Laser marking compositions and method

• US 6,503,310 B1
• Filed: 06/21/2000
• Issued: 01/07/2003
• Est. Priority Date: 06/22/1999
• Status: Expired due to Term

• Current Assignee: Ferro GmbH (Ferro Corporation)
• Original Assignee: dmc2 Degussa Metals Catalysts Cerdec AG (Vectra Corp.)
• Inventors: Sullivan, Robert Michael
• Primary Examiner(s): Klemanski, Helene
• Assistant Examiner(s): Faison, Veronica F.
• Application Number:
  US09/598,507
• Time in Patent Office: 930 Days
• Field of Search: 106/31.6, 106/4.6, 106/479
• US Class Current: 106/31.6
• CPC Class Codes: B41M 5/262 recording or marking of inorganic surfaces or materials, e.g. glass, metal, or ceramics marking of plastic artifacts with inorganic additives B41M5/267
• CPC Class Codes: B41M 5/267 Marking of plastic artifacts, e.g. with laser
• CPC Class Codes: B44C 1/005 by altering locally the surface material surface treatment to obtain special artistic surface effects or finishes B44D5/00
• CPC Class Codes: B44C 1/04 Producing precipitations producing precipitations by electrolysis C25D
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 29/00 Compounds of bismuth
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2004/80 Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2004/82 two phases having the same anion, e.g. both oxidic phases
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/34 Melting temperatures
• CPC Class Codes: C01P 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C01P 2006/90 Other properties not specified above
• CPC Class Codes: C03C 23/0025 by a laser beam
• CPC Class Codes: C04B 14/00 Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone expanding or defibrillating materials C04B20/00
• CPC Class Codes: C04B 2103/54 Pigments; Dyes
• CPC Class Codes: C04B 33/00 Clay-wares monolithic refractories or refractory mortars C04B35/66; porous products C04B38/00
• CPC Class Codes: C04B 35/00 Shaped ceramic products characterised by their composition porous ceramic products C04B38/00; ceramic articles characterised by particular shape, see the relevant classes, e.g. linings for casting ladles, tundishes, cups or the like B22D41/02; ceramic substrates for microelectronic semi-conductors H01L23/15; Ceramics compositions containing free metal bonded to carbides, diamond, oxides, borides, nitrides, silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides or sulfides other than as macroscopic reinforcing agents C22C; shaping of ceramics B28B; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products chemical preparation of powders of inorganic compounds C01; infiltration of sintered ceramic preforms with molten metal C04B41/51
• CPC Class Codes: C04B 41/0036 : Laser treatment working by laser beam B23K26/00
• CPC Class Codes: C04B 41/009 : characterised by the material treated
• CPC Class Codes: C04B 41/4539 : as a emulsion, dispersion or suspension
• CPC Class Codes: C04B 41/4572 : Partial coating or impregnation of the surface of the substrate
• CPC Class Codes: C04B 41/5027 : Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
• CPC Class Codes: C04B 41/87 : Ceramics
• CPC Class Codes: C09C 1/0084 : containing titanium dioxide
• CPC Class Codes: C09C 1/04 : Compounds of zinc C09C1/0003, C09C1/0009, C09C1/0015, C09C1/0078 take precedence

Abstract

Laser markable coatings include a marking pigment and a fixing material. The marking pigment may comprise titanium dioxide, zinc oxide, zinc sulfide or the like. The fixing material may comprise bismuth trioxide, antimony oxide and the like, and preferably has a melting temperature below 1,300° C. A preferred laser marking composition includes TiO₂ and Bi₂O₃ in a weight ratio of about 1:1. After application to a substrate and laser irradiation, the fixing material stabilizes the resultant mark.

Claims

1. A laser marking material comprising a mixture of:

at least one marking pigment; and

bismuth trioxide as a fixing material.

2. The laser marking material of claim 1, wherein the marking pigment comprises titanium dioxide, zinc oxide and/or zinc sulfide.

3. The laser marking material of claim 1, wherein the marking pigment comprises titanium dioxide.

4. The laser marking material of claim 1, wherein the marking pigment comprises titanium dioxide.

5. The laser marking material of claim 1, wherein the weight ratio of the marking pigment to the fixing material is from about 1:

10 to about 10;

1.

6. The laser marking material of claim 1, wherein the weight ratio of the marking pigment to the fixing material is from about 1:

5 to about 5;

1.

7. The laser marking material of claim 1, wherein the weight ratio of the marking pigment to the fixing material is about 1:

1.

8. The laser marking material of claim 1, wherein the fixing material has a melting point below about 1,300°

C.

9. A laser marking coating comprising:

a liquid carrier; and

a laser marking material, wherein the laser marking material comprises;

at least one marking pigment; and

bismuth trioxide as a fixing material.

10. The laser marking coating of claim 9, wherein the marking pigment comprises titanium dioxide, zinc oxide and/or zinc sulfide.

11. The laser marking coating of claim 9, wherein the weight ratio of laser marking material to carrier is from about 0.5:

1 to about 15;

1.

12. The laser marking coating of claim 9, wherein the marking pigment comprises titanium dioxide.

13. The laser marking coating of claim 9, wherein the marking pigment comprises titanium dioxide.

14. The laser marking coating of claim 9, wherein the weight ratio of the marking pigment to the fixing material is from bout 1:

10 to about 10;

1.

15. The laser marking coating of claim 9, wherein the weight ratio of the marking pigment to the fixing material is from about 1:

5 to about 5;

1.

16. The laser marking coating of claim 9, wherein the weight ratio of the marking pigment to the fixing material is about 1:

1.

17. The laser marking coating of claim 9, Wherein the fixing material has a melting point below about 1,300°

C.

18. A method of marking a surface of a substrate comprising:

applying a marking material comprising a marking pigment and a fixing material to the surface of the substrate with a thickness of from about 0.1 to about 300 microns; and

irradiating a portion of the marking material with at least one laser beam to adhere the irradiated marking material on the surface of the substrate and to form a permanent marking thereon comprising the marking pigment and the fixing material.

19. The method of claim 18, wherein the marking pigment comprises titanium dioxide, zinc oxide and/or zinc sulfide.

20. The method of claim 18, wherein the marking pigment comprises titanium dioxide.

21. The method of claim 18, wherein the fixing material comprises at least one compound selected from the group consisting of bismuth trioxide, antimony oxide, lead oxide, vanadium pentoxide, molybdenum trioxide, alkaline earth silicates, and alkaline earth aluminosilicates.

22. The method of claim 18, wherein the fixing material comprises bismuth trioxide.

23. The method of claim 18, wherein the marking pigment comprises at least one compound selected from titanium dioxide, zinc oxide, and zinc sulfide, and the fixing material comprises at least one compound selected from the group consisting of bismuth trioxide, antimony oxide, lead oxide, vanadium pentoxide, molybdenum trioxide, alkaline earth silicates, and alkaline earth aluminosilicates.

24. The method of claim 18, wherein the marking pigment comprises tit num dioxide and the fixing material comprises bismuth trioxide.

25. The method of claim 18, wherein the weight ratio of the marking pigment to the fixing material is frog about 1:

10 to about 10;

1.

26. The method of claim 18, wherein the weight ratio of the marking pigment to the fixing material is from about 1:

5 to about 5;

1.

27. The method of claim 18, wherein the weight ratio of the marking pigment to the fixing material is about 1:

1.

28. The method of claim 18, wherein the fixing material has a melting point below about 1,300°

C.

29. The method of claim 18, wherein the permanent marking has a thickness of from 0 to about 100 microns measured from the surface of the substrate.

30. The method of claim 18, wherein the permanent marking has a thickness of from 0.05 to about 30 microns measured from the surface of the substrate.

31. The method of claim 18, further comprising removing a non-irradiated portion of the marking material from the substrate.

32. The method of claim 18, wherein the marking material is adhered to a backing material.

33. The method of claim 32, wherein the backing material is removed from the substrate after the laser begs irradiation.

34. The method of claim 18, wherein the substrate comprises glass.

35. The method of claim 18, wherein the substrate comprises ceramic.

36. The method of claim 18, wherein the substrate comprises brick.

37. The method of claim 18, wherein the substrate comprises stone.

38. The method of claim 18, wherein the substrate comprises metal.

39. The method of claim 18, wherein the substrate comprises a composite.

40. The method of claim 18, wherein the substrate comprises plastic.