WO2001017784A1

WO2001017784A1 - Genuine printing refill and method

Info

Publication number: WO2001017784A1
Application number: PCT/IL2000/000006
Authority: WO
Inventors: Shlomo Dukler
Original assignee: Inksure Ltd.
Priority date: 1999-09-06
Filing date: 2000-01-03
Publication date: 2001-03-15
Also published as: AU1888000A; IL131753A0

Abstract

A method for preventing the use of non-original refills in printing apparatus, such as a printer or a copying machine, comprising labeling the refill material, which may be a toner or ink, with a material the presence of which can be detected using detection apparatus, and disallowing the use of the apparatus, and/or alerting the user of the non-genuine nature of the refill, if the required labeled material is not detected in the refill. The material is labeled using a material the presence of which can be detected using spectrophotometric techniques. The detection apparatus is a spectrophotometric detection apparatus. The toner or ink is marked with a single compound, emitting light in a known spectrum and characteristic. Two or more compounds having different spectra and/or characteristics may be mixed, so as to produce a characteristic 'code' or 'signature' as the result of their excitation with light.

Description

GENUINE PRINTING REFILL AND METHOD

Field of the Invention

The invention relates to the marking of refills for printing apparatus for the purpose of authentication, and to means for revealing the presence of the marks in the refill.

Background of the Invention

Printing machines, such as printer coupled to PCs and copying machines, operate using cartridges of toner or ink. Copying machines and laser printers employ most often solid toner, although liquid toner can also be used, while other printing apparatus, such as ink jet or bubble jet printers employ liquid ink.

All printing apparatus suffers from the problem that non-original and/or counterfeited refills are often sold. These refills are often sold at lower prices than the original refills, but their quality is almost always substantially inferior to that of the original product. This may lead to problems of malfunctioning of the apparatus, which eventually reflect on the manufacturer and its service organization. This may also lead to substantial monetary losses, since the maintenance cycle and costs of the various machines are always calculated on the basis of the use of original parts and refills.

Attempts have been made in the art to solve this problem by marking the toner or ink cartridge, so as to ensure its authenticity, but these attempts have not been substantially successful, since many cartridges are refillable, and although the cartridge sold to the customer is genuine, its contents are not.

It is therefore clear that it would be greatly advantageous to be able to provide a method by means of which the use of refills of this kind, containing no-original material, could be prevented.

It is therefore a purpose of this invention to provide means by which the use of non-original refills for printing apparatus, particularly for standard copying or printing equipment, can be prevented. The term "original", as used herein, is meant to indicate toner or ink manufactured by the manufacturer of the printing apparatus, or on its behalf and/or with its consent.

It is another purpose of this invention to provide marked materials, i.e., toner or ink, for printing apparatus, having identifying characteristics that are not visible to the naked eye, but the presence of which can be detected using detection techniques, such as spectrophotometric, magnetic, RF, optical or NMR techniques.

It is a further purpose of this invention to provide printing apparatus the use of which can be prevented or limited if non-original material is used in its operation.

It is yet another purpose of this invention to provide coded marked toner and ink compositions, which can be used to generate many different authentication codes for verifying that the material contained therein is original, through the use of combination of markers, or to distinguish between brands.

It is a still further purpose of this invention to provide means for recognizing the refill and distinguishing it from material not of original origin or between various brands.

Other purposes and advantages of this invention will appear as the

description proceeds.

Summary of the Invention

A method for preventing the use of non-original refills in printing apparatus, such as a printer or a copying machine, comprising labeling the refill material with a material the presence of which can be detected using detection apparatus, and disallowing the use of the apparatus if the required labeled material is not detected in the refill. The labeling is invisible to the naked eye and does not interfere with the contents of the printed document.

According to a preferred embodiment of the invention, the material is labeled using a material the presence of which can be detected using spectrophotometric techniques. However, the invention encompasses all other suitable techniques, and is by no means limited to spectrophotometric techniques. Other labeling materials, which can be detected using different apparatus, can also be employed, and the invention is not limited to the use of any particular labeling material.

In the context of this invention, the terms "labeling" and "marking", as well as "label" or "marker", or "dye", are use intechangeably. Likewise, the term "refill material" is intended to embrace any material contained in a disposable, or reusable, or recyclable cartridge for printing apparatus, whether the cartridge has been previously used and refilled, or whether the cartridge has been filled and is being used for the first time. Additionally, this term applies to all printing materials, such as ink or toner, no matter whether contained in an original cartridge or in a cartridge not manufactured by, or on behalf of, the original manufacturer.

According to a preferred embodiment of the invention the detection apparatus employed in conjunction with the invention is a spectrophotometric detection apparatus.

According to another preferred embodiment of the invention, the toner or ink is marked with a single compound, emitting light in a known spectrum. According to still another preferred embodiment of the invention, however, two or more compounds are mixed, having different spectra, so as to produce a characteristic "code" or "signature" as the result of their excitation with light.

In the context of the present invention the term "spectrum" is intended to embrace any suitable recognizable characteristic, including, but not limited to, shape, curve shape, intensity, spectral property, time interval, etc. However, the terms "spectrum" and "spectra" will be used herein, to represent all possible characteristics, for the sake of brevity.

Typically, but non-limitatively, the amount of marked toner or ink tested at a given point is preset as a threshold value, below which a refill is considered not authentic. The term "threshold" is used herein in its broadest sense, and includes any parameter and parameter value suitable to indicate the fulfillment of a predetermined condition. Thus, for instance, a correct mixture of predetermined different signals will be considered "threshold", regardless of its intensity, if the output of such mixture comprises minimal required characteristics.

The toner or ink can be checked within its cartridge, e.g., by a probe integral with the cartridge or introduced therein and coupled with the printing apparatus or a device coupled to it, or may be checked outside the cartridge, e.g., on the drum. According to a preferred embodiment of the invention, the toner or ink is tested on a printed document, which may be the first page copied or printed after cartridge replacement, or may be a sample printed after cartridge replacement, or at the time of any other periodic event.

The detection apparatus can be integral with the printing apparatus, or may be attached or added on to it. According to a preferred embodiment of the invention, the output of the detection apparatus generates a signal to the printing machines, which permits to operate it in a normal manner. Additionally, the presence of a non-genuine toner may generate warning messages, e.g., printed messages or displayed messages, and may further, according to another preferred embodiment of the invention, cause the event to be recorded in memory means attached to, or coupled with, the printing apparatus, which may be used to verify the validity of the warranty of the apparatus, or for any other purpose.

The testing of the refill material can be carried out at any suitable time, e.g., at the time of cartridge replacement, or periodically during operation of the machine.

According to a preferred embodiment of the invention the refill material to be verified is exposed to fight in the range of 200-800 nm, thereby exciting the marked toner or ink, and measuring the light emitted from the excited marked toner or ink by a spectrometer. According to a preferred embodiment of the invention a refill material is considered authentic if it emits fight having a spectrum identical to that preset for the specific cartridge.

Many different labeling materials can be used, and the invention is not limited to any particular marker or type of marker. According to a preferred embodiment of the invention, however, the labeling compound is a fluorescent dye. A particularly advantageous marker is N,N'-Ditridecyl-3,4,9,10-perylenetetracarboxylic diimide.

The invention is also directed to a refill cartridge for use in printing apparatus, comprising refill material labeled with a material the presence of which can be detected using detection apparatus. Of particular convenience are refill cartridges wherein the labeling compound is a fluorescent dye, e.g., the aforementioned N,N'-Ditridecyl-3,4,9,10- perylenetetracarboxylic diimide. In another aspect the invention is directed to printing apparatus comprising detection means for detecting the presence of a labeling material contained in the refill toner or ink, using detection apparatus, and circuitry for disallowing the use of the apparatus if the required labeled material is not detected in the refill, and/or to alert the user of the situation. Of particular interest as printing apparatus are printers and copying machines.

According to the invention any toner or ink of any type and color can be marked and used in conjunction with the invention.

Any material that satisfies the requirements of the invention, viz., that can be excited by light irradiation and, as a result, emits light in a detectable amount and with a recognizable wavelength, can be used for the purposes of the invention. Illustrative and non-limitative examples of suitable marker compounds, particularly useful for solid toner compositions (but not limited in use to such compositions), include:

7-diethylamino-4-methyl coumarin;

7-dimethylamino-4-trifluoromethyl coumarin;

7-amino-4-methyl coumarin;

7-amino-4-trifluoromethylcoumarin;

N-(4-anilino-l-naphthyl)maleimide;

Rhodamine 123;

Rubrene; N. -Bis substituted perylene 3,4,9,10 tetracarboxyl-diimides such as

N,N'-Ditridecyl-3,4,9, 10-peryleneteracarboxylic diimide,

N, -Bis(2,5-di-tertbutylphenyl)-3,4,9,10-perylenetetracarboximide, and N,N-Bis(2,6-dimethyphenyl)-3,4,9,10-perylenetetracorboxylic diimide; tetramethylrhodamineisothianate ;

2,5-bis[5-tert-butylbenzenzoxxyolyl(2)thiobenzene];

9,10-bis(phenyl-ethyl)antracene;

9(p-vinyphenyl)-10-phenyl-antracene;

Eosin B and Eosin Y;

Trans-4-[4(Dibutylamino)styryl]-l-(3-Sulfopropyl)pyridinium hydroxide;

Nile Red;

Nile Blue; and

4-(dicyanomethylene)-2-methyl-6-(4-dimethylamino-styryl)-4H-pyran.

As said, a particularly preferred compound is N,N'-Ditridecyl-3,4,9,10- perylenetetracarboxylic diimide. This compound is listed as CA # 95689-92-2. The use of this compound in the production of marked toners for the authentication of refills, is also a part of the present invention.

An advantage of this preferred compound is that its maximum fluorescence emission in its solid state, which is at 690 n , is far away and cannot be interfered by paper emission which could result from UV excitation. Additional examples of suitable labeling dyes for carrying out the invention are fluorescent compounds chosen from polycychc compounds in general, and coumarin derivatives in particular. Particularly preferred are:

Dansylchloride

4',6-diamidino-2-phenylindole

5-(4,6-dichlorotriazin-2-yl) aminofluorescein

4,4'-diisothiocyanopropyHn-2,2'-disulfonic acid teosin isothianate erythrosin B fluorescamine fluorescin and its derivatives

4-methylumbelliprone o-thaldialdehyde rhodamine B and its derivatives rhodamine 6-G and Rhodamine 6G Perchlorate

2,5 dibiphenylyloxazole p-bis[2(5-phenyloxazolyl)benzene]

Y₂03:Eu Lantinide Chelate.

The luminescent material is irradiated by UV light in the range between 250-366 nm and fluoresces in the visible spectrum between 400-700 n . Some of the compound materials will give an emission NIR. Other suitable luminescent compounds and the preparation of sohd or liquid ink comprising them, are known in the art and are described, e.g., in USP 5,554,480 and USP 4,865,937, the description of which is fully incorporated herein by reference.

Detailed Description of Preferred Embodiments

The toner colors and labeling dyes, which make up the toner compositions in particulate, such as granular or powdery form, may be associated into toner composition particles in various ways known in the art, and as exemplified hereinafter.

The fluorescent compound or compounds used should, as has been said, preferably be colorless and, therefore they may be considered colorless toners. They should also be such as not substantially to alter the colors of the toner colors, although some alteration is tolerable and can be taken into account. Likewise, it is desirable that the colorless toner should not affect substantially the electrostatic and thermal properties of the toner colors, and therefore nor interfere with their deposition on the print receiver or their setting by fusing in such processes as laser printing and the like.

All the above is of course applicable, mutatis mutandis, to the use of labeled liquid or semi-solid inks, e.g., for ink-jet or bubble-jet printers. The production of liquid inks, however, is much simpler than that of solid toners, and is therefore not described herein in detail, for the sake of brevity, since the addition of luminescent markers to liquid ink compositions is within the skill of the routineer.

When multiple application of different labeling dyes is desired, one carries out the labeling procedure twice or more, once with each labeling dye, or carry out the aforesaid process once by mixing with the water suspension of the toner colors a solution in a solvent of the mixture of the desired labeling dyes.

However, other methods can be used for producing the toner composition containing the toner colors and the labeling dyes. This can be done, for instance, by mixing them in sohd, finely particulate form.

The presence of the marked toner can be detected by any suitable apparatus, e.g., by spectrophotometric apparatus in case that the spectrum used is a spectrophotometric spectrum. An example of such apparatus is the FLM Aminco Bowman Series-2 spectrometer (ex Spectronic Instruments, Inc. - USA).

The method of the invention presents several important advantages. For instance, it can be applied to all kinds of printers, such as ink-jet or bubble jet printers, fax machines, photocopy machines and laser printers. It is possible to mark the toner or ink using different markers, so as to generate different "codes" or "signatures". The detection of the marked toner or ink is made by spectrophotometric apparatus, and therefore the determination of the authenticity of the refill is objective, and not human dependent. Example 1

30 mg of labeling dye, which in this example is 7-diethylamino-4-methylcoumarin, were dissolved in 1 ml of ethyl alcohol (analytical grade). 1 g of the coloring matter of the toner was suspended in 40 ml of water. The dye solution was added slowly to the suspension, while stirring vigorously. Mild heating was used to reach the

precipitation point. The process took two hours. The maximum temperature reached in the heating is 40°C. After the precipitation is

completed, the resulting toner composition is filtered and dried.

Example 2

In the case of organic ink, the luminescent pigment was dissolved in an organic solvent, such as, ethyl-alcohol, iso-propyl alcohol or ethyl-acetate but not limited to these solvents. This organic solution was poured into the organic ink and was mixed thoroughly for up to two hours using a laboratory mixer from 200-800 rpm. It was then ready for use.

By this method there were prepared cyan, yellow, magenta, and black toner and ink color, but the method is not limited to these colors and can be implemented on any color type including pigmentless or colorless

toners and inks. While embodiments of the invention have been described by way of illustration, it will be apparent that the invention may be carried out by persons skilled in the art with many modifications, variations and adaptations, without departing from its spirit or exceeding the scope of the claims.

Claims

1. A method for preventing the use of non-original refills in printing apparatus, comprising labehng the refill material with a material the presence of which can be detected using detection apparatus, and disallowing the use of the apparatus, and/or alerting the user of the non-genuine nature of the refill, if the required labeled material is not detected in the refill.

2. A method according to claim 1, wherein the material is labeled using a material the presence of which can be detected using spectrophotometric techniques.

3. A method according to claim 2, wherein the detection apparatus is a spectrophotometric detection apparatus.

4. A method according to any one of claims 1 to 3, wherein the refill material is a toner or ink.

5. A method according to claim 4, wherein the printing apparatus is a printer or a copying machine.

6. A method according to any one of claims 1 to 5, wherein the toner or ink is marked with a single compound, emitting fight in a known spectrum and characteristic.

7. A method according to any one of claims 1 to 5, wherein two or more compounds are mixed, having different spectra and/or characteristics, so as to produce a characteristic "code" or "signature" as the result of their excitation with hght.

8. A method according to any one of claims 1 to 7, wherein the amount of marked toner or ink tested at a given point is preset as a threshold value, below which a refill is considered not authentic.

9. A method according to any one of claims 1 to 8, wherein the toner or ink is checked within its cartridge.

10. A method according to any one of claims 1 to 8, wherein the toner or ink is checked on the drum, prior to being transferred to the printed page.

11. A method according to any one of claims 1 to 8, wherein the toner or ink is tested on a printed document.

12. A method according to claim 11, wherein the printed document is a sample printed after cartridge replacement.

13. A method according to any one of claims 1 to 12, wherein the detection apparatus is integral with the printing apparatus.

14. A method according to any one of claims 1 to 13, wherein the output of the detection apparatus generates an input signal to the printing machines, which permits to operate it and/or generates a notification of genuinity or not of the refill.

15. A method according to any one of claims 1 to 14, wherein the testing of the refill material is carried out at the time of cartridge replacement.

16. A method according to any one of claims 1 to 14, wherein the testing of the refill material is carried out periodically.

17. A method according to any one of claims 1 to 16, comprising exposing the refill material to be verified to light in the range of 200-800 nm, thereby exciting the marked toner or ink, and measuring the light emitted from the excited marked toner or ink by a spectrometer.

18. A method according to claim 17, wherein a refill material is considered authentic if it emits light having a characteristic identical to that preset for the specific cartridge.

19. A method according to any one of claims 1 to 18, wherein the labehng compound is a fluorescent dye.

20. A method according to claim 19, wherein the labeling compound is N,N'-Ditridecyl-3,4,9,10-perylenetetracarboxylic diimide.

21. A method according to any one of claims 1 to 16, wherein the presence of the labeling material is detected by detecting a characteristic detectably by using any suitable method, including but not limited to electromagnetic, radio frequency, colorimetric and the like techniques.

22. A refill cartridge for use in printing apparatus, comprising refill material labeled with a material the presence of which can be detected using detection apparatus.

23. A refill cartridge according to claim 22, wherein the material is labeled using a material the presence of which can be detected using spectrophotometric techniques.

24. A refill cartridge according to claim 23, wherein the detection apparatus is a spectrophotometric detection apparatus.

25. A refill cartridge according to any one of claims 22 to 24, wherein the refill material is a toner or an ink.

26. A refill cartridge according to claim 25, wherein the printing apparatus is a printer or a copying machine.

27. A refill cartridge according to any one of claims 22 to 26, wherein the toner or ink is marked with a single compound, emitting light with a known characteristic.

28. A refill cartridge according to any one of claims 22 to 26, wherein two or more compounds are mixed, having different spectra, so as to produce a characteristic "code" or "signature" as the result of their excitation with fight.

29. A refill cartridge according to claim 28, wherein the difference measured is in the reaction time and/or in the spectral shape.

30. A refill cartridge according to any one of claims 22 to 29, wherein the amount of marked toner or ink tested at a given point is preset as a threshold value, below which a refill is considered not authentic.

31. A refill cartridge according to any one of claims 22 to 30, wherein the toner or ink is checked within the cartridge.

32. A refill cartridge according to any one of claims 22 to 30, wherein the toner or ink is tested on a printed document.

33. A refill cartridge according to any one of claims 22 to 32, wherein at least part of the detection apparatus is integral with the cartridge.

34. A refill cartridge according to any one of claims 22 to 33, wherein the labeling compound is a fluorescent dye.

35. A refill cartridge according to claim 34, wherein the labehng compound is N,N'-Ditridecyl-3,4,9,10-perylenetetracarboxylic diimide.

36. Printing apparatus comprising detection means for detecting the presence of a labeling material contained in the refill toner or ink, using detection apparatus, and circuitry for disallowing the use of the apparatus if the required labeled material is not detected in the refill.

37. Printing apparatus according to claim 36, which is a printer or a copying machine.

38. Printing apparatus according to claim 36 or 37, wherein the detection means are suitable to detect a toner or ink marked with a single compound, emitting fight in a known spectrum.

39. Printing apparatus according to any one of claims 36 to 38, wherein the detection means are suitable to detect two or more compounds that have been mixed in the toner or ink, having different spectral characteristics, so as to produce a characteristic "code" or "signature" as the result of their excitation with fight.

40. Printing apparatus according to any one of claims 36 to 39, wherein the amount of marked toner or ink tested at a given point is preset as a threshold value, below which a refill is considered not authentic.

41. Printing apparatus according to any one of claims 36 to 40, wherein the toner or ink is checked within its cartridge.

42. Printing apparatus according to any one of claims 36 to 40, wherein the toner or ink is tested on a printed document.

43. Printing apparatus according to claim 42, wherein the printed document is a sample printed after cartridge replacement.

44. Printing apparatus according to any one of claims 36 to 43, wherein the detection apparatus is integral with the printing apparatus.

45. Printing apparatus according to any one of claims 36 to 44, wherein the output of the detection apparatus generates an input to the printing machines which permits to operate it.

46. Printing apparatus according to any one of claims 36 to 45, comprising means for testing the refill material at the time of cartridge replacement.

47. Printing apparatus according to any one of claims 36 to 46, comprising means for the periodical testing of the refill material.

48. Printing apparatus according to any one of claims 36 to 47, comprising light- generating apparatus for exposing the refill material to be verified to light in the range of 200-800 nm, thereby exciting the marked toner or ink, and hght-measuring apparatus for measuring the light emitted from the excited marked toner or ink by a spectrometer.

49. Printing apparatus according to any one of claims 36 to 48, wherein the tested labeling compound is a fluorescent dye.

50. Printing apparatus according to claim 49, wherein the tested labeling compound is N,N'-Ditridecyl-3,4,9,10-perylenetetracarboxylic diimide.

51. Printing apparatus according to any one of claims 36 to 50, wherein at least part of the detection apparatus is integral with the cartridge, and wherein the part of the detection apparatus coupled to, or integral with, the printing apparatus is in contact end/or in communication with said part of the detection apparatus which is integral with the cartridge.

52. A method for preventing the use of non-original refills in printing apparatus, substantially as described and illustrated.

53. A refill cartridge for use in printing apparatus, essentially as described and illustrated.

54. Printing apparatus comprising detection means for detecting the presence of a labeling material contained in the refill toner or ink, essentially as described and illustrated.