioglycolate waving composition is made by the following formulation: Ingredient Concentration (% by weight) Ammonium Thioglycolate Rate 5.1 Monoethanolamine 2.5 Brij35 (Polyoxyethylene lauryl ether)
1.2 Perfume 1.0 Opacifying agent 1.0 Addition of water Total amount 100.0 The invention is illustrated by the following examples, which are not intended to limit the invention. All parts and percentages are by weight unless otherwise specified. Example: Three strands of brown Caucasian human hair, each weighing 2 g, were wrapped around a 1/2 inch stick in an ordinary thioglycolate solution (0.6M ammonium thioglycolate, pH 9.2).
It was saturated. After 20 minutes, the waving lotion was washed off and the tresses on the wand were treated as follows: tress #1 was saturated with 1.2% H ₂ O ₂ at PH4 with phosphoric acid for 5 minutes. Bundle #2 was saturated with 1.2% H ₂ O ₂ containing 1.5% amodimethicone at PH 4 with phosphoric acid for 5 minutes. Bundle #3 was saturated with 1.2% H2O2 containing 1.5% amodimethicone, pH 3 with phosphoric acid and buffered with _0.25M citric _acid for 5 minutes. After 5 minutes, the hair was removed from the wand, the peroxide solution was poured into the hair strands, and the hair was left for another 3 minutes before being washed with running tap water.
It was then placed wet in a strain gauge carding machine and its work was recorded with the following results. Bundle #Combed work (gcm) 1 795 2 137 3 132 The removed hair was soaked in water again, taken out, and hung to air dry. The weights of the bundles immediately after being taken out of the water and after drying were recorded, and the moisture content of the bundles was calculated from the difference in dry and wet weights. Bundle #Water content (g/g hair) 1 2.5 2 1.5 3 1.6 After centrifugation, the amount of water retained in the hair (porous liquid retention) was as follows: Bundle #Liquid retention% 1 42.5 2 41.3 3 37.5 Finally, after shampooing the bundle twice, wet carding was re-tested. The combing work values were as follows: Bundle #combing work (gcm) 1 764 2 180 3 133 EXAMPLE The following experiment was conducted to determine the rapidity of hair drying after completion of the waving (or stretching) process. Summer. Four strands of hair (virgin Demeo brown), each weighing 2 g, were waved for 15 minutes at 35° C. using regular waving lotion. Wash your hair and neutralize 2 strands with a normal neutralizer (2.0% H ₂ O ₂ ) and the other 2 strands with H ₂ O ₂ (2.0%).
and amodimethicone (2.0%). All were neutralized for 10 minutes, washed with water, and each was placed on a stress gauge to accurately measure the weight. Changes in weight were checked for 45 minutes. The numerical values in the table indicate the weight change over time (average of two bundles). The less water content the hair has, the faster it dries.

[Table] Example 2 Thickening agent (Igepol CO 430 and Igepol
CO 630) and an additional emulsifier cetyl alcohol were added to prepare the composition according to the invention. Ingredient Concentrations Weight % Hydrogen Peroxide 2.0 Cetyl Alcohol 0.2 Igepol CO 430 4.0 Igepol CO 630 4.0 Phosphoric Acid 0.03 Dow Corning Emulsion 929 4.00 Water 85.77 A stable concentrated composition was obtained.

Claims (1)

[Claims] 1 Oxidizing agent aqueous solution and formula: (In the formula, R represents hydrogen or trimethylsilyl, R ₁ represents hydroxyl or methyl, R ₂
represents alkyl having 1 to 6 carbon atoms,
R ₃ represents alkyl having 1 to 4 carbon atoms;
x is a number of at least 4, y is a number of at least 2, and the sum of x and y is a number such that the molecular weight of the silicone polymer is from about 5,000 to about 100,000. A hair neutralizing and conditioning composition comprising an aqueous emulsion and having a pH of about 2.0 to about 5.0. 2 The silicone polymer is approximately
A composition according to claim 1, wherein the composition is present in an amount of 0.1 to about 10% by weight. 3. The composition of claim 2, wherein the amount of silicone polymer is about 1 to 2% by weight. 4 R is hydrogen, R ₁ is hydroxyl,
The composition according to claim 1, wherein _R2 is ( _-CH2 ) _-3 and _R3 is ( _-CH2 ) _-2 . 5. The composition according to claim 1, further comprising a buffering agent to maintain the composition PH at about 2.0 to 5.0. 6. The composition according to claim 5, wherein the buffering agent is citric acid-citrate and the composition is made acidic with phosphoric acid to a pH of about 3.0. 7 Hair that has been subjected to a waving or stretching treatment with a reducing agent capable of reducing keratinous disulfide bonds is treated with an aqueous oxidizing agent solution and the formula: (In the formula, R represents hydrogen or trimethylsilyl, R ₁ represents hydroxyl or methyl, R ₂
represents alkyl having 1 to 6 carbon atoms,
R ₃ represents alkyl having 1 to 4 carbon atoms;
x is a number of at least 4, y is a number of at least 2, and the sum of x and y is a number such that the molecular weight of the silicone polymer is from about 5,000 to about 100,000. A method of neutralizing and conditioning hair comprising applying a composition comprising an aqueous emulsion and comprising an effective amount of a pH neutralizing and conditioning composition of from about 2.0 to about 5.0. 8 Immediately before applying the neutralizing and condescending composition to the treated hair, when the treated hair still has alkalinity, apply the neutralizing and condescending composition to within the above PH range of 2.0 to 5.0. 8. The method according to claim 7, wherein a buffer capable of maintaining pH is further mixed into the composition.