PATTERNING OF NATURAL PRODUCTS

Abstract

A method is described for creating a pattern on a natural material of human or animal origin. In embodiments, the method deposits a liquid treatment composition including at least one acid on a natural material, which comprises calcium carbonate.

Claims

1. A method of creating a pattern on a natural material of human or animal origin, the method comprising the following steps: a) providing the natural material of human or animal origin, wherein the natural material comprises at least one external surface comprising calcium carbonate; b) providing a liquid treatment composition comprising at least one acid; and c) applying the liquid treatment composition onto the at least one external surface of the natural material to form the pattern.

2. The method of claim 1, wherein the natural material is selected from the group consisting of a reptile eggshell, a bird eggshell, a monotreme eggshell, a tooth, a bone, a tusk, ivory, a pearl, nacre, a mollusc shell, a cuttlebone, a gladius, a corallite, a crustacean exoskeleton, or a calcified fossil.

3. The method of claim 1, wherein the natural material comprises the calcium carbonate in an amount at least 1 wt.-%, based on the total weight of the natural material.

4. The method of claim 1, wherein the at least one acid is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid, sulphamic acid, tartaric acid, phytic acid, boric acid, succinic acid, suberic acid, benzoic acid, adipic acid, pimelic acid, azelaic acid, sebaic acid, isocitric acid, aconitic acid, -propane-1,2,3-tricarboxylic acid, trimesic acid, glycolic acid, lactic acid, mandelic acid, acidic organosulfur compounds, acidic organophosphorus compounds, HSO.sub.4.sup., H.sub.2PO.sub.4.sup. or HPO.sub.4.sup.2, being at least partially neutralized by a corresponding cation selected from Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.2+ or Ca.sup.2+, and mixtures thereof.

5. The method of claim 1, wherein the liquid treatment composition further comprises a surfactant, an ink, a dye, fluorescent dye, a phosphorescent dye, an ultraviolet absorbing dye, a near infrared absorbing dye, a thermochromic dye, a halochromic dye, metal ions, transition metal ions, magnetic particles, or a mixture thereof.

6. The method of claim 1, wherein the liquid treatment composition comprises the at least one acid in an amount from 0.1 wt.% to 100 wt.-%, based on the total weight of the liquid treatment composition.

7. The method of claim 1, wherein the pattern is a one-dimensional bar code, a two-dimensional bar code, a three-dimensional bar code, a security mark, a label, a number, a letter, an alphanumeric symbol, a logo, an image, a shape, a design, a braille marking, or a combination thereof.

8. The method of claim 1, wherein the liquid treatment composition is applied by spray coating, inkjet printing, offset printing, flexographic printing, screen printing, plotting, contact stamping, rotogravure printing, spin coating, reverse gravure coating, slot coating, curtain coating, slide bed coating, film press, metered film press, blade coating, brush coating and/or a pencil.

9. The method of claim 1, wherein the method further comprises a step d) of applying a protective layer and/or a printing layer above the pattern.

10. A natural material of human or animal origin comprising a pattern obtained by the method according to claim 1.

11. The natural material of claim 10, wherein the pattern is a hidden pattern, which is invisible when viewed at a first angle relative to the at least one external surface of the natural material, and visible when viewed from a second angle relative to the at least one external surface of the natural material.

12. The natural material of claim 10, wherein the pattern differs from the at least one external surface in surface roughness, gloss, light absorption, electromagnetic radiation reflection, fluorescence, phosphorescence, magnetic property, electric conductivity, whiteness and/or brightness.

13. The natural material of claim 10, wherein the pattern comprises a security feature and/or a decorative feature and/or a labelling.

14. The natural material of claim 10, wherein the pattern is a tactile pattern.

15. A tactile application, braille application, labelling application, security application, an overt security element, a covert security element, microlettering, a micro image, a decorative application, an artistic application, a visual application, or a packaging application, comprising an effective amount of the natural material according to claim 10.

16. The method of claim 3, wherein the calcium carbonate is present in the natural material in an amount selected from the group consisting of at least 5 wt.%, at least 10 wt.%, at least 25 wt.%, and at least 50 wt.%.

17. The method of claim 6, wherein the at least one acid is present in an amount selected from the group consisting of 1 wt.% to 80 wt.%, 3 wt.% to 60 wt.% and 10 wt.% to 50 wt. %.

18. The method of claim 8, wherein the liquid treatment composition is applied by inkjet printing or spray coating.

19. The natural material of claim 13, wherein the security feature and/or decorative feature and/or labeling are selected from the group consisting of one-dimensional bar code, a two-dimensional bar code, a three-dimensional bar code, a security mark, a label, a number, a letter, an alphanumeric symbol, a logo, an image, a shape, a design, and a combination thereof.

20. The natural material of claim 14, wherein the tactile pattern is a braille marking.

Description

DESCRIPTION OF THE FIGURES

[0106] FIG. 1 shows a digital image of a white and a brown chicken egg shell, on which a pattern in form of a logo has been formed using the method of the present invention.

[0107] FIG. 2 shows a digital image of a brown chicken egg shell (top) and a white chicken egg shell (bottom), wherein on both egg shells a pattern in form of a QR-code has been formed using the method of the present invention.

[0108] FIG. 3 shows a scanning electron microscope (SEM) micrograph of a section of a QR-code formed on a chicken egg shell by the method of the present invention.

[0109] FIG. 4 shows a scanning electron microscope (SEM) micrograph of a cross section of a pattern formed on a chicken egg shell by the method of the present invention.

[0110] FIG. 5 shows a digital image of a quail egg shell, on which a pattern in form of a logo has been formed using the method of the present invention.

[0111] FIG. 6 shows a digital image of the nacre-coated side of an abalone shell, on which a pattern in form of a logo has been formed using the method of the present invention.

[0112] FIG. 7 shows a scanning electron microscope (SEM) micrograph of a section of a logo formed on the nacre-coated side of an abalone shell by the method of the present invention.

[0113] FIG. 8 shows a digital image of a bone sample, on which a pattern in form of a logo has been formed using the method of the present invention.

[0114] FIG. 9 shows a scanning electron microscope (SEM) micrograph of a section of a logo formed on a bone sample by the method of the present invention.

EXAMPLES

[0115] In the following, measurement methods and materials implemented in the examples are described.

1. Methods

[0116] Digital Images

[0117] Digital images of the prepared samples were recorded with an EOS 600D digital camera equipped with a Canon Macro lens, EF-S 60 mm, 1:2.8 USM (Canon Japan).

[0118] Scanning Electron Microscope (SEM) Micrographs

[0119] The prepared samples were examined by a Sigma VP field emission scanning electron microscope (Carl Zeiss AG, Germany) and a variable pressure secondary electron detector (VPSE) with a chamber pressure of about 50 Pa.

2. Materials

[0120] Natural Materials

[0121] The tested substrates were: chicken egg shells (white, brown), quail egg, abalone shell, and bone.

[0122] Chicken and quail eggs are commercially available from local grocery stores or supermarkets. Abalone shells and bone samples for testing purposes are commercially available from Stewart-MacDonald, Athens, Ohio 45701, USA.

[0123] Liquid Treatment Composition

[0124] 41 wt.-% phosphoric acid, 23 wt.-% ethanol, and 36 wt.-% water (wt.-% are based on the total weight of the liquid treatment composition).

3. Examples

[0125] Patterned samples were prepared by applying the liquid treatment composition on the above-mentioned natural materials in form of a predetermined pattern (logo mozaiq or QR-code) with an inkjet printer (Dimatix DMP 2831, Fujifilm Dimatix Inc., USA) with 10 pl (pico litre) droplet size at varying droplet spaces between 10 to 30 m.

Example 1Logo and QR-Code on Chicken Egg

[0126] The logo mozaiq was printed on white and brown egg shells with a drop spacing of 15 m. As can be gathered from the digital image in FIG. 1, the logo is clearly visible on the printed egg shells.

[0127] A QR-code was printed on white and brown egg shells with a drop spacing of 15 m. As can be gathered from the digital image in FIG. 2, the QR-code is clearly visible on the printed egg shells. A SEM micrograph of a section of said QR-code is shown in FIG. 3. FIG. 4 presents a SEM micrograph of a cross section of the printed egg shell. As can be seen from said figure, the pattern formed on the surface of the egg shell has only a thickness of about 10 to 20 m, while the remaining egg shell has a thickness of about 400 m. Said figure confirms that the formed pattern does not enter deep into the egg shell, and thus, is safe from a food and health perspective.

Example 2Logo on Quail Egg

[0128] The logo mozaiq was printed on a quail egg with a drop spacing of 15 m. As can be gathered from the digital image in FIG. 5, the logo is clearly visible on the printed egg shell.

Example 3Logo on Abalone Shell

[0129] The logo mozaiq was printed on the nacre-coated side of an abalone shell with a drop spacing of 30 m. As can be gathered from the digital image in FIG. 6, the logo is clearly visible on the printed abalone surface. A SEM micrograph of a section of said logo showing the letter Z is presented in FIG. 7.

Example 4Logo on Bone

[0130] The logo mozaiq was printed on a bone sample with a drop spacing of 20 m. As can be gathered from the digital image in FIG. 8, the logo is clearly visible on the printed bone surface. A SEM micrograph of a section of said logo showing the letter

[0131] Z is presented in FIG. 9.