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Publication numberUS3479427 A
Publication typeGrant
Publication dateNov 18, 1969
Filing dateOct 22, 1965
Priority dateOct 22, 1965
Publication numberUS 3479427 A, US 3479427A, US-A-3479427, US3479427 A, US3479427A
InventorsLieberman George, Palmer Milton, Prussin Samuel B
Original AssigneeDart Ind Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Composition for application to hair
US 3479427 A
Abstract  available in
Images(4)
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Claims  available in
Description  (OCR text may contain errors)

Int. Cl. A61k 7/10 US. Cl. 424-47 1 Claim ABSTRACT OF THE DISCLOSURE A hair conditioning, setting and holding composition comprising from 1 to about 10% by weight,of hydrated dialdehyde starch having a dialdehyde number of at least 50 in a cosmetically acceptable vehicle.

This invention relates to compositions classified in the art of hair dressing as hair conditioning, setting and holding compositions.

Considerable effort has been devoted by cosmetic chemists towards formulation of compositions adapted to set human hair in a desired configuration and to hold the configuration for a period of time. Such formulations, for optimum acceptability and utility, must not only perform the desired function of holding the hair, but in addition must have good resistance to high relative humidity conditions. It is desirable that such compositions, upon application to the hair, not yield sticky or stiff films or films which result in flaking of the hair holding ingredient. Furthermore, the treated hair should possess good sheen, gloss and comba-bility.

Many formulations have been developed in the past which possess certain but not all of the above-mentioned desirable properties. One of the first materials used in hair setting formulations as a hair holding ingredient was shellac. The use of shellac-based formulations may impart stiffness to the hair which is not of optimum desirability. Many commercial formulations in recent years have been based upon polyvinylpyrrolidone as the hair holding, film forming agent. The resulting films have good physical characteristics, but may have poor resistance to high humidity and as a result may not hold the desired configurations for long periods of time.

It is an object of this invention to provide a hair setting, holding and conditioning composition which upon application to human hair conditions the hair and sets and holds it in a desired configuration for a long period of time with good resistance to high relative humidity conditions.

It is a further object of this invention to provide a composition which upon application to human hair is non-sticky, does not flake and is not stiff.

Other objects and the advantages of this invention will become apparent from the following detailed description.

The invention sought to be patented is described as residing in the concept of a composition of matter comprising about 1 to about 10% by weight of hydrated dialdehyde starch having a dialdehyde number of at least 50 in a cosmetically acceptable vehicle.

The manner and process of making and using the invention will now be generally described so as to enable one skilled in the art of cosmetic chemistry to make and use the same as follows:

The hair holding ingredient in compositions of matter in accordance with this invention constitutes a hydrated dialdehyde starch having a dialdehyde number of at least 50. The starch molecule consists of a long chain United States Patent 3,479,427 Patented Nov. 18, 1969 ICC of anhydroglucose units, each unit in the chain having the following formula:

CH2OH H OH It is known in the art of starch chemistry that starch can be selectively oxidized under the influence of periodate ion, resulting in the oxidation of the two adjacent hydroxyl groups in the anhydroglucose units of the starch molecule to the aldehyde form, each such selectively oxidized unit having the following structural formula:

CHgOH II II o o The resulting selectively oxidized starch is commonly known in the art as dialdehyde starch, the name derived from the fact that each anhydroglucose unit which has been selectively oxidized contains two aldehyde groups. A chemical procedure for carrying out the selective oxidation chemically is described in Journal of American Chemical Society, vol. 73: 4484 (1951) and electrolytic selective oxidation techniques are described in US. Patents 2,648,629 and 2,713,553.

By varying the conditions of the oxidation, it is possible to oxidize selectively varying percentages of the number of anhydroglucose units in the original starch molecule. The degree of such oxidation is referred to throughout the specification and in the claim by the term dialdehyde number, which means the number of the original anhydroglucose units of the starch molecule which are in the dialdehyde form for each units in the chain. It has been found that a dialdehyde number of at least 50 is required for dialdehyde starches useful in the preparation of compositions of matter in accordance with this invention.

Dialdehyde starch as prepared by the above-described oxidation techniques is in a physical form which is not adapted to the formulation of satisfactory compositions in accordance with the invention and it is necessary to hydrate the dialdehyde starch in order to convert it to a useable form. The technique of hydrating startch itselt is well known in the art of starch chemistry and is adapted as well to the hydration of dialdehyde starch. Hydration is effected by heating an aqueous dispersion of dialdehyde starch to at least 60 C. for a sutficient time to attain a substantially clear solution. The end point is readily determined by visual observation since the dispersion during the heat-treating step proceeds to thicken and then becomes substantially thinner at the same time that a clarification occurs. For best results it is desirable to include certain additives in the dispersion, the presence of which results in marked reduction in the time required for hydration. Among the additives which can be used to hydrate dialdehyde starch in accordance with the techniques of the prior art are hydrogen peroxide and alkaline materials such as sodium bicarbonate and borax. With the presence of such materials in the dispersion at a concentration of about 1 to about 15 percent of the weight of dialdehyde starch, the hydration takes place in between 30 and 60 minutes. As used throughout the specification and in the claims, the term hydrated dialdehyde starch means dialdehyde starch which has been hydrated as above described by heating in an aqueous medium with or without additives in accordance with well-known techniques in the art of starch chemistry.

It has been found that effective compositions in accordance with the invention can be prepared containing between about 1 and about by weight of hydrated dialdehyde starch having a dialdehyde number of at least 50. The amount actually selected within the above range for any particular composition depends upon the intended purpose. At lower percentages of hydrated dialdehyde starch within the above range, the compositions are for generally short term hair-holding use. Higher percentage compositions are designed for hair setting purposes with retention of the desired set for prolonged periods of time. All compositions of the invention are particularly useful in conditioning and bodying the hair.

Hydrated dialdehyde starches prepared as described above are generally referred to in the art as being of the nonionic type. It is known that dialdehyde starch can be converted to a cationic form by inactivating a small percentage of the aldehyde groups in the molecule by treatment with a compound having a cationic moiety, for example stearyldimethylbenzylammonium chloride, N-(stearoylcolaminoformylmethyl)pyridinium chloride, laurylisoquinolinium bromide, cyanoguanidine formaldehyde and the like. Both types are included within the scope of the term hydrated dialdehyde starch as used throughout the specification and in the claims, subject to the limitation that the resultant products have a dialdehyde number of at least 50.

In the formulation of compositions in accordance with this invention, it is generally preferred that the hydrated dialdehyde starch be combined with a cosmetically acceptable plasticizer which is designed to impart desirable properties upon application of the compositions to human hair. Such plasticizers can be selected from a wide class of materials and include dialkylpolysiloxanes such as dimethylpolysiloxanes, lower alkylene glycol ethers of dilower alkylpolysiloxanes such as the ethyleneglycol ether of dimethylpolysiloxane, polyethyleneglycols having a molecular weight in the range of about 200 to 1,000, aliphatic esters of phthalic acid such as dibutyl phthalate and dioctylphthalate, lanolin, modified lanolins such as acetylated lanolin and higher hydrocarbons, esters, ethers and alcohols containing more than 12 carbon atoms such as squalene, hexadecyl alcohol, isopropyl myristate, and the like. A plasticizer may be incorporated in the composition of this invention in an amount of up to 100% of the weight of the hydrated dialdehyde starch.

In the preparation of compositions of this invention, hydrated dialdehyde starch having a dialdehyde number of at least 50 is dispersed in a cosmetically acceptable vehicle. The vehicle is selected depending on the desired physical form of the finished product and can, for example, be a liquid or solid emulsified, cosmetically acceptable cream, a liquid, a gel or a pressurized vehicle for the application of the composition in the form of an aerosol spray. For the formation of liquid unpressurized compositions, water or an aqueous alcoholic solution are most generally preferred vehicles.

-In the formulation of a composition of this invention as a pressurized product, either a one or two phase liquid system can be prepared, depending on the choice of liquids used in the formulation. If a single phase liquid system is desired, propellants soluble in the liquid system must be used. A useful propellant that is soluble in water and alcohol-water mixtures is dimethyl ether.

In addition, compressed gas-propelled single liquid phase aerosols based upon nitrous oxide, carbon dioxide, nitrogen and the like can be formulated. Furthermore,

if sufiicient alcohol is used in the formulation, small amounts of water insoluble propellants, for example the chlorofiuorohydrocarbons' widely used and sold under the trademark Freon, or hydrocarbons such as isobutane, can be incorporated into a single phase system.

If a two liquid phase aerosol system is desired, a propellant that is immiscible with the aqueous or aqueous alcoholic solution of hydrated dialdehyde starch is used. If a propellant with a density greater than that of the aqueous dispersion of hydrated dialdehyde starch is used, such as the chlorofluorohydrocarbons, a two liquid phase system with the propellant in the bottom layer will be formed. -If a propellant with a density lower than that of the aqueous dispersion is used, for example a lower hydrocarbon such as propane, isobutane and the like, a two liquid phase system with the propellant phase on the top will be formed.

In all the classes of formulations, conventional ingredients to impart fragrance will be present and, in addition, preservatives such as alkyl para-hydroxybenzoates, ethylene oxide and the like.

The best mode contemplated by the inventors for carrying out their invention will now be set forth as follows:

EXAMPLE 1 Dialdehyde starch (dialdehyde number=) in water, 9.2% w./w., is heated to C. and 4% by weight hydrogen peroxide is added based upon the weight of dialdehyde starch solids. Heating is continued for 45 minutes at which time the mixture thins to form a clear solution of hydrated dialdehyde starch. A composition is prepared from this material with the following proportions:

Percent by weight Hydrated dialdehyde starch 3.75 Stearyldimethylbenzylammoniurn chloride 1.25 Polyethylene glycol (mol. wt.=400) 0.47 Perfume 0.19 Alcohol 12.50

Water, q.s. to 100.

in Example 1) 3.00 Stearyldimethylbenzylammonium chloride 1.00 Polyethylene glycol (mol. wt.=400) 0.38 Perfume 0.15

Alcohol 10.00

Isobutane 20.00

Water, q.s. to 100.

The resulting composition is a two liquid phase system with the propellant phase on top.

EXAMPLE 3 A pressurized composition is prepared with the composition of Example 2 except that the isobutane is replaced by dichlorodifluoromethane in an amount of 5% by weight of the composition. The resulting composition is a two liquid phase system with the propellant phase on the bottom.

The following two examples illustrate the formulation of compositions of this invention based upon hydrated dialdehyde starch of the cationic type.

Water, q.s. to 100.

1 Dialdehyde number QO 10% of dialdehyde groups cationized with stearyldirnethylbenzylammonium chloride.

The resulting composition is pressurized and is of the two liquid phase type with propellant phase on top.

EXAMPLE 5 Percent by weight Hydrated dialdehyde starch (as in Example 4) 3.75 Polyethylene glycol (mol. wt.=400) 0.47 Dimethyl polysiloxane 0.31 Perfume 0.13 Alcohol 18.79

Water, q.s. to 100.

The resulting formulation is an unpressurized single phase solution.

The following example is illustrative of single liquid phase pressurized compositions in accordance with the invention:

EXAMPLE 6 Percent by weight Hydrated dialdehyde starch (prepared as described in Example 1) 3.00 Polyethylene glycol (mol. wt.=400) 0.38 Dimethyl polysiloxane 0.25 Perfume 0.10 Alcohol 10.00

Water 66.27 Dimethyl ether 20.00

The following example is illustrative of compositions of the invention having high alcoholic content and adapted to fast drying:

EXAMPLE 7 Percent by weight Hydrated dialdehyde starch (as in Example 1) 3.75 Polyethylene glycol (mol. wt.=400) 0.47 Stearyl dimethylbenzylammoniumchloride 1.25 Perfume 0. l 9 Alcohol 60.00

Water, q.s. to 100.00.

The following example illustrates a composition of this invention where the dialdehyde starch is hydrated by use of sodium bicarbonate:

6 EXAMPLE 8 Dialdehyde starch (dialdehyde number=90), 4 parts, is dispersed in parts. distilled water and 0.53 part of sodium bicarbonate is added. The mixture is heated to C. for 40 minutes during which the mixture thickens and then thins to form a clear solution as the dialdehyde starch is hydrated. 20 parts ethyl alcohol are added and the mixture is blended with 2 parts plasticizer mixture (75% isopropyl myristate and 25% ethylene glycol ether of dimethylpolysiloxane), 0.2 part fragrance and 0.15 part methyl p-hydroxybenzoate.

The subject matter which the applicants regard as their invention is particularly pointed out and distinctly claimed as follows.

What is claimed is:

1. A pressurized composition adapted to set, hold and condition human hair which comprises water, alcohols, about 1 to 10 percent by weight of the composition of hydrated dialdehyde starch having a dialdehyde number of at least 50, a cosmetically acceptable plasticizer which is present in an amount up to 10 percent by weight of the composition, and from about 5 to 20 percent of a c0srnetically acceptable aerosol propellant.

References Cited UNITED STATES PATENTS 2,643,375 6/1953 Gant 167-871 2,995,278 8/1961 Clapp. 3,033,851 5/1962 Schaefer et a1. 16787 XR 3,144,391 8/1964 Goff. 3,186,911 6/1965 Rieger et al. 3,207,386 6/1965 Presant et a]. 3,208,911 9/1965 Oppliger l6787.1 XR 2,783,283 2/1957 Sloan et al 106213 XR 2,933,407 4/ 1960 Witt et a1 106213 XR 3,145,116 8/1964 Zienty 106213 XR 3,269,852 8/1966 Borchert et al 106213 3,293,057 12/1966 Rumberger 106213 XR 3,313,641 4/1967 Borchert 106213 OTHER REFERENCES Mellies et al.: Ind. and Eng. Chem., vol. 50, No. 9, pp. 1311-1314, 1958.

Sloan et al.: Ind. and Eng. Chem., vol. 48, pp. 1165- 1172, 1956.

LEON ZITVER, Primary Examiner HOWARD T. MARS, Assistant Examiner U.S. C1. X.R. 42470 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,479,427 November 18, 1969 George Lieberman et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 6, line 17, "alcohols" should read alcohol Signed and sealed this 27th day of October 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer Commissioner of Patents WILLIAM E. SCHUYLER, JR.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2643375 *Dec 26, 1951Jun 23, 1953Northwestern Res CorpMethod of treating hair
US2783283 *Nov 25, 1955Feb 26, 1957Hofreiter Bernard THydrogenolysis of dialdehyde starch to erythritol and ethylene glycol
US2933407 *Aug 8, 1956Apr 19, 1960Ohio Commw Eng CoDextrin-dextran adhesives
US2995278 *May 22, 1959Aug 8, 1961Western Filling CorpPackaged self-propelling liquid compositions
US3033851 *Apr 18, 1961May 8, 1962Russell Charles RHeterofunctional derivatives of dialdehyde starches and method of making same
US3144391 *Mar 28, 1960Aug 11, 1964Gillette CoHair-setting composition
US3145116 *Jul 7, 1960Aug 18, 1964Miles LabInsolubilization of starches with dialdehyde polysaccharides
US3186911 *Jul 16, 1962Jun 1, 1965Warner Lambert PharmaceuticalHair setting composition comprising an aqueous dispersion of a tertiary aminoalkyl ether of starch
US3207386 *Jun 1, 1962Sep 21, 1965Aerosol Tech IncAerosol dispenser producing non-flammable spray with fluid system having a flammable propellant
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US3293057 *Jul 1, 1963Dec 20, 1966Brown CoModified starch composition
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4134968 *Feb 10, 1977Jan 16, 1979Lever Brothers CompanySingle phase water containing aerosol compositions
US4192862 *Jul 26, 1978Mar 11, 1980Lever Brothers CompanyHairspray containing a hairspray resin and a drag reducing agent
US4452261 *Jan 29, 1982Jun 5, 1984The Gillette CompanyHair setting composition and method
US4861583 *Nov 20, 1987Aug 29, 1989S. C. Johnson & Son, Inc.Hot curling hair treatment
US5520200 *Dec 16, 1994May 28, 1996L'orealProcess for the non-lasting reshaping of keratinous fibres
US6344183Mar 29, 1999Feb 5, 2002National Starch And Chemical Investment Holding CorporationAerosol hair cosmetic compositions containing non-ionically derivatized starches
US6413505Mar 29, 1999Jul 2, 2002Nationa L Starch And Chemical Investment Holding CorporationNonionically derivatized starches and their use in non-aerosol, low VOC hair cosmetic compositions
US6562325Mar 29, 1999May 13, 2003National Starch And Chemical Investment Holding CorporationUse of stabilized starches in low VOC, polyacrylic acid-containing hair cosmetic compositions
WO1989001771A1 *Aug 27, 1987Mar 9, 1989S.C. Johnson & Son, Inc.Hot curling hair treatment
Classifications
U.S. Classification424/47, 424/70.13
International ClassificationA61Q5/12, A61Q5/06, A61K8/04, A61K8/73, A61K8/72
Cooperative ClassificationA61Q5/06, A61Q5/12, A61K8/732, A61K8/046
European ClassificationA61Q5/12, A61Q5/06, A61K8/04F, A61K8/73F