WO1999026591A2

WO1999026591A2 - Improved hair perming agent

Info

Publication number: WO1999026591A2
Application number: PCT/US1998/025169
Authority: WO
Inventors: John R. Lau
Original assignee: Sdg, Inc.
Priority date: 1997-11-24
Filing date: 1998-11-24
Publication date: 1999-06-03
Also published as: WO1999026591A3; AU1605799A

Abstract

The present invention is directed to the use of a water-soluble tertiary phosphine as a reducing agent for altering the physical structure of hair. In this regard, phosphines can be used as the reactive agent needed to break disulfide bonds within an insoluble substrate, namely hair. This initiates the reducing sequence leading to the practice of permanent hair waving and hair straightening.

Description

IMPROVED HAIR PERMING AGENT

Field of the Invention

The present invention is directed to compositions and processes for altering the physical structure of hair. More particularly, the invention is directed to compositions and processes for perming hair.

Background of the Invention This invention relates to the discovery of hair perming compositions and therefore will be directed primarily to the hair perming industry. There are volumes of reports on the prior art effort to change the physical structure of hair. One example is The Science of Hair Care, Marcel Dekker, Inc., New York, NY© 1986.

At the present, the method of choice for perming hair is to use mechanical devices to form hair around tubular rollers, and use alkaline-based sulfhydryl chemical reducing agents to disrupt the hair disulfide bonds. The hair is then flexible and able to set in a new configuration.

It is possible to change the hair structure without mechanical devices, but the bulk of hair perming is done either to straighten hair or to produce hair that is styled with curls and waves. Consequently, the perming of hair will be the primary teaching disclosure of this specification.

The chemical reaction for the sulfhydryl based system is shown below:

0

II

Rι-CH -S-S-Cr.₂-Kι + HS-CH₂-C-OH hair protein disulfide thioglycollic acid

pH 9.5

0 +

II

R₁-CH₂-S-S-CH₂-C-OH HS-CH2-R2 mixed disulfide of hair protein hair protein sulfhydryl cysteine

The disulfide bond (R1-S-S-R₂) in hair protein is reacted on by a chemical reducing agent containing a free sulfhydryl functional group, such as thioglycollic acid. As a result of the above reaction, two essential products are formed. The first product is a mixed disulfide compound containing a component of hair protein and a compound of thioglycollic acid. The second product is formed as a result of the cleavage of the original disulfide bond. Half of this original bond is now manifested as a free sulfhydryl compound capable of engaging in further reaction toward any disulfide linkage.

Thioglycollic acid is effective, but unpleasant and sometimes harmful to use. Because it functions in a harsh alkaline environment, it must be used in a careful manner to prevent eye damage and skin irritation. The odor of the perming reaction can be offensive and the time for completion of the procedure is often tiring to the recipients. Thioglycollic acid is used at an elevated pH usually between pH 9-12. During the time required for perming, the harsh alkaline environment leads to severe cuticle damage. This results in hair that is brittle and has an abrasive or rough texture. Naturally curly hair can be straightened during combing by first applying a reducing agent which reacts with the disulfide bonds. Also, if only partial straightening is desired, tight curly hair may be made straight using milder reducing conditions. It is recognized that hair strands, whether straight or curly, are held in a given physical configuration by disulfide bonds. It has long been practiced to shape straight hair by physically stressing the hair shaft. Thus, by wrapping the hair around curlers, the hair will take on a new configuration. This procedure takes a considerable amount of time, and is very responsive to humidity. Human hair has chemical and physical properties which make it both strong and elastic. A key structural component of hair is a molecule of cystine created by two cysteine moieties joined by a disulfide bond. This structure of cystine is depicted as (R₁-S-S-R₂). The abbreviations Ri and R₂ are representative of hair protein strands connected by a disulfide bond.

The reactivity of a disulfide bond is dependent upon its polarity. A molecule is considered to be polar if the center of negative charge does not coincide with the center of positive charge. A molecule that exhibits this disparity in charge is called a dipole. Dipoles possess dipole moments (μ) which are equal to the magnitude of the charge, expressed in electrostatic units (e.s.u.), multiplied by the distance (d) in angstroms between the centers of charge. Thus, by obtaining dipole moments which belong to specific classes of molecules, a comparison can be made of their polarity. The overall polarity of a molecule is represented by a composite of the various polarities manifested by the individual bonds within a given molecule.

For example, molecules, such as H₂, 0₂, N₂, Cl₂ and Br₂, have zero dipole moments, and as a result they exhibit non-polar properties and characteristics. Since two identical atoms in each of these molecules have the same electronegativity and share electrons equally, the charge (e) is zero and therefore (μ) is also zero.

However, a molecule such as hydrogen fluoride (H:F) has a large dipole moment of 1.75 D where (μ) is expressed in Debye units of (D). Although H- F is a small molecule dimensionally because the (d) in angstroms is small, the very high electronegative fluoride atom pulls bonding electrons strongly toward its nucleus. Thus (e) or the charge is large and therefore (D) is also large. The reason that H-F represents a significant dipole is because the size of the nucleus of the fluoride atom is large and positively charged relative to the size and charge of the nucleus of the hydrogen atom. As a consequence of this disparity in nuclear size and charge, δ⁺ δ^" fluorine attracts the electrons of the H ^"F bond more strongly than hydrogen and thus fluorine assumes a partial negative charge expressed as δ^" while hydrogen assumes a partial positive charge expressed as δ⁺.

Molecules such as methane and carbon tetrachloride also have zero dipole moments because these molecules possess a tetrahedral structure which is symmetrical in nature. As a result of this symmetry, the partial charges are canceled. In other words, the movement of electrons toward a positive nucleus, which would create a relative electronegative center, is counterbalanced by a similar kind of movement in the opposite direction. Furthermore, molecular dipole moments can be enhanced or made larger if there is a pair of unshared electrons associated with the molecule. For example, ammonia has a dipole moment of

1.46D and water has a dipole moment of 1.86 D. Both of these molecules possess at least one pair of unshared electrons which contribute to the electronegativity of either the oxygen or nitrogen atom.

As a result of charge redistribution the polarity of a bond will often times be an important factor in regard to its potential reactivity. This is thought to be the case with disulfide bonds found in the polypeptide chains of hair protein.

The hypothesized polarity of this bond is shown as follows: phosphine and sulfhydryl nucleophiles

or

Ψ δ⁺ δ^" δ⁺ δ^" RιS — S — R₂ - *^■ RιS — S — R₂ — S— S— S— R₂

^| transition complex

disulfide bond | δ⁺ δ^"

— P— S— S— R₂

transition complex

During attack by a water-soluble phosphine or sulfhydryl nucleophile, the δ⁺ end of this disulfide dipole possesses a slightly stronger affinity for the unshared pair of electrons on the incoming phosphorus or sulfur atom than does the δ^" sulfur atom in the disulfide bond. As a result, the reaction sequence of disulfide bond breaking commences with the formation of a transition complex between the phosphine and the δ⁺ sulfur of the disulfide bond. The disulfide bond assumes a polar character because it resides in a polar aqueous medium and is influenced by the electron environment of the incoming nucleophile. This disclosure addresses the possibility that solvent polarity can either retard or facilitate the cleavage of a disulfide bond by a reducing agent residing within a water-insoluble proteineous matrix such as hair. Disulfide bonds that reside in relatively non-polar regions, such as within the centers of polypeptide helices, are not as accessible nor as readily cleaved as soluble disulfide bonds in aqueous media.

When processing and perming Caucasian hair, the penetration of the cuticle and the accessibility of the microfibril structure of the hair shaft by reducing agents are limiting factors, and this lack of accessibility is often observed in the overall poor appearance of the hair perm. In spite of early successes at low pH, the inhibition to hair shaft penetration has been observed with the use of a highly charged Tris-(2-carboxyethyl) phosphine (TCEP) reducing reagent as shown below:

O O

II II

O CH₂CH₂C-OH O CH₂CH₂C-O^"

II I PH 4.0 _ I I

HO-CCH₂CH₂-P: _. O-CCH₂CH₂-P:

I pH 2.0 I

CH₂CH₂C-OH CH₂CH₂C-O^"

II II

O O protonated ionized

Many of the earlier investigative experiments with TCEP centered on the evaluation of the reducing capability of the molecule at acidic pHs between pH 2.0 and pH 3.0. Results of hair perming at these pHs showed good promise in polar aqueous media. It is believed that these positive effects were due to the suppressed ionization of the carboxy functional groups of TCEP at low pH. Since TCEP contains three carboxyl groups it is necessary to suppress the ionization of these functional groups which exhibit a pKa somewhere between pH 2.0 and pH 4.0 in order to facilitate hair penetration by the reducing agent. Above pH 4.0, the molecule becomes ionized due to the charge contribution made by the carboxyl functional groups. Thus when ionized TCEP comes in contact with positively charged amino acid residues found in hair polypeptide chains such as lysine, amino terminal glycine, histidine and arginine, ionic linkages are produced that prevent the penetration of the negatively charged TCEP molecules into the hair shaft. This effect is shown as follows:

H-N

O C=O

O CH₂CH₂C-O ^• NH⁺ ₃-CH₂CH₂CH₂CH₂CH

O-CCH2CH2-P: N-H lysine

CH₂CH₂C-O -NH⁺ ₃ C=O

O CH₂ O R₂

\ / C TCEP \

N / \ H R₃ glycine

The overall nucleophilic reactivity of TCEP does not appear to be a limiting factor in the reduction of disulfide bonds. This contention is supported by spectrophotometrics studies which show that water-soluble disulfides, such as 2,2'- dithiodipyridine (DTDP) is reacted upon and cleaved almost instantly by TCEP over a broad pH range from pH 2 to pH 7. Therefore, TCEP has good reducing activity toward soluble disulfides in an aqueous environment and this activity can be increased by elevating the pH of the media. Since laboratory tests have demonstrated that in aqueous systems

TCEP has the chemical ability and adequate necleophilic activity to cleave disulfide bonds, the various means to enhance the penetration of TCEP through the hair cuticle and into the polypeptide structure of the microfibril were investigated. Accordingly, an experiment was conducted on virgin hair that had not been previously conditioned or treated with any reducing agents. When this hair was exposed to a TCEP perming treatment a modest sulfur odor was observed. However, if this same hair was clipped with scissors into short lengths of approximately 1/8" to 1/4" long and then treated with TCEP there was a pronounced and noticeable odor of sulfur. The sulfur odor can be positively correlated with the degree and extent of disulfide bond cleavage. The experiment showed that by snipping the hair and exposing the cut ends of the polypeptide chains to a solution of TCEP, the reducing agent was able to gain immediate and easy access to the exposed protein disulfide bonds. The above findings are supported by the observation that there is difficulty in establishing a good hair perm and curl when using TCEP at high pH's. This result may be due to the lack of hair penetration by TCEP and not necessarily related to the reactivity of the TCEP molecule. Therefore, finding a catalyst that will lower the activation energy barrier of the reduction reaction may be viewed as having a lower priority than solving the penetration problem. Thus, other means have been explored that will enhance the penetration of TCEP into the hair shaft.

It is therefore an object of this invention to provide a useful and efficient means of disrupting the disulfide bonds in hair which leads to the successful practice of hair perming and hair straightening. An additional object of this invention is to avoid the use of strong reducing chemicals, requiring high pH for activity and provide instead, a medium in which the water-soluble phosphine reducing agent can engage in the necessary chemical reactions that lead to significantly improved hair perming, better hair styling and better overall hair care. Summary of the Invention

The present invention is directed to the use of a water-soluble tertiary phosphine as a reducing agent for altering the physical structure of hair. In this regard, the phosphine compound of Formula (I) can be used as the reactive agent needed to break disulfide bonds within an insoluble substrate, namely hair.

: P [(-R,) (-R₂) (-R₃)] (I) wherein R1 , R2 and R3 are independently linear or branched alkyl groups of 2 to 12 carbon atoms optionally substituted with a carboxy or hydroxy group. The phosphine compound initiates the reducing sequence leading to the practice of permanent hair waving and hair straightening.

In Formula (I), Rι, R₂ and R₃ are preferably the same. More preferably, Ri, R₂ and R₃ are -(CH₂)₃-OH, namely Tris-(3-hydroxypropyl)phosphine (THPP) or Ri, R₂ and R₃ are -(CH₂)₂-COOH, namely Tris-(2- carboxyethyl)phosphine (TCEP).

Organic solvents are combined with these agents to lower the polarity of the composition thereby increasing the penetrating ability of the composition. The composition may also advantageously contain a penetration enhancing agent. Detailed Description of the Invention

It has been discovered that changing the polarity of the solvent in which a phosphine of Formula (I) is solubilized facilitates penetration of the reducing agent into the central regions of the hair shaft.

Lowering the polarity of the solvent system by adding a given percent of methanol, ethanol, or butanol will probably not augment the intrinsic nucleophilic activity of the phosphine compound. However, a solvent that is less polar than water, such as ethanol or butanol, has been shown to penetrate into the hydrophobic regions of the microfibril structure of hair and thereby enable solubilized phosphine to reach the interior disulfide bonds linking adjacent polypeptide chains. By starting with a solvent system containing 4% to 5% (v/v) methanol, covering a pH range between 4.0 - 9.0 and using the phosphine at a concentration of 1 % to 30% (w/v), increased penetration of the active was noted to lead to positive hair perming results when using bleached blond hair. Prior to treatment the bleached blond hair showed physical evidence of being damaged. Damaged hair has some of the disulfide bonds and a portion of the internal bonding structure already compromised, thus the hair is more porous and readily penetrated by a reducing agent to a greater extent than undamaged hair.

Additionally, other water soluble tertiary phosphines of Formula (I), such as Tris-(3-hydroxyalkyl)phosphine, preferably Tris-(3- hydroxypropyl)phosphine (THPP) also has superior hair perming ability and will help to circumvent some of the aforementioned problems. THPP is a phosphine derivative that is water-soluble and lacks functional groups which can manifest a formal charge. This new molecule is shown below: CH₂CH₂CH₂OH

I HOCH₂CH₂CH₂-P:

I CH₂CH₂CH₂OH

Tris-(3-hydroxypropyl) phosphine

THPP can penetrate into the interior polypeptide chains in the hair shaft because it lacks a formal charge and cannot form ionic bonds with positively charged functional groups. Also the treated hair can accept a stronger and longer lasting perm because THPP is a better nucleophile. The increased nucleophilicity is due to the electron releasing effects of the three hydroxypropyl chains attached to the phosphorus atom. As a consequence, the unshared pair of electrons on THPP phosphorus atom becomes more available for nucleophilic reactivity. More importantly, THPP can penetrate the hair effectively due to the absence of an acid chloride salt. In earlier perming reactions which utilized TCEP, it was necessary to neutralize the acid component of TCEP • HCI with base prior to use.

It is known that when TCEP is used in hair perming formulations above a concentration of 5% to 10% (w/v) a large amount of NaOH is required for the neutralization of HCI and this reaction can produce a very high salt concentration. It has been documented that the presence of some salt is useful as an aid to hair shaft penetration by interrupting salt linkages. Conversely, having too much salt available as an ion-pair unnecessarily clogs ports of entry into the hair shaft thereby denying TCEP access to the interior of the polypeptide chains. The high concentration of salt has been shown to diminish the hair perming capability of TCEP. THPP is easily managed as a laboratory reagent. It is shipped as a water-soluble stock solution and can be dispensed by aliquoting. Since no neutralization is required, the time-consuming titration to achieve neutralization with mineral acid is eliminated.

Solvent Polarity - Increasing the Effectiveness of TCEP and THPP It has been discovered that by lowering the polarity of the solvent system used to deliver the reducing agent, better hair penetration of the active as well as improved perming characteristics can be achieved.

The following list of compounds depicted in Table I are shown with their respective dipole moments and can be incorporated into a hair perming formulation for transforming the polarity of the solvent systems:

TABLE I

Other suitable solvents include glycerine, low molecular weight glycol of CnH2n(OH)2 wherein n is 1-4, or polyethylene, polypropylene or polybutylene glycol of low, intermediate or high molecular weight, methyl end-cap glycol, monoglyme (ethylene glycol dimethyl ether), diglyme (2-methoxyethyl ether) and methylal (dimethoxymethane). Formulations that have been investigated and evaluated for their ability to transport TCEP and THPP into the hair shaft have utilized a relatively mild nonpolar solvent system such as 4% and 5% (v/v) methanol and 5% and 6% (v/v) ethanol. Results to date indicate that a 6% (v/v) solution of ethanol in H₂0 when used in conjunction with TCEP at a 5% (w/v) concentration between pH 4.0 and pH 9.0 is the best solvent system for effective TCEP disulfide bond reduction and hair perming. Likewise a 6% (v/v) solution of ethanol in H₂O is used to solubilize THPP over a concentration range from 5%-10% (w/v) results in good hair penetration of the active between pH 6.0 and pH 8.0 as well as superior hair perming performance when compared to TCEP. At a 10% (w/v) concentration of TCEP there is an accumulation of Na⁺CI^" produced by the neutralization reaction between TCEP«HCI and NaOH. This neutralization step is not a prerequisite in the formulation of the THPP perming agent. Also noted is the fact that a 30% (w/v) concentration of TCEP in the presence of methanol at 5% (v/v) and at pH 8.0 produces conditions that are not favorable for perming either brown or dark brown hair which thus far has been found to be the most difficult kind of hair to perm. The conclusion reached in the evaluation of TCEP and THPP perming performance is that negative charge, high polarity and high salt concentration all play a part in lowering the penetration effectiveness of TCEP; while the absence of charge, relatively low polarity and low salt concentration contribute to the effectiveness of THPP. In a complementary fashion the non-polar solvent systems are beneficial to both reducing agents in regards to hair penetration. The procedures for perming hair with a TCEP formulation at low pH and a THPP formulation at a pH between pH 4.0 and pH 9.0 are outlined in the Formulation examples set forth below.

FORMULATION EXAMPLES

A. TCEP formulation and perming procedure

Step ! Shampoo 10.0% sodium lauryl sulfate 1.3% thioglycolate

10.0% urea 2.0% triethanolamine 2.5% benzyl alcohol

0.04% ethylenediaminetetraacetic acid (EDTA) q.s. 50.0% sodium hydroxide (NaOH) to pH 9.0

This formulation is foamed and allowed to remain on the hair for I0 minutes. Step 2. Glycine buffer rinse 100rnM glycine»HCI buffer

10.0% TCEP q.s. 50.0% sodium hydroxide at pH 2.4

This formulation is allowed to remain on the hair for 10 minutes. Step 3. TCEP Perm formulation

30.0% TCEP 8.0% Triton x-200 anionic surfactant

6.0% Crodacet TD-7C 0.5% Surfadone LP-300 surfactant 0.04% EDTA q.s. 50.0% NaOH to pH 2.2 This formulation is worked into the hair and the temperature maintained at 60° for 40 minutes. Step 4. Neutralization

15.0% sodium bromate The neutralizer is allowed to remain on the hair for 10 minutes and then rinsed away.

B. THPP formulation and perming procedure Step 1. Shampoo

Use any shampoo to wash and clean hair. Step 2. Glycine buffer rinse lOOmM glycine

To be used for 10 minutes but only if the subsequent perming time is less than 15.0 minutes. If perming time is longer than 15.0 minutes, then the glycine buffer rinse is not to be used. Step 3. THPP Perm formulation

5% to 10.0% THPP 100mM glycine

6.0% ethanol pH will be at 7.7 After the hair is in the desired set, this formulation is worked into the hair and allowed to remain on the hair anytime between 5 minutes and 20 minutes at any temperature between 45°C and 60°C depending on the amount of perm desired. Step 4. Neutralization

3.0% hydrogen peroxide The neutralizer is allowed to remain on the hair for 10 minutes and then rinsed away. So far this disclosure has focused on a binary solvent system composed of water and ethanol, etc. This approach should be broadened to include using a ternary solvent system and/or a quaternary solvent system. Such systems are utilized in thin layer chromatography to provide numerous polarity options and they should be applicable to facilitating hair penetration of active reducing agents and other compounds.

Since it appears that the penetration of the hair shaft with TCEP and THPP is a necessary first step to permit the reduction of the disulfide bonds, it follows that other penetrating agents which preferentially break hydrogen bonds may also be likely penetration enhancers. These include urea, thiourea, acetamide, ammonia, ethanolamine, primary, secondary or tertiary Cι_-4 alkylamine derivatives wherein the alkyl group is optionally substituted with a carboxy or hydroxy group, glycerine, formamide, bromine derivatives and organic solvents. It is also evident that hair which has been previously bleached with hydrogen peroxide or permed with other thioglycolate reducing agents has demonstrated internal structural protein damage. The damaged hair is more porous and therefore more readily penetrated by perming agents. Most of the initial tests with TCEP using non-polar solvents, which have shown good perming success, have used blond bleached hair which by definition shows some aspects of hair damage. However, in subsequent experiments a 5% (w/v) solution of TCEP in 6% (v/v) ethanol, between pH 4.0 and pH 9.0, showed no perming capability towards dark brown hair at 60°C during a 30-minute incubation period. In contrast, a 5% (w/v) solution of THPP in 6% (v/v) ethanol, between pH 4.0 and pH 9.0, demonstrated pronounced perming of dark brown hair over a temperature range of 45°C to 60°C during a 10-minute incubation period. Tris-(3-hydroxypropyl) phosphine has been tested as a perming agent for hair is water-soluble and does not have the acid chloride salt present. Therefore a small amount of Na⁺CI^" could be added to the perming formulation in order to disrupt polypeptide salt linkages and further augment the penetration of the reducing agent into the hair. The amount of salt that may have to be added is calculated as shown in Table II:

TABLE II

NaOH + HCI - NaCI + H₂0

How many mg of NaOH are in 40μl of 20N NaOH which is the amount of base required to neutralize 1.0ml of 5% w/v TCEP ^• HCI?

I N = 40g/l, 20N = 800μg/1 μl

How many mg of NaCI are produced?

.-. 40g = 58.5σ

32.0mg x x = 46.8 mg of NaCI is produced in the neutralization reaction.

Thus 32.0mg of NaOH is required to neutralize a 5% (w/v) solution of TCEP. There is approximately 46.8 mg of NaCI/ml produced in this reaction. This is probably excessive salt. Since 46.8 mg of NaCI/ml = 46.8 g/l and

46.8g = 0.8 Molar NaCI

A salt concentration in the hair perming solution ranging from 0.01 %- 5.0% (w/v) NaCI should be adequate for disrupting salt linkages.

This disclosure has focused on considering the role played by the polarity of the solvent system used to deliver the aforementioned phosphine reducing agents to the hair shaft polypeptide chains. Also considered was the need to remove the ionic charge from the phosphine reducing agent in order to deliver a more neutral molecule to the microfibril regions of the hair shaft. Moreover, the role of Na⁺CI^" was evaluated as an additive to enhance THPP activity. However, when high salt concentration of sodium chloride were produced during the neutralization of TCEP, salt was found to inhibit the perming process.

In addition to polarity, viscosity and vapor pressure are intrinsic properties of any solvent system under consideration. A lowering of the viscosity of the solvent system with 5% (v/v) methanol or 6% (v/v) ethanol in water, effectively translates into a lowering of solvent surface-tension which in turn leads to improved wetting of the hair shaft. This alteration in solvent properties permits the active reagents greater access to the internal microfibril structure of the hair shaft thereby leading to a better perming of hair.

In addition to viscosity, the vapor pressure of the solvent system plays an important role in helping to separate and open up the fine microfibril structure of hair. An increased vapor pressure leading to enhanced solvent volatility with accompanying heat ranging in temperature from 45°C to 60°C facilitates the opening of interstitial spaces between the polypeptide chains and allows for the improved penetration of non-polar solvents along with reducing reagents.

Thus it has been shown that both TCEP and THPP reducing agent activity is enhanced when organic solvents such as methanol and ethanol are introduced to lower the solvent polarity. THPP, because of its lack of charge, is a more effective perming agent than TCEP. THPP is better able to penetrate deeply into the hair shaft and it has a slightly increased nucleophilicity in comparison to TCEP. All of these properties contribute to the superior hair perming performance of THPP. It is also possible to incorporate a phosphine composition with a penetration enhancer and glucose in a liposomal package in order to reduce the disulfide bonds and position glucose for subsequent oxidation of the sulfhydryl groups. Then, a second liposome, containing glucose oxidase is applied to the hair shaft which will react with the glucose previously deposited. There and only there, will hydrogen peroxide be generated in situ to set disulfide bonds into a permanent condition. This reaction leads to localized concentrations of hydrogen peroxide where glucose is deposited and avoids the traditional pitfalls using commonly applied oxidizing agents where hydrogen peroxide is used in excess and puts the consumer at risk.

The invention has been described with reference to the preferred embodiment. Obviously, modifications and alterations will occur to others upon a reading and understanding of the preceding detailed description. It is intended that the invention be construed as including all such alterations and modifications insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims

We claim:

1. A hair perming composition comprising

(a) an effective amount of at least one phosphine compound represented by the following formula

: P [(-Ri) (-R₂) (-R₃)] (I)

wherein Ri, R₂ and R₃ are independently linear or branched alkyl groups of 2 to 12 carbon atoms optionally substituted with carboxy or hydroxy groups, and (b) a penetration enhancer.

2. The hair perming composition of Claim 1 wherein R-i, R₂ and R₃ are the same.

3. The hair perming composition of Claim 2 wherein R_{1 t} R₂ and R₃are -(CH₂)₃-OH, namely Tris-(3-hydroxypropyl)phosphine (THPP).

4. The hair perming composition of Claim 2 wherein Ri, R₂ and

R₃ are -(CH₂)₂-COOH, namely Tris-(2-carboxyethyl)phosphine (TCEP).

5. The composition of Claims 1 -4 wherein the phosphine compound is present at a concentration of from about 1 % to about 30% (w/v).

6. The composition of Claim 1 further comprising a solvent system.

7. The composition of Claim 6 wherein the solvent system comprises one or more compounds selected from the group consisting of phenol, isobutanol, 1 -butanol, 2-propanol, 1-propanol, ethanol, methanol, water, acetone, dimethyl sulfoxide, dimethyl sulfone, glycerine, low molecular weight glycol of C_nH_2n(OH)₂ wherein n is 1-4; polyethylene, polypropylene or polybutylene glycol of low, intermediate or high molecular weight; methyl end-cap glycol, monoglyme (ethylene glycol dimethyl ether), diglyme (2-methoxyethyl ether) and methylal (dimethoxymethane).

8. The composition of Claim 7 wherein the solvent system compounds are ethanol, methanol, water or mixtures thereof.

9. The composition of Claim 1 wherein the penetration enhancer is present at a concentration of about 0.25% to about 10.0% by weight.

10. The composition of Claim 1 wherein the penetration enhancer is selected from the group consisting of urea, thiourea, acetamide, ammonia, ethanolamine, primary, secondary or tertiary d-₄ alkylamine derivatives wherein the alkyl group is optionally substituted with a carboxy or hydroxy group, glycerine, formamide, bromine derivatives and organic solvents.

11. The composition of Claims 1 -10 wherein the pH is from about pH 4.0 to about pH 9.0.

12. The composition of any one of Claims 1 -11 further comprising a polypeptide salt linkage disrupting amount of Na⁺CI\ 13. The composition of Claim 12 wherein the concentration of

NaCI is from about 0.01 % to about 5.0% (w/v).

14. A hair perming composition comprising a hair care perming effective amount of Tris-(3-hydroxypropyl) phosphine (THPP), a solvent system, a penetration enhancer and a polypeptide salt linkage disrupting effective amount of NaCI.

15. The composition of Claim 14 wherein the THPP is present at a concentration of from about 1 % to 30% (w/v).

16. The composition of Claim 14 wherein the solvent system comprises ethanol, methanol, water or mixtures thereof.

17. The composition of Claim 14 wherein the NaCI concentration is from about 0.01 % to about 5.0% (w/v).

18. The composition of any one of Claims 14-17 wherein the pH is from about pH 4.0 to about pH 9.0.

19. A hair perming composition comprising a hair care perming effective amount of Tris-(3-hydroxyalkyl) phosphine, preferably Tris-(3- hydroxypropyl)phosphine (THPP) or Tris-(2-carboxyalkyl) phosphine, preferably Tris-(2-carboxyethyl)phosphine (TCEP) along with a solvent system.

20. The composition of Claim 19 wherein the solvent system comprises of one or more compounds selected from the group consisting of ethanol, methanol, and water.

21. The composition of Claim 19 wherein the THPP or TCEP is present at a concentration of from about 1% to about 30% (w/v).

22. The composition of Claim 19 wherein the solvent system compounds are present at a concentration of about 70% to about 99% (v/v).

23. A hair perming composition comprising a first liposome containing a phosphine composition of Claim 1 and glucose, and a second liposome with glucose oxidase, whereby the first liposome will break the disulfide bonds and hold the glucose at the location of bond reduction, and the second liposome is applied to react with the glucose to produce hydrogen peroxide.

24. A method for breaking the naturally occurring disulfide bonds in hair that is to be permed which comprises applying to the hair to be permed a composition as set forth in any one of Claims 1 -22 in an amount effective to penetrate and break the naturally occurring disulfide bonds in hair.