DE19621966A1 - Use of natural or nature-identical synthetic dyes for the temporary marking or coloring of solid and liquid materials - Google Patents

Abstract

The use of natural colorants or synthetic colorants identical to natural ones selected from the group chlorophyll, flavonoids, retinoids, betalains, carotinides or plant extracts containing these colorants, their natural or synthetic derivatives or mixtures of the colorants, plant extracts containing them or their natural or synthetic derivatives, for the temporary marking or colouring of solid or liquid materials except for foodstuffs.

Description

The invention relates to the use of natural or natural identical synthetic dyes or pigments for the past going marking or coloring of solid or liquid Ma terialien. Furthermore, the invention relates to inks, cheeks and paints containing dyes selected the group chlorophyll, flavonoids, retinoids, betalaine, Carotenoids or plant extracts containing these dyes, their natural or synthetic derivatives, or mixtures of the dyes, the dye-containing plant extracts or their natural or synthetic derivatives.

Natural dyes such as carotenoids, chlorophyll, anthocyanins, Retinoids, betalains or flavonoids are widely used in nature spreads. They color in nature z. As fruits, anthers, pollen, Roots, sprout, leaves and flowers. Carotenoids are widely available use in the coloring of foods such as butter, margarine, Cheese, salmon and fruit juices.

Especially nature-identical synthetic carotenoids such as β-carotene, β-apo-8-carotenal, cantaxanthin, citranaxanthin or astaxanthin are used in the food sector in the form of special formulations used for permanent coloring.

Synthetic dyes or pigments come because of their Ge fastnesses such as their lightfastness for a temporary marking or coloring is out of the question. They are in usually also not readily biodegradable or have allergenic effect.

The high light fastness of the synthetic dyes is in eini areas a problem. For example, children paint with felt pencil on paper, it always comes back to undesirable Soiling of other items such as tablecloths, tables, Chairs, upholstery, rugs or children's clothing the felt pen colors. A cleaning of the soiled objects or clothing is complex and usually not completely possible, so that stains remain. Since the felt pens also often in the Mouth be plugged, the colors must be non-toxic.  

In medicine, the surgical field is a colored Desin fektionslösung disinfected several times in succession and thereby marked. The deep penetration of the skin disappears only after several days to weeks by gradual Ab skin the skin. Moreover, it is disadvantageous that the color substances are generally not safe.

It was therefore the task of a dye for temporary Mar. cation or coloring, which is non-toxic, ecologically harmless, biodegradable and no al has a lerogenic effect.

It has now been found that natural or nature-identical syn thetic dyes have the desired advantageous properties have and for a temporary marking or coloring of solid or liquid materials are suitable.

Natural or nature identical synthetic in accordance with the invention Stable dyes are, for example, the following dyes:

• - Chlorophyll such as chlorophyll a, b, c, d, Bacteriochlorophyll a and their various chlorophyll-protein complexes;
• - Flavonoids are z. Anthocyanidins, chalcones, flavanones, Flavones, flavonols, isoflavonoids, their glycosides and earth alkali or alkaline salts such as pelargonidin, cyanidin, delphi nidin, päonidine, petunidin, malvidin, hirsutidine, tuberidin, Apigenidine, aurantinidine, luteolinidine, rosinidine, muningin, Biochanin, prunetin, promiferin, cladrin, chrysin, galangin, Gossypetin, Apigenin, Myricetin, buteolin, Kämpferol, Morin, Robinetine, Durmillone, Derrusnin, Chrysin, Baicalein, Prime tin, wogonin, aluetin, sericetine, acetacetin, populin, dacty lin, tamarixetin, spirosides, gardenin, cannin, naringin, Ficinin, hesperidin, diosmin, quercetin, primuletine, fisetin, Rhoifolin or Selinone (see Handbook of Naturally Occurring Compounds Vol. I, Eds. Devon, T.K., Scott A.J., Academic Press Inc. 1975: Flavone p. 117-170, isoflavonoids p. 179-189, Bi flavonoids p. 191-205, anthocyanidins p. 207-213);
• Retinoids such as retinol, retinal, retinoic acids, retrovitamin A, their double bond isomers, their esters (preferably acetate, Propionate, palmitate), their glycosides, their galactosides, theirs Ethers, their amides or their synthetic derivatives (D.L. New ton, W.R. Henderson and M.B. Spur, Cancer Research 40, 3413-3425);  
• Betalines like Betacyane, Betaxanthine, Betanin and theirs free aglyca;
• - carotenoids such as carotenes or xanthophylls. As an an example are β-carotene, lycopene, lutein, astaxanthin, citranaxan thin, canthaxanthin, zeaxanthin, bixin, narbixin, capsorubin, Neurosporaxanthin, β-apo-8-carotenal, violaxanthin, crypto xanthine, neoxanthine, zeinoxanthin, myxoxanthin, echinenone, Fucoxanthin, capsanthin, β-apo-8-carotenoic acid ethyl ester, α-carotene, γ-larotin, δ-carotene, ξ-carotene, rubixanthin, Plec taniaxanthin, flavoxanthin, phytofluene, azafrin, crocetin, Crocin, Neurosporin, α-Zeacarotene, β-Zeacarotene, Bacterioru bin, decaprenoxanthin, diadinoxanthin, adonirubin. In Carotenoids as Colorants and Vitamin A Precursors (Ed. J.C. Bauernfeind, Academic Press, 1981: 883-916) or Carotenoids (Vol. 1A, Eds. Britton G., Liaaen-Jensen S., Pfander H., 296-316, Vol. 1B, 47-61, 1995) become further carotenoids described, which are used in the invention.

Preference is given to the marking or coloring according to the invention Carotenoids such as carotenes or xanthophylls are used. Especially preferred are β-carotene, β-apo-8-carotenal, citranaxanthin, Canthaxanthin, astaxanthin, bycopin, zeaxanthin, bixin, norbixin, butein, capsorubin, capsanthin or neurosporaxanthin. Very particularly preferred are synthetically produced Carotenoids such as β-carotene, β-apo-8-carotenal, β-apo-8-carotenoic acid reester, citranaxanthin, canthaxanthin, astaxanthin and zeaxan thin. In Paust (Chimia, 48, No. 11, 1994: 494-498) a Overview of the different carotenoid syntheses given.

For the marking and coloring according to the invention can Advantageously plant extracts, immediately after digestion the corresponding plants or parts of plants without further Rei or after purification of the natural dyes or pigments are used. The dyes can be in the form of ih rer crystals or natural derivatives z. B. as glycosides or bound to proteins and / or lipids or as free color substances after cleavage z. As the sugar residues or after chemical Modification or derivatization, for example in the form of synthetic isomers, glycosides, esters, ethers or amides or other derivatives.

Plant extracts, for example, by extraction of the Plant material with hot water or solvent Herge be made or mortar the plant material with quartz sand or homogenize the material with a blender and on  closing extraction with water or solvent z. Eg ace clay, ethanol, ether, ethyl acetate or MTB.

Naturidenti are also suitable for the inventive use synthetic dyes or pigments such as flavonoids, reti noide, betalaine or carotenoids and / or their crystals or Derivatives such as their esters, diesters, ethers, thioethers, polyethers, Amides, amines, glycosides, lipids, protein conjugates, phosphates, Carbonates, urethanes, sulfoxides, sulfones, sulfates, nitriles, Acrylates, urea, seleno or halogen derivatives or Ein terminations z. In dextrins.

The dyes or pigments from the chemical synthesis or from Plant extracts may be used directly or after formulation become. Among formulations are for the inventive Use of optimal application forms such as Mikroni sate, the z. B. produced by precipitation processes (EP-A-0 065 193) and dye particles smaller in size 1 micron, or solubilizates, which after z. EP-A-0 055 817 were made to understand. They are preferably for one Use in aqueous systems, since they are water-soluble or are water-miscible. They are therefore more advantageous wise for aqueous pickling, emulsion paints, lacquers on water base or aqueous pesticide formulations. The durability of the Dyes is less of the formulation than rather affected by the application. Without a formulation, the Dyes directly or in organic solution in solvent containing systems such as baking or pickling.

The formulated dyes or pigments contain advantage conveniently adjuvants such as powdered or granular carriers protective colloids such as pectins, lipids, gelatin, lecethine, Gum arabic, dextrins, partially hydrolyzed soy protein or Ca emulsifiers, solvents, dispersants, wetting agents, Stabilizers, defoamers, viscosity regulators, hydrophobicity agents, antioxidants such as 2-aminobenzenethiol, t-butylhy droxyanisole, t-butylhydroxytoluene, p-toluidine, 1,8-diaminonaph thalin, phenyl-α-naphthylamine, 4-aminodiphenylamine, N, N'- Diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydro cuinolin, 1-phenylsemicarbazide, phenothiazine, vitamin E or Vi tamin C, and optionally other formulation auxiliaries.

By the appropriate choice of excipients or their combination can the instability of the dyes or pigments and their Influence the color tone in the desired way, d. H. reinforce or if necessary mitigate. For example, by adding of antioxidants prolong the duration of staining. Also  by the addition of film formers, for example in inks can the duration of staining be extended.

Particularly suitable are formulations in which the dye or the pigment in aqueous phase in very finely divided form lies. Formulations of this kind are used, for example, for Carotenoids are described in EP-A-0 055 817 and EP-A-0 065 193.

In the formulation according to EP-A-0 055 817 one adjusts Solubilizate of β-carotene in water by adding a dispersion heated by β-carotene in a nonionic emulsifier, so that Forms a molecular disperse solution by addition of Water produces mixed micelles of β-carotene and the emulsifier.

According to EP-A-0 065 193, β-carotene is rendered water-miscible Solvent dissolved in the presence of a protective colloid and a Subjected to mixing chamber micronization. It creates a colloid disperse carotenoid formulation.

Also advantageously suitable are formulations, wherein the carotenoids are first dissolved in oil and then in an emulsifier / water mixture are stirred and so in fine emulsified form.

All formulation types can then be spray dried and then before use z. B. be redispersed in water.

Read by appropriately grinding the dye particles or crystals also, as with the various types of formulation for a marking or coloring advantageous particle or Create crystal sizes. Advantageous particle sizes are in Range </ = 10 μm, particularly advantageous below 1 μm, very special This is advantageous below 0.1 microns.

The dyes used in the invention are therefore so good suitable for temporary marking or coloring because they are resistant to external influences such as temperature, radiation effect, for example UV light or daylight or exposure of oxidants such as Luftsauersoff sense are faint and completely fade.

Usually they are yes after whether they are free or formulated Dyes can be used within a few hours up to completely faded in a few days or weeks.  

For example, the dyes bleach in emulsion paints within hours under sunlight exposure.

If the dyes are used in baking, they bleach For example, on wood depending on the light and light intensity within 1 to 7 days. Dyes used in inks for Board markers are used, decolorize on the white, rewritable tablet within a few hours to one Day. The dye lines can be used at any time without leaving any traces leave with a cloth or sponge to be removed.

According to the invention materials are temporarily marked or colored, which are not otherwise dyed for this purpose.

For coloring, the synthetic dyes and pigments or the dye or pigment containing plant extracts directly, after derivatization or formulation or in any Blends between the different synthetic colors substances, pigments, plant extracts and / or derivatizations or formulations are used. Preference is given to colloiddis perse formulations of dyes. These formulations have proven especially in carotenoids.

According to the invention, the dyes or pigments are used in Inks, d. H. in writing fluids, in addition to the aqueous solution Dye contains very little or no binder, for Fountain pens, ink pens, ballpoint pens, ball pens, Fiber or felt pen or for inkjet printers, or in Showering, d. H. in writing fluids containing pigmentation mung or a greater amount of binder-containing dye solution contain. Crayaw crayons can be used with dye formulations in Be stained powder form.

Further expedient uses of the unstable dyes and Pigments are baking, baking or electrophoretic Coating of metal, ceramics, porcelain, stone, wood or pla are suitable; Paints such. Water, dispersion, Oil, synthetic resin or silicate paints for painting, spraying, dew flooding or electropheretic coating; stamp colors for example, ink pads, ribbons, copy paper or Color towels; Printing inks for, for example, high, low and low and printing in book, offset, screen, flexo and gravure printing rich.  

According to the invention, furthermore, the unstable dyes are used or pigments for marking or coloring in the leather, Textile, wood, paper or wallpaper production.

Advantageously, the dyes or mixtures thereof used there for coloring, where the intrinsic color of the materials a clear mark by the dyes of the invention allows.

Further examples of use according to the invention are the short-term term marking of surgical fields by means of dye enthal tender disinfectant solution or colored pencils on the skin or the temporary coloring of plant protection product or fertilizer to control the already treated area, the mark in Packaging area of labels, the packaging film a perishable product, so that a quality con troll the product by fading the unstable color fabric or pigment in the labels, foil or pro in case of improper storage (eg long exposure to light or air) Temperature exposure) is possible.

The dyes in the labels, foils or in the product show that way the integral load of the product by the degree of its ver Pale. Likewise one can use such labels to the light incident on a planting over a longer period of time easy to measure. For this purpose, the colored label ge impregnated with water and at a suitable place within the Planting attached.

Another application is to mix with other unstable or stable real colors. In real Far Then you get a color change by fading the Dyes.

Like the formulations, depending on the matrix to be stained, you can also For example, carotenoids directly to achieve a transient use existing coloring. The light instability of carotenoids can be used to advantage the burden of materials which are sensitive to sunlight and ver scent. Such a material is for example spinnaker nylon, which embrittles after a certain period of use and tearing inclines. By staining the nylon fiber with carotenoids can be Achieve a coloring that reduces the burden of the material through it indicates slow fading.  

The effect of bleaching can be beneficial for other applications be used. So it is possible for writers to label To produce boards, the presentation purposes only for a short time be described and cleaned with a dry fleece can. When using, for example, β-carotene as a pigment is the disturbing, permanently coloring abrasion of pigments ver avoided. Furthermore, β-carotene can be used in foliar pencils be used for explaining captions of slides during a presentation can be used. After a short storage time the additional caption has disappeared and the on wender has his professional-looking original film again.

The colloidally disperse carotenoid formulations described above can be after drying in a water-dispersible powder convict. From this powder can be by rising with water make an ink that is viscous enough for use in ball is writing.

Further uses of the dyes according to the invention are Kenn Drawings of the pattern in the textile and leather area for example, corresponding ballpoint pens or felt pens instead of the usual tailor's chalk, the first by an after treatment must be removed, the addition of the dyes to Cleaning, hygiene or impregnation sprays for temporary Labeling and thus control of the treated or purified Field or wildlife marking to study their Le bensgewohnheiten. The dyes can also be used for flow studies in rivers, streams or in the air or to mark underwater dischen water courses or glaciers and thus enlightenment of their Course and their migration can be used.

The following examples serve to further illustrate the Invention without restricting it in any way.

Examples example 1

A commercial felt-tip pen is used with .beta.-carotene solubilisate Weight concentration of 4% filled. The solubilizate has a average particle size of the β-carotene particles of about 20 nm. Due to this small particle size of the dye is uniform picked up by the absorbent web that holds the ink. The so filled felt pen results in a uniform orange-yellow Line. To proof the bleaching with this felt pen a Surface of approx. 30 mm by 30 mm evenly coated and the Color of this area measured as a function of exposure time.  

The exposure source is a Abmusterungskammer with the Illuminant D65, for reference will be the same piece of paper, however used an unstained area.

The color values thus obtained are converted into color distances ΔE * (CIELAB system) and plotted as a function of time. The results of this application are shown in Fig. 1 (fading of felt pen marks on paper under illumination with D65 light).

Example 2

A commercial white board becomes with the felt-tip pen after Bei game 1 described. The stroke disappears overnight. It ver remains on the board a thin, colorless coating of the used Solubilizer, which does not disturb the further labeling, but in cleaning is beneficial because it is a nonionic emulsifier. In addition, the obtained Stroke immediately again with the belonging to the panel fleece ent be removed.

Example 3

As in Example 1, β-carotene solubilizate is used. The solubilizate is, however, doctored onto paper to obtain a uniform, extremely intense color. The dyed paper is bleached again under D65 light and the color distance to an untreated paper surface is noted as a function of time (see FIG. 2). It is observed at the beginning of the bleaching Ver a delay, which is due to the fact that the staining was already in the saturation color value of the solubilizate. Thereafter, as with the felt pen stroke, a rapid bleaching is again achieved until no color difference to the untreated paper is present.

Example 4

A commercial ball pen is emptied and the ink through Substitutes β-carotene solubilisate. You get a uniform Stroke without gradient on the paper, so that with the pen very good at writing. The dark yellow font fades overnight.

Example 5

100 g of commercial emulsion paint for woodchip wallpaper who the stained with 0.06 g of a 4% β-carotene solubilisate (24 ppm β-carotene in the paint). This gives a clear yellow color. The color obtained in this way is applied to woodchip wallpaper and then the color difference between this surface and a reference surface without β-carotene coloration are determined. In order to determine the color difference, the reflection is measured and the ΔE * calculated according to CIELAB. The values obtained are listed in the table below and in Fig. 3 (bleaching of coated with β-carotene solubility Rauhfasertapete) is provided.

Time [hours] AE * 1 5.96 2 2.94 3 1.65 4 1.05 5 0.86 6 0.82 7 0.82 8th 0.85 9 0.83

The remaining residual color distance of 0.8 is in the range of Reproducibility of the paint job and is essentially up attributed to the rough structure of the rough-hued wallpaper.

Example 6

Commercially available Desmodur / Desmophenlacke or acid hardening PV varnishes were labeled with β-carotene solubilisate as in Example 5 ben, colored. For the staining of polyurethane varnish was the β-carotene Solubilisat previously diluted with a solubilizer (staining as example 5). With the baking wooden buttons were painted. The color does not fade to the level within a week painted control buttons.

Claims (14)

1. Use of natural or nature-identical syntheti dyestuffs selected from the group chlorophyll, Fla vonoids, retinoids, betalains, carotenoids or this color containing plant extracts, their natural or synthetic derivatives, or mixtures of the dyes, the dye-containing plant extracts or their na natural or synthetic derivatives for temporary Marking or coloring of solid or liquid Materia except food. 2. Use according to claim 1, characterized in that one used as a dye carotenoids. 3. Use according to claims 1 or 2, characterized gekennzeich net, that as carotenoids carotenes or xanthophylls used. 4. Use according to claims 1 to 3, characterized net, that the dyes in the form of their crystals, solutions or aqueous solutions unbound or bound to proteins, Lipids or sugars used. 5. Use according to claims 1 to 4, characterized net, that the dyes in colloidally disperse Formulierun gene with particle sizes in the range of less than or equal 10 μm used. 6. Use according to claims 1 to 5, characterized that the dyes in medicine, in plant protection, in the Textile, leather, hygiene, plastic, wood, paper or Used packaging material area. 7. Use according to claims 1 to 5, characterized that the dyes in inks, paints, varnishes, paints, Stamp or ink used.   8. inks or inks containing dyes selected from Group chlorophyll, flavonoids, retinoids, betalaine, Carotenoids or plant extracts containing these dyes tract, their natural or synthetic derivatives, or Mixtures of the dyes containing the dye Plant extracts or their natural or synthetic Derivatives. 9. paints containing dyes selected from the group Chlo rophyll, flavonoids, retinoids, betalains, carotenoids or these dyes containing plant extracts whose naturli che or synthetic derivatives, or mixtures of the color substances containing the dye-containing plant extracts or their natural or synthetic derivatives. 10. paints containing dyes selected from Group chlorophyll, flavonoids, retinoids, betalaine, Carotenoids or plant extracts containing these dyes tract, their natural or synthetic derivatives, or Mixtures of the dyes containing the dye Plant extracts or their natural or synthetic Derivatives. 11. Use according to claims 1 to 7, characterized gekennzeich net, that one uses the dyes in clearcoats. 12. Use according to claims 1 to 7, characterized gekennzeich net, that the dyes for coloring Disperse Far ben used. 13. Use according to claims 1 to 7, characterized gekennzeich net, that the dyes as inks or inks used. 14. Use according to claims 1 to 7, characterized net, that one labels or packaging materials from ver colors of common products.