TRACKING HIDE AND LEATHER IN A SUPPLY CHAIN PROCESS

Abstract

A process is provided for marking leather manufactured from hide with an XRF-identifiable marker, the process comprising treating a hide or processed leather with a formulation comprising at least one XRF-identifiable marker to embed said marker in the hide or processed leather, to thereby obtain a marked hide or marked leather, wherein the XRF-identifiable marker is not a native material to a hide or leather or involved in a process for its manufacturing.

Claims

1-33. (canceled)

34. A process for marking leather manufactured from hide with an XRF-identifiable marker, the process comprising treating a hide or a processed leather with a formulation comprising at least one XRF-identifiable marker to embed said marker in the hide or processed leather, to thereby obtain a marked hide or marked leather, wherein the XRF-identifiable marker is not a native material to a hide or leather or involved in a process for its manufacturing.

35. A process for identifying a production and/or commercial history of a leather or a product made therefrom, the leather 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 leather 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 leather or product made therefrom.

36. The process according to claim 34, wherein the hide or processed leather is treated more than once with different marker formulations, each of the marker formulations provides a latent marking identifying a different property or information.

37. The process according to claim 36, wherein the latent marking identifies any one or more of origin of the hide or leather, a slaughterhouse, a processing facility, date of processing, processing protocol, type of leather, quality of leather, type of animal, date of tanning, tannery, supplier of the hides, operational information and marketing information.

38. The process according to claim 35, wherein the production and/or commercial history comprises origin of hide or leather, a slaughterhouse, a processing facility, date of processing, processing protocol, type of leather, quality of leather, type of animal, date of tanning, tannery, supplier of the hides, operational information and marketing information.

39. The process according to claim 34, wherein the marker formulation is applied to the hide during production in a preparatory stage of leather production prior to tanning.

40. The process according to claim 34, wherein the marker formulation is applied to the hide during tanning.

41. The process according to claim 34, wherein the marking is applied to the hide during dyeing and/or during the finishing processes.

42. The process according to claim 34, the marker formulation is applied to the hide in the slaughterhouse prior to or during salting the hide, or after the salting process.

43. The process according to claim 34, wherein treating comprises continuous washing or spraying with the marker formulation or soaking in a water-based marker formulation or solution.

44. The process according to claim 34, comprising pre-soaking of the hide or processed leather.

45. The process according to claim 34, wherein the treating of the hide or processed leather is carried out in an ultrasonic bath.

46. The process according to claim 34, wherein the marker formulation comprises a processing agent and an intermediate or bridging agent.

47. The process according to claim 46, wherein the processing agent is selected from surfactants, catalysts and enzymes.

48. The process according to claim 46, wherein the intermediate or bridging agent is selected to chemically associate the marker to a region, a material or an atom of the hide or processed leather.

49. The process according to claim 48, wherein the intermediate or bridging agent is a bifunctional molecule comprising at least two functionalities, capable of associating to active residues in amino acids making up collagen in the hide and to the XRF identifiable marker.

50. The process according to claim 49, wherein the intermediate or bridging agent is an aldehyde containing molecule, sulfide containing molecules, mercaptan containing molecules, epoxide containing molecules, imine containing molecules, imide containing molecules, chitosan, lignin, glutaraldehyde or EDTA.

51. The process according to claim 34, the process comprising two or more marking sessions, each session comprising treating the hide or leather with a marker formulation comprising same or different XRF identifiable marker.

52. The process according to 50, wherein the two or more marking sessions are carried out at different stages of the leather production process.

53. The process according to claim 52, wherein a first session is carried out on a hide before a preparatory stage of production and a further session during tanning and/or during dyeing or a finishing stage of leather production.

54. A process for identifying a production and/or commercial history of a leather, the process comprising treating a hide with a formulation comprising a first XRF-identifiable marker at a first stage prior to tanning of said hide, to embed said first marker in the hide; following tanning of the hide, treating the tanned hide with a second XRF-identifiable marker to embed said second marker in the tanned hide; and analyzing the presence of the first and/or second XRF-identifiable markers in said tanned hide or in a product manufactured therefrom.

55. The process according to claim 54, wherein the analyzing step comprises directing an X-ray or Gamma-ray radiation towards the leather 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 leather or product made therefrom.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

Example 1: Formulations According to the Invention

[0068] Various hides and processed lathers have been treated with a marking formulation according to the present invention. Non-limiting examples of such treatment protocols are listed in Table 1 below.

[0069] Shown in Table 1 are the marker molecule containing a marker atom or element, the hide exposure time (Mix. Time A), the mixing method (Mix Method B), the second exposure time (Mix Time B) and whether or not additional treatment steps have been included. These may be treatment with an ionic surfactant, a non-ionic surfactant, an enzymatic surfactant, lignin, chitosan, EDC, NHS or hydrogen peroxide.

TABLE-US-00001 TABLE 1 formulations according to embodiments of the present invention. Mix. Mix. Mix. Non Time Method Time Ionic ionic Enzymatic Marker molc. A B B surfactant surfactant surfactant Lignin Chitosam EDC NHS H.sub.2O.sub.2 VOSO4•xH2O 15 min. US 2 min. Yes Yes Yes No No No No Yes bis-Br-ethyl- 15 min. US 2 min. Yes Yes Yes No No No No Yes propanediol Co(NO3)2•6H2O 15 min. US 2 min. Yes Yes Yes No No No No Yes Co(NO3)2•6H3O 15 min. US 2 min. No Yes Yes No Yes No No Yes COAcAc 15 min. US 2 min Yes Yes Yes No No No No Yes CoCO3 15 min. US 2 min. Yes Yes Yes No No No No Yes CsCO3 15 min. US 2 min. No Yes Yes No Yes No No Yes Na28eO4 30 min. US 2 min. Yes Yes Yes No No No No No Nb2O5 15 min. US 2 min. Yes Yes Yes No No No No Yes NH4Br 15 min. US 2 min. Yes Yes Yes No No No No No Ni(NO3)2*6H2O 1 h US 2 min. Yes Yes Yes No No No No Yes Ni(NO3)2*6H2O 30 min. US 2 min. Yes Yes Yes No No No No No Ni(NO3)2*6H2O 15 min. US 2 min. No Yes Yes No Yes No No Yes NiAcAc 15 min. US 2 min. Yes Yes Yes Yes No No No No NiAcAc 15 min. US 2 min. Yes Yes Yes Yes No No No Yes NiAcAc 15 min. US 2 min. Yes Yes Yes No No No No Yes Sc(CH3CO2)3 1 h US 2 min. Yes Yes Yes No No No No Yes Sn Ethyl 15 min US 2 min. Yes Yes Yes Yes No No No Yes Hexanoate SnCl2 15 min. US 2 min. No Yes Yes No Yes No No Yes SnCl2*2H2O 1 h US 2 min. Yes Yes Yes No No No No Yes Tetrabromobenzo- 15 min. US 2 min. Yes Yes Yes No No No No Yes furandione Tribromoaniline 15 min. US 2 min. Yes Yes Yes No No No No Yes Tribromoaniline 15 min. US 2 min. No Yes Yes No No Yes No No Tribromoaniline 15 min. US 2 min. No Yes Yes No No No Yes No Trichloroaniline 15 min. US 2 min. No Yes Yes No No No Yes No Trichloroaniline 15 min. US 2 min. No Yes Yes No No No No Yes WO2 15 min. US 2 min. Yes Yes Yes Yes No No No Yes Y(NO3)3*6H2O 1 h US 2 min. Yes Yes Yes No No No No Yes Y(NO3)3*6H2O 15 min. US 2 min. Yes Yes Yes No No No No No Y(NO3)3*6H2O 15 min. US 2 min. No Yes Yes No Yes No No Yes

[0070] In additional examples, the exemplary markers listed in Table 1 where mixed in the presence of an ionic surfactant in water or an aqueous formulation over a period of several minutes to several hours to embed the marker in the hide or processes leather, in various processing steps.

Example 2

[0071] A 10 gr piece of hide was soaked in a solution of 30 gr water and 0.01-0.07 gr of anionic surfactant at a temperature of 25° C. for a duration of 15 minutes. The hide was then washed by soaking it in clean water for 5 minutes. In the next step the hide was soaked in a solution of 30 gr of buffer solution including 0.03-0.2 gr of a marking composition comprising, 0.02-0.08 gr of anionic surfactant, 0.01-0.08 gr enzyme, 0.01-0.08 gr of non-ionic surfactant in an ultrasonic stirrer, fora duration of 2 minutes, after which 0.01-0.04 gr of hydrogen peroxide were added to the solution and stirred for further 1 minute in the ultrasonic stirrer.

[0072] The hide was then examined by an XRF analyzer and the presence of the marking composition was detected.

[0073] Different hide samples were marked at each of the other leather processing steps and the presence of the marker was established subsequently.

[0074] Following these marking processes the hide has further undergone common leather production processes of soaking, liming, deliming and tanning.

[0075] At the end of the entire process, namely after the soaking, liming, deliming, and tanning the hide was examined by XRF analyzer and the presence of tha marker was detected.

Example 3

[0076] A 10 gr piece of hide was soaked in a solution of 30 gr of water and 0.01-0.07 gr of anionic surfactant minutes at a temperature of 25° C. for a duration of 15 min. The hide was then washed by soaking it in clean water for 5 minutes. In the next step the hide was soaked in a solution of 30 gr of buffer solution including 0.01-0.5 gr of marking composition comprising WO.sub.2, 0.01-0.08 gr of anionic surfactant, 0.01-0.08 gr of enzyme, 0.01-0.08 gr of non-ionic surfactant, 0.01-0.08 gr of bridging agent (lignin), in an ultrasonic stirrer, for a duration of 2 minutes, after which 0.01-0.04 gr of hydrogen peroxide were added to the solution and stirred for further 1 minute in the ultrasonic stirrer. The hide was then washed by soaking it in clean water for 5 minutes. In the next steps the hide underwent regular soaking, liming, deliming and tanning processes similar to ones described in example 1. At the end of the process after soaking, liming, deliming, and tanning the hide was examined by an XRF analyzer. The presence of the marking composition was detected.

Example 4

[0077] A 10 gr piece of hide was soaked in a solution of 30 gr of water and 0.01-0.07 gr of anionic surfactant at a temperature of 25° C. for a duration of 15 minutes. The hide was then washed by soaking it in clean water for 5 minutes. In the next step the hide was soaked in a solution of 30 gr of buffer solution including 0.02-0.1 gr of marking composition comprising trichloroaniline, 0.01-0.08 gr enzyme, 0.01-0.08 gr of non-ionic surfactant, 0.01-0.08 gr of enzyme, and 0.04 gr of 0.01-0.05 NHS (N-Hydroxy Succinimide) in an ultrasonic stirrer, for a duration of 2 minutes, after which 0.03 gr of hydrogen peroxide were added to the solution and stirred for further 1 minute in the ultrasonic stirrer. The hide was then washed by soaking it in clean water for 5 minutes. In the next steps the hide underwent regular soaking, liming, deliming and tanning processes similar to ones described in example 1. After soaking, liming, deliming, and tanning the hide was examined by an XRF analyzer. The presence of the marking composition was detected.

Example 5

[0078] A 10 gr piece of hide was soaked in a solution of 30 gr of water and 0.01-0.07 gr of anionic surfactant at a temperature of 25° C. for a duration of 15 minutes. The hide was then washed by soaking it in clean water for 5 minutes. In the next step the hide was soaked in a solution including 20 gr of buffer solution, 0.05-0.3 gr of marking composition comprising Y(NO.sub.3).sub.3, 5-20 gr of Chitosan, 0.01-0.08 gr enzyme, 0.01-0.08 gr of non-ionic surfactant, 0.01-0.05 gr of H.sub.2O.sub.2 in an ultrasonic stirrer, for a duration of 2 minutes, after which NaOH 1M solution were added to set the solution a PH into level of 6 and stirred for further 2 minutes in the ultrasonic stirrer. The hide was then washed by soaking it in clean water for 5 minutes. In the next steps the hide underwent regular soaking, liming, deliming and tanning processes similar to the ones described in example 1. After soaking, liming, deliming, and tanning the hide was examined by an XRF analyzer. The presence of the marking composition was detected.

Example 6

[0079] A 10 gr piece of hide was soaked in a solution of 30 gr of water and 0.01-0.07 gr of anionic surfactant at a temperature of 25° C. for a duration of 15 minutes. The hide was then washed by soaking it in clean water for 5 minutes. In the next step the hide was soaked in a solution including 20 gr of buffer solution, 0.05-0.3 gr of marking composition comprising SnCl.sub.2, 5-20 gr of Chitosan, 0.01-0.08 gr enzyme, 0.01-0.08 gr of non-ionic surfactant, 0.01-0.05 gr of H.sub.2O.sub.2 in an ultrasonic stirrer, for a duration of 2 minutes, after which NaOH 1M solution were added to set the solution a PH into level of 6 and stirred for further 2 minutes in the ultrasonic stirrer. The hide was then washed by soaking it in clean water for 5 minutes. In the next steps the hide underwent regular soaking, liming, deliming and tanning processes similar to the ones described in example 1. After soaking, liming, deliming, and tanning the hide was examined by an XRF analyzer. The presence of the marking composition was detected.

Example 7

[0080] A 10 gr piece of hide was treated according to the production steps until the tanning phase. After the pickling step, the markers were added in the drum at a concentration between 0.0025% and 0.06% and mixed for 20 minutes. The pH was adjusted to between 3.2 and 3.5 with an acid used in the pickling step (formic acid, sulfuric acid or others). Tanning was carried out by adding into the drum 6.5% chromium salts, 0.025%-0.30% of biocide or detergent. The tanning reaction can comprise also other additives such as wetting agents 0.8%, fixing agent 0.65%-0.70%, or slipping agents 0.15%. The reaction was mixed overnight at temperature between 27-30° C. at a pH between 2.8 and 3.0. The hide was successively washed by soaking with water and 0.05% of degreasing agent for 10 minutes and then in solution of water and 0.05% biocide for 20 minutes. The hide was placed on a paper towel to absorb the excess of water and examined by an XRF analyzer. The presence of the marking composition was detected.