MARKING SILK PRODUCTS

Abstract

A process is provided for identifying a production and/or commercial history of a silk fiber or a product made therefrom.

Claims

1. A process for marking silk manufactured from silkworms with an XRF-identifiable marker, the process comprising: feeding silkworms with leaves treated with a formulation comprising at least one XRF-identifiable marker or feeding silkworms with a feeding composition enriched with a formulation comprising at least one first XRF-identifiable marker under conditions permitting said marker to be taken up by the silkworms, and/or treating a bave with a formulation comprising at least one XRF-identifiable marker, during the bave treatment stage, and/or treating a cocoon with a formulation comprising at least one XRF-identifiable marker, and/or treating a silk fiber during a degumming stage or during an ennobling stage to thereby mark the bave, the cocoon, and/or the silk fiber with the at least one marker, wherein the XRF-identifiable marker is not a native material to a silk fiber or silk manufacturing process.

2. A process for identifying a silk, the process comprising marking the bave, cocoon or silk according to the process of claim 1 and analyzing the presence of the XRF-identifiable marker in a silk fiber or a product made from said bave, cocoon or silk fiber, to thereby identify the silk.

3. The process according to claim 1, wherein the XRF-identifiable marker is selected to identify a property or information relating to the processed silk.

4. The process according to claim 1, wherein the silk fiber is treated more than once with different marker formulations, each of the marker formulations being configured to provide a latent marking that identifies a different property or information.

5. The process according to claim 1, wherein the marker is configured to identify any one or more of: origin of the silkworm; the farm where the silkworms were grown; the processing facility; date of processing; the processing protocol; the supplier of the bave or reeled silk; and/or information relating to operational and logistical data.

6. A process for identifying a production or commercial history of a silk product, the process comprising feeding silkworms or treating a silkworm cocoon or a silk fiber produced therefrom with a formulation comprising a first XRF-identifiable marker at a first stage, to embed said first marker in the silk fiber or bave; treating the silk fiber at a second stage with a second XRF-identifiable marker to embed said second marker in the silk fiber; and analyzing the presence of the first and second XRF-identifiable markers in said silk fiber or product made therefrom to thereby identify the production or commercial history of the silk fiber.

7. The process according to claim 1, wherein the silk fiber is marked during a stage of destroying chrysalis, or during a stage of loosening sericin or during a stage of degumming.

8. The process according to claim 7, the process comprising: treating the cocoon or bave with a formulation comprising a first set of one or more XRF-identifiable markers to embed said first marker in the silk fiber; wherein the first set of markers encoding at least one parameter relating to the facility or process conditions; during reeling treating the silk fiber with a formulation comprising a second set of one or more XRF-identifiable markers to embed said second set of markers in the silk fiber; wherein the second set of markers encoding at least one parameter relating to the grade of the silk fiber after undergoing treatment; after reeling treating the silk fiber with a formulation comprising a third set of one or more XRF-identifiable markers to embed said third set of markers in the silk fiber; wherein the third set of markers encoding at least one parameter relating to the destination of the silk fiber or an intended further processing; optionally during ennobling treating the silk fiber with a formulation comprising a further set of one or more XRF-identifiable markers; and analyzing presence of the first and/or second and/or third and/or further sets of XRF-identifiable markers in said silk or in a product manufactured therefrom to determine production or commercial history of the silk fiber or product made therefrom.

9. The process according to claim 8, wherein the analyzing step comprises directing an X-ray or Gamma-ray radiation towards the silk fiber or product made therefrom and detecting a response X-ray signal emitted from the marker in response, such that said response signal is indicative of presence, concentration or relative concentration of the marker to thereby provide information encoded by the marker on the production or commercial history of the silk fiber or product made therefrom.

10. The process according to claim 1, wherein the silk fiber is marked by immersing the cocoon in a water-based solution comprising one or more markers and optionally one or more additives.

11. The process according to claim 1, wherein the silk is marked by utilizing a dyeing solution comprising one or more markers.

12. The process according to claim 1, wherein the XRF-identifiable marker is in a form of a metal atom, a metal oxide, or a metal salt, or an organometallic or an organohalide material.

13. The process according to claim 12, wherein the marker is a metal or a metal containing material, the metal atom being optionally selected from aluminum, titanium, cobalt, nickel, yttrium, cadmium, tin, scandium, titanium, niobium, silver, tungsten, zinc, zirconium, vanadium, manganese, copper, lead, molybdenum, vanadium, bismuth, antimony, tantalum and cesium.

14. The process according to claim 12, wherein a metal-based marker is selected from aluminum oxide, scandium acetate, titanium oxide, cobalt acetyl acetonate, cobalt carbonate, cobalt dibromo, nickel acetyl acetonate, nickel acrylate, yttrium oxide, niobium oxide, silver carbonate, silver chloride, tin ethyl hexanoate, tungsten oxide and others.

15. The process according to claim 12, wherein a halide-based marker is selected from tri-iodine phenol (TIP), tribromophenol (TBP), tri chlorophenol (TCP), 2,2-bis(bromomethyl) propane-1,3-diol, 2,4,6-tribromo aniline, Penta-bromobenzyl acrylate, 4,5,6,7-tetrabromoisobenzofuran-1,3-dione and ammonium bromide.

16. A fibroin rich silk fiber produced from a silk-producing animal, the fiber being associated, embedded or adsorbed with at least one XRF-identifiable marker.

17. A silk product comprising at least one silk fiber according to claim 16.

18. A fabric comprising at least one silk fiber according to claim 16.

19. A system for managing a supply chain of silk and silk products, the system comprising a database system (central or distributed) comprising data relating to silk and their marking with an XRF-identifiable marker.

20. A process for identifying a production and/or commercial history of a silk fiber or a product made therefrom, the fiber or product having been marked with at least one XRF-identifiable marker, the process comprising directing an X-ray or Gamma-ray radiation towards the fiber or product made therefrom and detecting a response X-ray signal emitted from the marker in response, such that said response signal is indicative of presence, concentration or relative concentration of the marker to thereby provide information encoded by the marker on the production or commercial history of the silk fiber or product made therefrom.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0106] In order to better understand the subject matter that is disclosed herein and to exemplify how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

[0107] FIG. 1 depicts a process of the invention in accordance with some of its embodiemnts.

DETAILED DESCRIPTION OF EMBODIMENTS

Example 1

[0108] Silk used in the textile industry is produced by larvae of moth caterpillars, the best known of which is silk obtained from the cocoons of the larvae of the mulberry silkworm. The marking of the silk is obtained by adding a marking composition to the food consumed by the silk caterpillar. The silk fibers are produced by two glands and is naturally extruded from two openings (spinnerets) in the caterpillar’s head. By allowing the caterpillar to consume a one or more marking compositions the silk fiber produced by caterpillar may include or attached to the markers.

[0109] The marking compositions may for example include soluble or insoluble inorganic salts, oxides, substituted phenols, carbide, inorganic salts such as salt of sulfides, carbonates, bicarbonate, sulfate, phosphate, nitrate, acrylates, acetate, acetylacetonate, ethylexanoate, gluconate, glycinate and anilines. In an example, the dry food or consumable dry material is added to a water-based solution (marking solution) comprising one or more marking compositions. The solution with the dry material may be heated and then dried such that a solid consumable (for the caterpillar) material is obtained. The marked solid material is then fed to the caterpillar.

[0110] In another example, the caterpillar is allowed to consume the one or more marking compositions by applying it directly to the leaves, or plant-parts eaten by the caterpillar, such as mulberry leaves. In this example the one or more marking composition may be applied to the leaves by spraying, dripping, brushing or any method for applying a liquid solution the leaf surface. In another example, the leaves are marked by immersing the leaves in a marking solution comprising one or more marking compositions.

Example 2

[0111] Silk is produced from the cocoon of the silkworm caterpillar by extracting continuous threads from the cocoon. This follows a process of degumming in which the cocoons are placed and boiled in a water-based solution in order to soften and dissolve the gum that is holding the cocoon together.

[0112] The cocoons are marked by a separate process in which the cocoons are immersed in a water-based marking solution. The marking solution includes one or more marking compositions each including one or more markers (e.g. materials and elements that may be detected by XRF reader). The solution may also include at least one of processing agents such as surfactants classified as anionic, cationic, zwitterionic polymeric and/or non-ionic with various HLB (hydrophilic- lipophilic balance), catalyst, enzymes, radical initiator and fixation agents; and intermediate or bridging agents comprising intermediate molecules which will bond the marking composition to proteins in the silk fiber.

[0113] The one or more marking compositions may include oxides, substituted phenols, carbide, inorganic salts such as salt of sulfides, carbonates, bicarbonate, sulfate, phosphate, nitrate, acrylates, acetate, acetylacetonate, ethylexanoate, gluconate, glycinate and anilines. The marking composition may also include organo-halides.

[0114] The intermediate molecules are utilized for attaching or bonding the marking composition and or/the marker elements to the silk fibers. Specifically, the intermediate molecules function as a bridge connecting the active residues in the amino acids comprising the proteins in the silk fiber to the marking molecules and/or elements within the marking composition. The intermediate molecules may bond with the Carboxylic, hydroxylic, sulfides and the amine active residues in the amino acids. In an example the amino acids are glycine, alanine, and serine. In an example the intermediate molecules may be aldehydes such as aromatic aldehydes. In a particular example, the intermediate molecules may be one of the following: polymer, polysaccharide and/or aldehydes and its derivatives.

[0115] The marking of the cocoon by a separate marking process may be carried out either prior to the degumming process or after the degumming process or both before and after the degumming process. Furthermore, it may be carried out as a separate process during all stages of silk production.

Example 3

[0116] Silk worms were divided into two groups: a control group and a marked group which was fed on an artificial food:

[0117] (https://www.wwb.co.uk/index.php?route=product/product&keyword=silkworm&product_id=6174 ) containing marking materials according to the invention.

[0118] The marking materials were dissolved in water to a concentration of between 0.001% and 1% w/w the XRF identifiable atom. The marking materials were selected from AgNO.sub.3, Ba(NO.sub.3).sub.2, BiCl.sub.3, NH.sub.4Br, CdCl.sub.2, Co(NO.sub.3).sub.2•6H.sub.2O, Cu(NO.sub.3).sub.2.Math.3H.sub.2O, La(CH.sub.3CO.sub.2).sub.3 • xH.sub.2O, MnSO.sub.4 .Math. H.sub.2O, Na.sub.2SeO.sub.4 and others.

[0119] Mulberry leaves were soaked in a solution of the marker material and thereafter were fed to the worms. When dry food was used, it was absorbed with the marking solution to absorb the solution to 200% of its original weight and thereafter was fed to the worms. Feeding was over a period of 3 weeks.

[0120] After the cocoon was developed, three independent measurements were taken: 5 days after cocoon formation, and 10 days after cocoon formation. The empty cocoon was also measured.

[0121] The markers were read and identified in the cocoon in all cases.

Example 4

[0122] Cocoons were added into a marker solution containing up to 2000 ppm of the XRF identifiable atom. The markers were selected as in Example 3 above. The ratio cocoon to solution was between 1:60 and 1:200.

[0123] For some of the solutions, functional materials such as chitosan or chitosan derivatives and others were added to assist association between the marker materials and the substrate. The amount of the functional material was not greater than 25 ppm or higher.

[0124] Typically, the cocoons were left in the solution at a temperature between 40 and 100° C. for a period between 4 and 10 minutes, to mimic many of the processing conditions used in silk processing.

[0125] For the degumming step, a soap solution containing 1% natural soap was prepared to a pH between 9 and 9.8. The cocoons were soaked in the solution for a period of about two hours at a temperature between 85 and 95° C. Thereafter the cocoons were removed from the solution, washed and dried.

[0126] A dyeing solution containing 0.01% a water soluble dye and 0.1% acetic acid was prepared. At a temperature between 75 and 90° C. the cocoons were soaked for a period of 1 hour.

[0127] At the end of the complete process, markers were read.

Example 5

[0128] A wetting solution containing 5-15% of a material mixture was prepared. The material mixture contained one or more of softening agents, natural and synthetic waxes, Anionic and non-ionic emulsifiers, glycols, fatty acids having between 14 and 20 carbon atoms, natural esters and others. To the solution markers selected as in Example 2 were added at a concentration of 0.01 and 1% or between 0.002% and 0.03% w/w.

[0129] Cocoons were soaked in the solution at a temperature below 30° C. for a period of between several minutes and 1 hour. The cocoons were thereafter removed and dried.

[0130] Degumming and dyeing was carried out as in Example 4 and the markers were thereafter measured.

Example 6

[0131] Marking of the silk may be performed during degumming by introducing one or more marking compositions (each including one or more markers, and optionally additional additives), into a solution used in the degumming process. In an example one or more soluble marking composition are added into the aqueous solution in which degumming is carried out. In another example one or more marking compositions together with at least one of processing agents (such as surfactants, enzymes, and catalysts) and a bridging agent comprising intermediate molecules.

Example 7

[0132] In a similar fashion to solutions prepared as above, ennobling solutions were prepared and used. Marker formulations suitable for each of the following steps were prepared and tested to confirm the ability to mark and read the cocoon or silk fiber generated therefrom.