Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3480377 A
Publication typeGrant
Publication dateNov 25, 1969
Filing dateApr 28, 1965
Priority dateMay 6, 1964
Also published asDE1519516A1
Publication numberUS 3480377 A, US 3480377A, US-A-3480377, US3480377 A, US3480377A
InventorsJames Ralph Lyons
Original AssigneeLever Brothers Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Solvent dyeing of living human hair
US 3480377 A
Images(4)
Previous page
Next page
Description  (OCR text may contain errors)

United States Patent US. Cl. 8--10.1 4 Claims ABSTRACT OF THE DISCLOSURE A process for dyeing human hair which comprises contacting the hair with a dyeing composition comprising an aqueous solution, suspension or dispersion of a dye, an organic solvent for the dye, and a dissolved aromatic compound which is solid at the dyeing temperature and acts to increase the rate of uptake of the dye by the hair.

This invention relates to dyeing.

It is well known that the dyeing of a wide variety of materials by treatment with an aqueous solution, dispersion or suspension of a dye can be improved by including an organic solvent for the dye in the aqueous dyeing composition. 7

Thus, it is known from British patent specification 856,381 to include in the aqueous solution, dispersion or suspension of a dye with which keratinous fibers, such as silk and wool, orregenerated protein fibers are to be contacted to effect the dyeing thereof, an organic compound which is a solvent for the dye, and which is a liquid under the conditions of dyeing an insoluble or only slightly soluble in water, the solubility of the dye in the organic compound being greater than the solubility of the dye in water. Organic compounds (solvents) which may be used in the process include: aliphatic alcohols, for example n-butyl alcohol and amyl 'alcohol; aromatic hydroxy compounds, for example benzyl alcohol; esters, for example amyl lactate; aldehydes; ketones; and aromatic hydrocarbons.

British patent specification 872,506 describes a dyeing process similar to that described in the above specification although in specification 872,506 the treatment is applied to leather, skins and/or animal fibers attached thereto. The solvents that can be used are similar to those that can be used in the process of specification 856,381.

British patent specifications 826,479 and 918,597 also describe a dyeing procedure similar to that described in patent specification 856,381, although in specifications 826,479 and 918,597 the process is applied to the dyeing of human hair. The solvents used in the hair dyeing process of these patents include aliphatic and aralkyl alcohols, for example amyl alcohol and benzyl alcohol, and esters, for example amyl lactate.

British patent specification 840,904 describes a dyeing process similar to that described in British patent specification 826,479 although in this case the organic solvent must be one of a number of specified alcohols and it must be miscible with water in the proportion in which it is present. Alcohols for use in the process described in spec ification 840,904 include butyl alcohol; aralkanols, for example benzyl alcohol; and cycloaliphatic alcohols, for example cyclohexanol.

British patent specification 979,405 discloses the use as solvents of certain urea derivatives which are liquid at the dyeing temperature.

Benzyl alcohol as well as other slightly water miscible and .water immiscible solvents referred to in the above specifications increase the rate of dyeing of the fiber or other material treated. This effect is particularly useful in the dying of living human hair because it enables a good uptake of dye to be obtained even at the relatively low temperatures that have to be employed for such dyeing.

British patent specification 669,192 which concerns the dyeing of furs and skins also disclosesa dyeing procedure in which an organic solvent for the dye is included in the dyeing composition. In the procedure described in specification 669,192 the solvent employed is a partially or completely Water miscible aliphatic low molecular alcohol, ketone or ester or mixture thereof. The dyeing composition described contains 10% or more of the solvent. The dyeing can be carried out at relatively low temperatures, for example between 20 and C. Examples of the solvents employed are ethyl alcohol, glycol, acetone and ethyl acetate.

British patent specification 819,184 which relates to the dyeing of keratinous fibers, particularly hair, also describes the use of an organic solvent which is completely miscible with-the water in the proportion in which it is present. In this instance the solvent employed is one having the general formula:

.where R represents a monovalent aliphatic or araliphatic hydrocarbon group containing not more than 8 carbon atoms and n is from 1 to 4. Examples of these solvents are 2-butoxyethanol and 2-[(beta-ethoxy)-ethoxy]-etha- 1101. The use of these solvents increases the rate of uptake of the dye on the hair and enables keratinous fibers, e.g. live hair, to be dyed at ambient temperatures.

We have now discovered that the increase in the rate of dye uptake that results from the use of solvents as mentioned in the above specifications can be further improved by including dissolved in the dyeing composition a wide range of aromatic compounds which are solid at the dyeing temperature; such a compound will hereinafter be referred to as a solid aromatic compound.

Accordingly, the present invention provides a dyeing composition which comprises an aqueous solution, suspension or dispersion of a dye and an organic solvent for the dye, the composition additionally comprising dissolved therein a solid aromatic compound so as to improve the rate of uptake of the dye on the material to be dyed. Dye is used in this paragraph and hereinafter to include direct dyestuffs, i.e. dyestuffs capable of being fixed directly and in the final shade by the product to be dyed, without it being necessary to interpose any chemical transformation, and water insoluble colored organic compounds.

The invention also provides a process which comprises contacting the material to be dyed with a dyeing composition comprising an aqueous solution, suspension or dispersion of a dye and an organic solvent for the dye, which solvent is liquid under the conditions of dyeing, the dyeing composition additionally comprising a solid aromatic compound which acts to increase the rate-of uptake ofthe dye by the material contacted.

The invention may be applied to the dyeing of the various materials mentioned in the prior patent specifications referred to. In the case of fibers, these can either be in the natural state or Woven or otherwise made up into fabrics or garments. The invention is particularly applicable to the dyeing of keratinous fibers such as hair.

Experiments carried out have indicated that the solid aromatic compounds effective as increasing the rate of uptake of the dye from dyeing compositions containing solvents are those containing an aromatic ring and at least one of the following groups as substituents of the ring: carboxylic acid, amide and substituted amide, hydroxyl and esters thereof, nitrile, aldehyde, ketone, halogen, amine, alkoxy, ureido, and aliphatic groups, for example saturated or unsaturated groups containing up to 6 carbon atoms, which aliphatic groups are themselves substituted by at least one hydroxyl or carboxyl group.

The solid aromatic compound molecule may contain a phenyl or naphthyl ring.

The classes of compounds from which the solid aromatic compound may be chosen include: carboxylic acids, e.g. benzoic, cinnamic, salicylic, hippuric, and naphthoic acids; monoand polyhydric phenols; and chloro benzenes.

Examples of compounds containing more than one of the above substituent groups are o-anisaldehyde, o-amino phenol and p-chloro phenol. The substituent groups may be the same as in, for example, p-dichlorobenzene and o-dimethoxy benzene.

Examples of compounds containing a substituted aliphatic group are methoxy phenyl acetic acid, p-nitro benzyl alcohol and cinnamic acid.

The solid aromatic compound may comprise an unsubstituted hydrocarbon group attached to the aromatic ring. Such a group may be a phenyl group or an aliphatic group such as an alkyl or alkenyl group having up to 6 carbon atoms, for example. Other groups may be present, for example nitro, nitroso, sulphonic acid or substituted sulphonic acid groups.

Examples of compounds having other substituents present are o-cresol, thymol, sulphanilic acid, rn-nitrobenzaldehyde, p-nitro-benzyl alcohol, sulphanilanilide, pnitrobenzyl alcohol and 2,4-dichloronitrobenzene.

The optimum amount of the solid aromatic compound to be used will to some extent be dependent on the other components of the dyeing composition such as the dye and solvent. In most cases an amount of at least 0.5% by weight of the dyeing composition will be necessary to produce a significant increase in the dyeing effect. For the dyeing of hair usually amounts in the range 1 to give the best results. Amounts of the solid aromatic compound in excess of its solubility in the dyeing composition are not objectionable but do not give any significant advantage and usually such an excess will not be used.

As the dyeing of living hair is usually carried out below 45 C. the solid aromatic compound used in this instance can have a melting point as low as 45 C., or even lower depending on the actual dyeing temperature used. Higher temperatures may be used in other dyeing treatments, for instance in wooldyeing, but then the range of solid aromatic compounds that can be used is smaller. Thus for W001 dyeing one employs solid aromatic compounds having a melting point above about 80 C. or in any event above the actual dyeing temperature used.

As is known from the abovementioned specifications, a wide variety of dyes can be used in solvent-containing dye systems and those mentioned can be employed in performing this invention.

Among the dyes that can be used are reactive dyes which contain chromophoric groups linked to a reactive group such as monoor di-chlorotriazine, dior tri-chloropyrimidine or vinyl sulphone. Reactive dyes free from a sulphonic or non-chelated carboxylic acid group such as described in British patent specification 953,230 can also be used.

As examples of dyes which may be employed in carrying out this invention are mentioned the following- C.I. classification 13390 Acid Blue 92 19140 Acid Yellow 23 45190 Acid Violet 9 Solway Purple R 60730 Acid Violet 43 Brilliant Alizarine Milling Blue 61585 Acid Blue 80 Carbolan Violet 2RS 62165 Acid Violet 51 Carbolan Blue HR 62075 Acid Blue 138 Premetallized dyes:

Both 1:1 and 2:1 complexes e.g. Neolan Black 2R 15691 Acid Black 43 Mordant dyes, e.g.:

Solochrome Black 6RN 14640 Mordant Black 3 Acid Alizarine Black N 15690 Mordant Black 15 Solochrome Black F 26695 Mordant Black 5 Disperse dyes, e.g.:

Celliton Blue B 61500 Disperse Blue 14 Celliton Fast Blue FFB 62050 Disperse Blue 6 Celliton Blue 36 64505 Disperse Blue 31 Direct dyes, e.g.:

Melanthine BH 22590 Direct Blue 2 Diphenyl Fast Black B 27720 Direct Black 51 Diphenyl Brilliant Violet BC 27905 Direct Violet 51 Solvent dyes, e.g.:

Zapon Fast Violet R 15680 Coomassie Violet 2RS 45190 Solvent Violet 10 As will be seen from the above mentioned specifications, a large number of different solvents are known to be used in dyeing compositions and those mentioned can be used in carrying out this invention. Among the solvents which may be used in accordance with the present .invention are:

aliphatic alcohols, e.g. those containing 1-6 carbon atoms,

including cyclohexanol;

aralkanols, e.g. benzyl alcohol;

alkoxy alcohols e.g. 3-methoxybutanol, ethoxyethanol and methoxyethanol;

aliphatic ketones, e.g. ethyl methyl ketone and methyl isobutyl ketone; higher glycols, e.g. hexylene glycol; aliphatic esters, e.g. amyl lactate;

as well as ethanol 2-methoxyacetate, geraniol, Carbitols and digols, and tetraethyl urea. Carbitols are monoethers and monoesters of dihydroxyethyl ether.

As is known, the more miscible the solvent the greater the proportion that is to be used.

The dyeing composition may also contain further ingredients known in the art. For instance, in compositions intended for dyeing human hair there may be included thickeners, surface active agents or aliphatic acids, such as acetic or lactic acid. One may also include where the solvent is not miscible with water, a liquid miscible with both the water and solvent.

In a modification of the invention the material to be dyed is contacted successively with an aqueous solution or dispersion of the dye and also with a liquid organic solvent for the dye (either the said solution or solvent being applied first), the solid aromatic compound being dissolved in either the aqueous solution or in the organic solvent or in both of them.

In a further modification of the invention the material to be dyed is contacted successively with a solution of the dye in a liquid organic solvent for the dye and also with water (either the organic solvent or the water being applied first), the solid aromatic compound being dissolved in either the organic solvent or in the water or in both of them.

The following examples illustrate the invention. All percentages are by weight.

The dyeing compositions employed in the following examples each comprised an organic solvent, a solid aromatic compound (in solution in the composition), 1% dye, 1% monoethanolamine lauryl sulphate and the balance water. The pH of the dyeing composition in each case was about 4.

The dye in each of Examples 1 to 34 was the acid dye Solway Purple R 125 (C.I. 60730 Acid Violet 43).

In Examples 1 to 26 the amount of the solvent was in Examples 27-30, 5%; and in Examples 31-34, In Examples 1 to 9 the concentration of the solid aromatic compound was 2% and in Examples 10-34, 3%.

The solvent and solid aromatic compound used in Examples 1 to 34 are set out in Table I TABLE I Solid aromatic compound Benzolc acid.

Cinnamic acid. Methoxy phenyl-acetic acid. Salicylic acid.

p-Amino benzoic acid.

. Hippuric acid.

. Acetyl salicylic acid.

. Phthalic acid.

. Sulphanilic acid.

Solvent Resorciuol.

Hydroquinone.

. Thymol.

o-Amino phenol. p-Chloro phenol. p-Nitro-benzyl alcohol.

. Phenylurea.

...- m-Nitrobenzaldehyde. o-Anisaldehyde.

24dichloronitro benzene.

Benzyl alcohol- Benzoic acid. ....-do Salicylic acid.

-.. p-Amino benzoic acid.

-. Thymol. Benzoic acid. Salicylic acid. p-Aminobenzoic acid.

In Examples 35 to 40 the composition employed was the same as that in Example 27 except that the dye employed was Coomassie Dark Blue BL (CI. 50330 Acid Blue 61) and instead of benzyl alcohol the solvent was as set out in Table 11.

TABLE II Example: Solvent 35 Cyclohexanol. 36 3-methoxybutanol. 37 Ethyl methyl ketone. 38 Hexylene glycol. 39 Ethanol Z-methoxy acetate. 40 2-[( 8-ethoxy)-ethoxy]-ethanol.

41 Tetraethyl urea.

In Examples 42 to 52 the composition employed was the same as that in Example 31 except that the dye employed was as indicated in Table HI.

TABLE III Example Name of dye C.I. classification of dye 42 Coomassie Blue R.L 13390 Acid Blue 92. 43. Resorcine Brown 20170 Acid Orange 24. 44. Disulphine Blue 42045 Acid Blue 1. 45 Coomassie Voilet; 2R8 45100 Acid Violet 9. 46 Nigrosine 50420 Acid Black 2. 47 Neolan Black 2R 15691 Acid Black 43. 48.- Solochro'me Black GRN 14640 Mordant Black 3. 49. CellitonBiue B... 61500 Disperse Blue 14. 50- Melan thine BH.-. 22590 Direct Blue 2.

Coomassie Violet 212s I 45190 Solvent Violet Switches of human hair were dyed with each of the compositions ofithe above examples by immersing the switches for 10 minutes in the dyeing compositions at 25 C. They were then washed with water and dried. Switches of hair" were also treated in a similar manner with the corresponding compositions from which the solid aromatic compound had been omitted. In every case the intensity of the color of the hair was noticeably greater in the case of dyeings with the compositions set out in the tables than with those compositions from which the solid organic compounds had been omitted.

In Examples 53 to 55 materials other than human hair were dyed. The dyeing composition used in each case consisted of Percent Monoethanolarnine lauryl sulphate 0.3 n-Propanol 15.0 Benzoic acid 3.0 Solway Purple R 1.0 Water to 100.0%.

The materials used are indicated in Table IV.

The fibers were dyed by immersing them for 10 minutes in the dyeing composition at 25 C. They were then washed with water and dried. The intensity of color of the dyed fibers was in each case greater than that obtained using dyeing compositions of the same pH but containing no benzoic acid or containing in place of the npropanol and benzoic acid, 6% of benzyl alcohol.

What is claimed is:

1. A process for dyeing human hair attached to the head which comprises contacting the hair at a temperature below about 45 C. with an effective amount of a dyeing composition comprising an aqueous solution, suspension or dispersion of a direct dye and an organic solvent for the dye which solvent is liquid at the dyeing temperature and is selected from the group consisting of aliphatic alcohols, aralkanols, alkoxy alkanols, aliphatic ketones, hexylene glycol, aliphatic esters, tetraethyl urea and 2-(betaethoxy)-ethoxyethanol, the dyeing composition additionally comprising dissolved therein from about 1% to about 5% by weight of the composition of an aromatic compound which compound is solid at the dyeing temperature, acts to increase the rate of uptake of the dye by the hair and contains one phenyl or naphthyl ring.

2. A process as claimed in claim 1, in which the organic solvent is benzyl alcohol.

3. A process as claimed in claim 2, in which the aromatic compound is a carboxylic acid.

4. A process as claimed in claim 3, in which the carboxylic acid is benzoic acid.

(References on following page) References Cited FOREIGN PATENTS UNITED STATES PATENTS 918,597 2/1963 Great Britain. 12/1931 Kern et a1 X 1,227,621 3/1960 France. 1,296,934 5/1962 France.

1/1940 Krltchevsky 16788 1 I X 5 70,067 10/1958 France. 2/ 946 Heman (Addition to No. 1,138,955 11/1960 Bashford 1,159,331 2/1958 France.

5/1961 Seemuller 167-88 7/ 1965 Brechner 167-88 ALBERT T. MYERS, Primary Examiner 8/1965 Sherburne 10 v. c. CLARKE, Assistant Examiner 9/1965 Lecher et a1. 167-88 11/1967 Lerner et a1. 167-88

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1834314 *May 31, 1927Dec 1, 1931Du PontPrinting paste and process of producing the same
US2185467 *Oct 3, 1938Jan 2, 1940Rit Products CorpHair dyeing composition and method
US2394688 *Jan 7, 1944Feb 12, 1946American Viscose CorpMethod of dyeing
US2960381 *Sep 10, 1958Nov 15, 1960Courtaulds LtdDyeing of threads, filaments, fibres and the like
US2983651 *Dec 10, 1956May 9, 1961OrealDyeing of animal fibres
US3194735 *Feb 4, 1964Jul 13, 1965Warner Lambert PharmaceuticalHair coloring comprising a basic dye, a glycol and an amphoteric surfactant
US3203753 *May 31, 1961Aug 31, 1965Atlas Chem IndTextile dye carrier-emulsifier compositions
US3206363 *Aug 29, 1962Sep 14, 1965Clairol IncComposition and process for solvent dyeing with tetraloweralkyl ureas
US3352755 *Aug 4, 1961Nov 14, 1967Gillette CoAcid dye composition for human hair
FR70067E * Title not available
FR1138955A * Title not available
FR1159331A * Title not available
FR1227621A * Title not available
FR1296934A * Title not available
GB918597A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3619102 *Jun 7, 1968Nov 9, 1971OrealDyeing keratinic fibers with aqueous solutions of direct dyes and organic solvents
US3933422 *Apr 25, 1974Jan 20, 1976Avon Products, Inc.Non-staining keratinic coloring product
US4145413 *Aug 15, 1977Mar 20, 1979The Gillette CompanyArtificial skin darkening composition and method of using the same
US4185958 *Aug 18, 1978Jan 29, 1980Andree BugautHair dyes
US4873079 *Dec 14, 1987Oct 10, 1989Clairol IncorporatedWith cosolvents consisting of branched chain hydrocarbon diols and bis(hydroxyalkyl) cycloalkenes; better dye take
US6440175 *Jun 28, 2001Aug 27, 2002Stanley, Iii Virgil E.Mix or formulate a plurality of different hair color compositions. the kit includes a base composition or hair spray, a group of color concentrates, and a dispenser. one or more of the color concentrates is mixed with the base
DE2836300A1 *Aug 18, 1978Mar 1, 1979OrealFaerbemittel fuer keratinfasern
EP1555012A1 *Dec 21, 2004Jul 20, 2005Clariant GmbHHair dyeing composition containing anthraquinones
Classifications
U.S. Classification8/433, 8/435, 8/917, 8/616, 8/607, 8/598, 8/597, 8/594, 8/611, 8/613
International ClassificationD06P1/642, D06P1/653, D06P1/90, D06P3/14, D06P1/645, D06P1/92, D06P1/64, D06P1/651, D06P1/62, D06P1/649, D06P3/32
Cooperative ClassificationA61K2800/432, D06P1/6422, D06P1/65118, D06P1/628, D06P1/645, Y10S8/917, D06P1/6536, D06P1/924, A61K8/368, A61Q5/065, D06P3/14, D06P1/928, D06P1/65112, D06P1/6491, D06P3/32, A61K8/34
European ClassificationD06P1/92B2, D06P1/651B2, D06P1/62D, D06P1/92D, D06P1/645, D06P1/651B4, D06P3/32, D06P1/653D, D06P1/649B, D06P1/642D, D06P3/14, A61Q5/06D, A61K8/368, A61K8/34