USES OF CO-CRYSTALS

Abstract

The present invention discloses new uses of coloured co-crystals and associated salts formed by co-crystallization reactions in the dye, ink and paint industries. The present invention also provides novel co-crystals for use in, for example, the dye, ink and/or paint industries.

Claims

1. (canceled)

2. A hair dye, ink and/or paint composition comprising a coloured co-crystal formed from a first and a second coformer.

3-14. (canceled)

15. The hair dye, ink and/or paint composition according to claim 2 wherein a first component is selected from the group consisting of: p-phenylenediamine (PPD) or a derivative thereof, N-Phenyl-Para-Phenylene Diamine, 1,5-Naphthalenediamine, 4-lodoaniline, 1-anilinonaphthalene-8-sulfonic acid, 1,3-Dichloro-7-hydroxy-9,9-dimethyl-2(9H)-acridinone, 1,4-bis-p-cyanostyrylbenzene, 2-((E)-4-((E)-4-cyanostyryl)styryl)benzonitrile, 2,2′4(1E, 1′E)-1,4-phenylenebis(ethene-2,1-diyl))dibenzonitrile, 2-Methylbenzoxazole, 2,7-dichlorofluorescein, 2″,7′-bis-(2-carboxyethyl)-5-(and-6)-carboxyfluorescein 2,5-diphenyloxazole, 4-Dimethylamino-4′-nitrostilbene, 5(6)-Carboxyfluorescein, 5(6)-Carboxynaphtofluorescein, 5(6)-Carboxytetramethylrhodamine B, 5-(and-6)-carboxy-2′,7′-dichlorofluorescein, 5-(N-hexadecanoyl)aminoeosin, 5-Chloromethylfluorescein, 5-carboxyfluorescein, 6,8-difluoro-7-hydroxy-4-methylcoumarin, 6-carboxyrhodamine 6G, 7-hydroxy-4-methylcoumarin, Acridine (orange and yellow), Alexa Fluor, Alcian yellow GXS, Alizarin, Alizarin red S, Alizarin yellow GG, Alizarin yellow R, Anthoxanthin, Arylide yellow, ATTO, Auramine O, Azophloxin, Azo compound, Bilin, Bismarck, Bistre, Bone char, brown R, Bismarck brown Y, Brilliant cresyl blue, Calcein, Caput mortuum, Carmine, Chrysoidine R, Chrysoidine Y, Coumarin, Congo red, Crimson, Crystal violet, Doxorubicin, Diarylide pigment, Dragon's blood, Fluorescein, Fuchsin acid, epicocconone, Gamboge, Gentian violet, Indian yellow, Indigo dye, Janus green, Lissamine fast yellow, Marina Blue, Martius yellow, Meldola blue, Metanil yellow, Methyl orange, Methyl red, Methylene Blue, Monobromobimane, Monochlorobimane, Naphthalene black 12B, Naphthofluorescein, Naphthol green B, Naphthol yellow S, Naphthol Red, nile blue, nile red, Oxazin, Ommochrome, Orange G, Perinone, Phthalocyanine Blue BN, Phthalocyanine Green G, Pigment Yellow (10,16, 81, 83), Piroxicam, Quinacridone, Riboflavin, Rose bengal, Rose madder, Rylene dye, Sepia (color), Sudan II, Sulforhodamine, Titan yellow, Tyrian purple, Tropaeolin O, Tropaeolin OO, Tropaeolin OOO, Victoria blue 4R, Victoria blue B, Victoria blue R, and Xylene cyanol FF.

16. The hair dye, ink and/or paint composition according to claim 2 wherein the second coformer is selected from the group consisting of: carboxylic acid, alcohol, amines, aldehydes, nitro, nitroso, ketones, ethers, esters, amides, acetals, ketals, imide, nitrile, isonitrile, halo, acylhalide, nitroso, pyridine, sulfoxide, sulfinic acid, sulphonic acids, cyanates, isocyanates, thiols, thial, thione, thiocyanates, isothiocyanates, semicarbazones, thiosemicarbazones, ureas, thioureas, amides, phosphonic acids, phosphine, phosphate, phosphodiester, boronic acids, boronic esters, borinic acids and borinic esters functionalities.

17. The hair dye, ink and/or paint composition according to claim 16 wherein the second coformer is selected from the group consisting of aliphatic and aromatic mono, di or polycarboxylic acids and alcohols of variable chain lengths (e.g acetic acid, oxalic acid, malonic acid, maleic acid, lactic acid, tartaric acid, citric acid, fumaric acid, succinic acid, acetylenedicarboxylic acid, mesaconic acid, trans-acotinic acid, thiodiglycolic acid, diglycolic acid, glutaric acid, adipic acid, hexanoic acid, pimelic acid, suberic acid, octanoic acid, azelaic acid, sebacic acid, decanoic acid, undecanedioic, dodecanedioic, oleic acid, arachidic acid, stearic acid, palmitic acid, erucic acid, arachidonic acid, linoleic acid, linolenic acid, phthalic acid, isophthalic acid, terephthalic acid, benzenetricarboxylic acids, benzenetetrracarboxylic acids, benzenepentacarboxylic acids, benzenehexacarboxylic acid, disubstituted benzoic acids 3,5 dinitrobenzoic acid, phenylenediacetic acids, phenols, benzenediol, benzenetriols, benzenetetraols, benzenepentaols, benzenehexaols, and aliphatic alcohols containg one of more hydroxyl groups.

18. The hair dye, ink and/or paint composition according to claim 17 wherein the second coformer is selected from the group consisting of alcohols and ketones include flavonoids, such as flavones, flavanols, isoflavones, chalcones and catechins; terenoids and isoprenoids; naphthoquinones and anthraquinones; alkaloids, naphthoquinones and anthraquinones, naphthoquinone, juglone, lawsone, alkannin, anthraquinone and alizarin.

19. The hair dye, ink and/or paint composition according to claim 18 wherein the second coformer is Lawsone.

20. A coloured co-crystal for use as a hair dye formed from p-phenylenediamine (PPD) or a derivative thereof in combination with an alcohol or ketone.

21. The coloured co-crystal according to claim 20, wherein the alcohol or ketone is selected from the group consisting of flavonoids, flavones, flavanols, isoflavones, chalcones, catechins, terenoids, isoprenoids, naphthoquinones, anthraquinones and alkanoids.

22. The coloured co-crystal according to claim 20 wherein the alcohol or ketone is selected from the group consisting of naphthoquinones, anthraquinones, naphthoquinone, juglone, lawsone, alkannin, anthraquinone and alizarin.

23. The coloured co-crystals according to claim 20 formed from PPD or a derivative thereof and lawsone.

24. A coloured co-crystal for use as a hair dye formed from PPD, or a derivative cocrystallized with fumaric (FA), succinic (SA), glycolic, malonic, glutaric, thiodiglycolic (TDGA), adipic (AA), suberic (SubA) and azelaic (AzeA), sebacic (SebA), 1,3-phenylenediacetic, (1,3-PDAA), 1,4-phenylenediacetic, (1,4-PDAA) or trimesic (TMA) acids.

25. The hair dye, ink and/or paint composition according to claim 2, or coloured co-crystal according to claim 20, wherein the PPD derivative is selected from the group consisting of: p-toluenediamine; 2-chloro-p-phenylenediamine; N-phenyl-p-phenylenediamine; N-2-methoxyethyl-p-phenylenediamine; N,N-bis-hydroxyethyl-p-phenylenediamine; 2-hydroxymethyl-p-phenylenediamine; 2-hydroxyethyl-p-phenylenediamine; 4,4′-diaminodiphenylamine; 2,6-dimethyl-p-phenylenediamine; 2-isopropyl-p-phenylenediamine; N-(2-hydroxypropyl)-p-phenylenediamine; 2-propyl-p-phenylenediamine; 1,3-bis-(N-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol; and 2-methyl-4-dimethylaminoaniline.

26. A hair dye composition comprising a coloured co-crystal according to claim 20 or cocrystals of fluorescein and acridine, or a methanol solvate of 4-iodoanailine and 3,5 dinitrobenzoic acid, together with one or more hair dye formulation components.

27. A hair dye composition according to claim 26, wherein the one or more hair dye components is a wetting agent, emulsifying agent, surfactant, thickener, conditioner, pH adjuster, lanolin or lanolin derivative, cholesterol, pantothenic acid, an adjuvant or cosmetic additive.

28. A preformed hair dye solution comprising a formulation according to claim 2.

29. The coloured co-crystal according to claim 20, wherein the PPD derivative is selected from the group consisting of: p-toluenediamine; 2-chloro-p-phenylenediamine; N-phenyl-p-phenylenediamine; N-2-methoxyethyl-p-phenylenediamine; N,N-bis-hydroxyethyl-p-phenylenediamine; 2-hydroxymethyl-p-phenylenediamine; 2-hydroxyethyl-p-phenylenediamine; 4,4′-diaminodiphenylamine; 2,6-dimethyl-p-phenylenediamine; 2-isopropyl-p-phenylenediamine; N-(2-hydroxypropyl)-p-phenylenediamine; 2-propyl-p-phenylenediamine; 1,3-bis-(N-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol; and 2-methyl-4-dimethylamino aniline.

Description

DETAILED DESCRIPTION

[0056] The present invention will now be further described by way of example and with reference to the figures which show:

[0057] FIG. 1 shows (a) Colour change observed during the co-crystallisation reaction between (b) PPD and L and (c) Crystal structure of salt between PPD and L;

[0058] FIG. 2 shows (a) Comparision of PXRD patterns of phase pure materials formed between PPD and L by LAG (x), solution crystallization (y), with the simulated pattern obtained from their crystal structure (z). (b-d) Comparision of IR, DSC and TGA spectra of the materials obtained via solution and LAG;

[0059] FIG. 3 shows (a) Undyed hairs. Dyed hairs (with PPDL dye) after washing continuously in hot soapy solution for (b) 30 minutes and (c) 24 hours;

[0060] FIG. 4 shows the colour change observed during co-crystallisation of PPD with suberic acid;

[0061] FIG. 5 shows the Recognition pattern observed in the crystal structures of (a) PPD-FA, (b) PPD-SA, (c) PPD-TDGA, (d) PPD-AA, (e) PPD-SubA, (f) PPD-AzeA, (g) PPD-SebA (h) PPD-1,3-PDAA (i) PPD-1,4-PDAA (j) PPD-TMA

[0062] FIG. 6: (a) Undyed hairs. Dyed hairs after washing continuously in hot soapy solution for (b) 30 minutes and (c) 24 hours

[0063] FIG. 7 shows (a) Writing with PPD-SA ink immersed in hot water (70° C.) (b) Dried paper after 4 hour of hot water treatment (c) different coloured inks formed by cocrystallization between PPD and various acids; and

[0064] FIG. 8 shows the Deinking of paper by washing with methanol.

[0065] FIG. 9 (a) Undyed hairs. Dyed hairs after washing continuously in hot soapy solution for (b) 30 minutes and (c) 24 hours

EXAMPLE 1: PPD/LAWSONE CO-CRYSTAL DEVELOPMENT

[0066] We developed a new type of PPD based hair dyes by cocrystallization. Lawsone (L) was chosen as coformer. Lawsone is an orange coloured molecule and is present in henna. Our choice of coformer was based upon the fact that lawsone molecules bind well with the hairs and because of it henna is widely used as a hair dye (it imparts orange colour to the hairs). Henna is not only popular as a hair dye, but is also widely used for making henna tattoos, especially on palms and feet. Worldwide use of henna over skin, and that too for centuries, indicate that lawsone molecule is safe even for topical application. The safety of henna was recently confirmed by SCCS.

[0067] An attempt was made to form an adduct between PPD (colourless when freshly prepared) and lawsone (yellow in colour) by dissolving them in 1:1 molar ratio in methanol solution. The formation of adduct was first indicated by change of colour (FIG. 1 (a)). The blackish-brown solution so obtained was kept for slow evaporation and it resulted in the formation of blackish-brown crystals in 3 days. The crystal structure analysis revealed the formation of salt in the 1:2 molar ratio between PPD and L (FIG. 1 (b)) in which the molecules of PPD and lawsone interacted with each other by N.sup.+—H•••O.sup.− and N+—H•••O interactions (FIG. 1 (c)).

[0068] We attempted to form the adduct in phase pure form by liquid assisted grinding (LAG) of PPD and L in 1:2 for 60 minutes at 30 Hz in the presence of 50 μL of the methanol or by mixing their methanol solutions in the same ratio as that observed in the crystal structure. Comparison of the PXRD patterns of material obtained from LAG and solution crystallization with the simulated pattern of the crystal structure indicated that we were successful in obtaining the same adduct by both the techniques (FIG. 2a), which was further confirmed by IR, TGA and DSC. An attempt was made to scale up the production of PPDL adduct to 20 gm by LAG and solution crystallizations, which was successful.

EXAMPLE 2: HAIR DYING ABILITY OF PPDL

[0069] The dye obtained from co-crystallisation reaction between PPD and L in 1:2 molar ratio from methanol solution was tested for its dying performance. We chose grey hairs, which are considered to be toughest to dye (FIG. 3(a)). Hairs were dyed by immersing roughly 1 gm of hairs in 5 ml of supersaturated hair dye solution for 30 minutes, which resulted in reddish-brown hairs. Such saturated solutions were found to be containing around 0.75 g of PPDL per 10 ml of the solution. Supersaturated solutions may be obtained by just letting the solution evaporate under room temperature. We employed rotavapor to speed up this process.

[0070] The excess of hair dye was removed with the help of hot water. Dyed hairs were initially tested for its performance by stirring in hot soapy water maintained at 50° C., for 30 minutes. During this time the soapy water was changed 5 times. The PPDL hair dye worked very well and retained the colour (FIG. 3 (b)). In view of the initial product performance, we tested PPDL hair dye performance under extreme washing conditions for a longer period. Thus, dyed hairs were washed for 24 hrs by stirring in hot soapy water maintained at 50° C. During this washing, we changed the soapy water some 20 times. The 24 hr. washing experiment demonstrated that the hair dye was retained even under these extreme washing conditions (FIG. 3 (c)).

[0071] It is widely believed that the dye molecules interact with hairs by hydrogen bonds. (see for example Morel, O. J. X.; Christie, R. M. Chemical Reviews 2011, 111, 2537) Without wishing to be bound by theory, it is noted that the PPDL hair dye is a salt, which can form stronger charge-assisted hydrogen bonds with the hairs, as compared to currently marked hair dyes which can only form neutral hydrogen bonds. It is also noteworthy that this dye works even without the ammonia. In the currently marketed PPD-based hair dye products ammonia is added to open up the pores of the hairs, so that the big hair dye molecules can enter into the hairs. Since the molecules used in PPDL hair dye are much smaller, it is thought that they can enter through smaller pores, avoiding the need for use of ammonia.

[0072] As can be seen, the present invention provides hair dyes which are ammonia free and do not require H.sub.2O.sub.2 for colour generation. The exemplified hair dye shows a great colour fastness, and the dyed hairs retained their colour even after washing in hot soapy water for 24 hrs. The significance of this new class of hair dyes is further enhanced, due to recent reports relating the currently marketed PPD-based oxidative hair dyes with cancer (if they come in topical contact with the skin http://ec.europa.eu/health/scientific_committees/consumer_safety/does/sccs_o_094.pdf.).

EXAMPLE 3: CO-CRYSTALLISATION OF PPD WITH ORGANIC ACIDS

[0073] We cocrystallized PPD with various acids fumaric (FA), succinic (SA), thiodiglycolic (TDGA), adipic (AA), suberic (SubA) and azelaic (AzeA), sebacic (SebA), 1,3-phenylenediacetic, (1,3-PDAA), 1,4-phenylenediacetic, (1,4-PDAA) and trimesic (TMA) acids. In all the reactions, the formation of adduct was strongly indicated by colour change observed during all the cocrystallization experiments. A typical example demonstrating colour change observed during these cocrystallizations is as shown in FIG. 4. The cocrystallization reactions were initially carried out in 1:1 molar ratio between PPD and various acids from methanol solution. Single crystal X-ray diffraction measurements were taken and the molar ratio of PPD with various acids was confirmed. This ratio allowed synthesis of the products from the correct ratio of starting components.

[0074] All the co-crystals were structurally characterized using single crystal XRD. The analysis of their crystal structures revealed that all the co-crystallizations yielded salts by proton transfers from the acid to the PPD molecules (FIG. 5).

[0075] It has also been possible to make the various coloured cocrystals described above using a LAG route as mentioned in Example 1.

EXAMPLE 4: USE OF PPD/ORGANIC ACID CO-CRYSTALS AS HAIR DYES AND INKS

[0076] The dyes obtained from co-crystallisation reaction between PPD and various acids were tested for their dying performance. We chose grey hairs, which are considered to be toughest to dye (FIG. 6(a)). Hairs were dyed by immersing roughly 1 gm of hairs in 5 m of saturated hair dye solution and allowing it to remain in contact with the hair until the desired hair color has been attained. The excess of hair dye was removed with the help of hot water. Dyed hairs were initially tested for its performance by stirring in hot soapy water maintained at 50° C., for 30 minutes. During this time the soapy water was changed 5 times. The hair dyes worked very well and retained the colour. The dying performance of some of these dyes is as shown in FIG. 6 (b). We then tested the hair dyes under extreme washing conditions for a longer period. Thus, dyed hairs were washed for 24 hrs by stirring in hot soapy water maintained at 50° C. During this washing, we changed the soapy water some 20 times. The 24 hr. washing experiment demonstrated that the hair dye was retained even under these extreme washing conditions (FIG. 6 (c)).

[0077] We explored the potential of these coloured solutions obtained during cocrystallization reactions as inks. For this purpose the solutions were concentrated, simply by evaporation under room temperature for 2 days. These solutions can be added to writing implements and used as inks. A point of note is that these inks are resistant to water despite being in an ionised form; even copious amounts of water failed to make any measurable impact in the spread of the ink. To test the resistivity of the ink we tested our inks by immersing the text in hot water (70° C.) for 4 hours (see FIG. 7 (a)). Very encouragingly, this new product proved to be water resistant (see FIG. 7 (b)) and we were able to obtain inks of different colours and shades, as demonstrated in FIG. 7 (c). It is noteworthy to mention most of the marketed inks are a complex mixture containing following 8 components: (1) Colourants, (2) solvent, (3) dispersants, (4) polymeric resins, (5) humectants (retard premature drying), (6) antiforming agents, (7) wetting agents and (8) pH modifiers. The colourant are usually inorganic or organic dyes or pigments molecules and costs around 50% of the cost of the ink. We carried out SEM analysis of the blank paper to have a better insight into its structural features. The analysis revealed that the main components of the paper were cellulose fibres and CaCO.sub.3. CaCO.sub.3 is routinely used by the paper industry, mainly to make it white. Analysis of paper and ink indicated the possibility of formation of strong hydrogen bonds between cellulose fibres and ink. Again without wishing to be bound by theory, we believe that due to ionic nature of the ink, it may also form some ionic interactions with the CaCO.sub.3 present in the paper. It may be due to these two reasons that the ink binds strongly with the paper.

[0078] With the increase in the demand of the paper, there is a growing concern about the reclycing of paper. According to an estimate 1 tonne of recycled paper prevents around 17 mature trees from cutting. One way to achieve this goal is to design the inks which can be easily removed. We tested erasing our inks by simply washing the paper with methanol solvent. The results were very encouraging and the ink was removed to a great extent by briefly washing the paper with methanol (FIG. 8). The ease with which the ink has been removed is remarkable and very significant given the drive to more ecologically friendly means of manufacture and processing.

[0079] The above describes the ability of forming inks by cocrystallization reactions. The technology bypasses synthetic pathways for the generation of coloured molecules. The inks were smooth to use and showed a great water resistance. Analysis of the crystal structure of the co-crystals within the ink releaved a proton transfer from acids to the PPD molecules, forming salt. The strong interaction between ink and paper, which also led to water-resistant behaviour might be linked to the possibility of formation of strong hydrogen bonds between ink components and cellulose fibres, as well as the possibility of ionic interactions between ions of ink and CaCO.sub.3.

EXAMPLE 5: USE OF OTHER COLOURED CO-CRYSTALS AS HAIR DYES

[0080] In an analogous manner to Examples 3 and 4, further coloured co-crystals were prepared using various combinations of co-crystal forming molecules and the resulting coloured co-crystals tested for their hair dying ability.

[0081] Coloured co-crystals were formed from the following mixtures of molecules, with the molar ration indicated in brackets: [0082] NPPPD;DGA=N-Phenyl-Para-Phenylene Diamine+Diglycolic acid (1:1) [0083] NPPPD;FA=N-Phenyl-Para-Phenylene Diamine+Fumaric acid (1:1) [0084] 1,5-DAN;MA=1,5-Naphthalenediamine+Malonic acid (1:1) [0085] 1,5-DAN;DGA=1,5-Naphthalenediamine+Diglycolic acid (1:1) [0086] 1,5-DAN;GA=1,5-Naphthalenediamine+glutaric acid (1:2)

[0087] In addition we also tested the dyeing potential of already known coloured cocrystals e.g. of [0088] F;Acr.=Fluorescene+Acridine (1:2) [0089] 4-IA;3,5-DNBA=4-lodoaniline+3,5-Dinitrobenzoic acid+methanol (2:2:1)

[0090] Solutions comprising the coloured co-crystals resulting from the above co-crystallisation reactions were used to dye hair and the results are shown in FIG. 9. As can be seen from FIG. 9, a variety of coloured co-crystal solutions, in addition to the PPD/FA solution described above, were made by the present inventors and tested for their hair-dying ability. These additional coloured co-crystal solutions were all capable of dying grey-hair in a variety of colours, ranging from yellow to brown/black. The F/Acr co-crystal solution even provided the dyed hair with a fluorescent property, which some users may find appealing. The various coloured co-crystal solutions also displayed significant colour fastness, as there was little de-colouration following washing.

[0091] Surface analysis of the dyed hair revealed no significant change in the surface properties of the hairs after dyeing indicating that these dyes are not harsh on the hair surface.

[0092] Scale-up: From an industrial prospective, scalability and ease of processing are very important factors. Considering this in mind, a cocrystal hair dye (PPD-SebA) was chosen for scale up, based upon the cost and availability of the chemicals. The system was scaled up to 275 g scale both by LAG and solution methods, as discussed herein. The materials obtained from LAG (pinkish-white) and solution crystallizations (dark bluish-black) differ in color, but PXRD analysis shows (data not shown) that the products of both these methods are the same.

[0093] Supramolecular hair dye formulation: After bulk preparation, we attempted to formulate the PPD-SebA cocrystal into a formulation that could be applied to hairs directly by potential customers. For this purpose, 4 ml of a concentrated solution of PPD-SebA in methanol was diluted with the addition of 2 ml of water to form a solution. To this 6 g of solid PPD-SebA (obtained from solution crystallization from methanol) was added to form a paste. During the paste formation the mixture was kneaded to break up the solid that had agglomerated. This paste was used to dye wet grey hairs (soaked in water for 2 minutes to swell the hair) for 30 minutes. The excess hair dye, which was adhering to the surface of the hairs, was easily recovered by rubbing the hairs between the finger tips. The dyed hairs were tested for their dying performance by washing them 25 times with soapy water and found to retain the colour. To investigate the reusability of the cocrystals for dying, 3 g of the recovered material was again converted to a paste by adding 1 ml of water and 2 ml of concentrated solution of PPD-SebA. Dyeing was done for 30 minutes, which was followed by 25 washings with soapy water. The dyeing performance of the recovered material was same as that of dye used for the first time. It is noteworthy to mention that conventional oxidative hair dyes are not reusable and any hair dye left after use is simply discarded.

[0094] Binding Forces: Hair dye performance is determined by the binding forces between hairs and dye. The dye molecules primarily bind the hairs using hydrogen bonds. Hair dye companies aim at increasing the strength of these hydrogen bonds for better product performance. The hair dyes presented herein are ionic and hence have the potential to form stronger charge assisted hydrogen bonds with the hairs in comparison to the neutral molecules formed via the oxidative reaction.

[0095] Potential of cocrystals to form a range of colors (color palette): One of the prime requirements of the hair dye industry is to produce a range of colors. The oxidative hair dye (OHD) industry relies on changing the dye precursor-coupler combination to achieve the same. The precursors and couplers are chosen in such a way that they can form the more conjugated colored end product. Unfortunately, OHD industry is limited in terms of the number of approved safe molecules (around 100) which they can use as dye precursors and couplers. The present hair dyes may have an advantage over OHDs in terms of the number of safe molecules (thousands of safe coformers for the hair dyes which can be chosen from EAFUSand GRAS lists).