BLACK MIXED OXIDE MATERIAL AND METHOD FOR MANUFACTURING SAME

• US 20200131373A1
• Filed: 06/07/2018
• Published: 04/30/2020
• Est. Priority Date: 06/15/2017
• Status: Active Grant

• Current Assignee: Nakashima Kogyo Corporation, Okuno Chemical Industries Co., Ltd.
• Original Assignee: Nakashima Kogyo Corporation
• Inventors: NAKASHIMA, Mikio, KATO, Takashi
• Granted Patent: US 10,759,943 B2
• Time in Patent Office: Days
• CPC Class Codes: C01F 17/229 Lanthanum oxides or hydroxides
• CPC Class Codes: C01G 3/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/12 Manganates manganites or permanganates
• CPC Class Codes: C01G 45/1221 Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
• CPC Class Codes: C01P 2002/32 spinel-type (AB2O4)
• CPC Class Codes: C01P 2002/34 perovskite-type (ABO3)
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/54 one element only
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2006/42 Magnetic properties
• CPC Class Codes: C01P 2006/62 L* (lightness axis)
• CPC Class Codes: C01P 2006/63 a* (red-green axis)
• CPC Class Codes: C01P 2006/64 b* (yellow-blue axis)
• CPC Class Codes: C03C 8/14 Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
• CPC Class Codes: C04B 2235/3227 Lanthanum oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3263 Mn3O4
• CPC Class Codes: C04B 2235/3281 Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
• CPC Class Codes: C04B 2235/5436 : micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/763 : Spinel structure AB2O4
• CPC Class Codes: C04B 2235/768 : Perovskite structure ABO3
• CPC Class Codes: C04B 2235/80 : Phases present in the sintered or melt-cast ceramic products other than the main phase
• CPC Class Codes: C04B 2235/9661 : Colour
• CPC Class Codes: C04B 35/016 : based on manganites
• CPC Class Codes: C04B 35/6261 : Milling
• CPC Class Codes: C04B 35/62645 : Thermal treatment of powders or mixtures thereof other than sintering
• CPC Class Codes: C09C 1/0081 : Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound C09C1/0015, C09C1/0078 take precedence
• CPC Class Codes: C09C 1/62 : Metallic pigments or fillers C09C1/0015 takes precedence
• CPC Class Codes: C09C 3/04 : Physical treatment, e.g. grinding, treatment with ultrasonic vibrations C09C3/006 takes precedence
• CPC Class Codes: C09C 3/041 : Grinding
• CPC Class Codes: C09D 17/00 : Pigment pastes, e.g. for mixing in paints artists' paints C09D5/06
• CPC Class Codes: C09D 201/00 : Coating compositions based on unspecified macromolecular compounds
• CPC Class Codes: C09D 7/61 : inorganic

Abstract

Provided are a black mixed oxide that contains chromium per se of any valency as a main component, and fails to contain cobalt as the main component material, and has a high safety, an excellent color tone and economical efficiency, and a method for producing the same, and various products using the black mixed oxide material. The mixed oxides comprise oxides containing La, Mn and Cu as main components but containing neither Cr nor Co as a main component, wherein the contents of La, Mn and Cu in the mixed oxides satisfy the following ratios, as oxide equivalent amount with respect to 100% by weight of the oxide equivalent amount: the La content as La₂O₃ being 35-70 wt %; the Mn content as MnO₂ being 25-60 wt %; and the Cu content as CuO being 0.5-10 wt %.

Claims

1. A black pigment containing an oxide containing La, Mn and Cu as main components, and not containing Cr and Co as the main components, wherein

Mn is made from Mn₃O₄, the contents of La, Mn, and Cu in the black pigment satisfy the following ratio:

35 to 70% by weight as La₂O₃; and

25 to 60% by weight as MnO₂; and

0.5 to 10% by weight as CuO, respectively, as oxide equivalent amounts in which the total weight is 100% by weight,

the black pigment has an average particle size of 20 urn or less,

the black pigment in a L*a*b* color system pursuant to JIS-Z-8729 presents a black color with the degree of black (L value) of 25.0 or less,

the black pigment has a perovskite phase exhibiting a maximum intensity diffraction peak in a range of 31°

to 34°

of a diffraction angle 2θ

in X-ray diffraction measurement using CuKα

ray as an X-ray source, and

the black pigment contains Mn₃O₄ that has a spinel structure, as an oxide of Mn.

4. The black pigment according to claim 1, wherein

the black pigment further contains an oxide of Mo as the main component, and

in an oxide equivalent amount in which the total weight of three kinds of oxides that are La₂O₃ as an oxide of La, MnO₂ as an oxide of Mn, and CuO as an oxide of Cu is 100% by weight, the black pigment contains Mo as MoO₃ at a ratio of 5% by weight or less with respect to 100% by weight of the oxide equivalent amount.

5. The black pigment according to claim 1, wherein

the black pigment contains any one or more of Li, B, Na, Mg, Al, Si, P, K, Ca, Ti, V, Fe, Zn, Sr, Y, Zr, Nb, Sn, Sb, Ba, Ta, W, Bi, Ce, Pr, Nd or Er as accessory components besides the main components, and

the black pigment contains Li₂O, B₂O₃, Na₂O, MgO, Al₂ O₃, SiO₂, P₂O₅, K₂O, CaO, TiO₂, V₂O₅, Fe₃O₃, ZnO, SrO, Y₂O₃, ZrO₂, Nb₂O₃, SnO₂, Sb₂O₃, BaO, Ta₂O₅, WO₃, Bi₂O₃, CeO₂, Pr₆O₁₁, Nd₂O₅ or Er₂O₃ as the accessory components at a ratio of 20% by weight or less as oxide equivalent amounts in which the total weight of three types of oxides that are La₂O₃ as an oxide of La, MnO₂ as an oxide of Mn, and CuO as an oxide of Cu is 100% by weight.

7. The black pigment according to claim 1, wherein the black pigment is a nonmagnetic material.

8. The black pigment according to claim 1, wherein the black pigment is an insulating material.

9. A method of manufacturing the black pigment for obtaining a black pigment according to claim 1, the method comprising:

a primary grinding step of mixed grinding oxide materials of La, Mn and Cu to obtain a primary ground product with an average particle diameter of 5 μ

m or less, Mn being made from Mn₃O₄;

a material baking step of baking the primary ground product at 700 to 1200°

C. to obtain a baked starting material; and

a secondary grinding step of grinding the baked starting material to an average particle diameter of 20 μ

m or less.

11. The method of manufacturing the black pigment according to claim 9, wherein

the black pigment further contains an oxide of Mo as the main component, and

as an oxide equivalent amount in which the total weight of three kinds of oxides that are La₂O₃ as an oxide of La, MnO₂ as an oxide of Mn, and CuO as an oxide of Cu is 100% by weight, the black pigment contains Mo as MoO₃ at a ratio of 5% by weight or less with respect to 100% by weight of the oxide equivalent amount.

12. A method of manufacturing the black pigment for obtaining the black pigment according to claim 1, the method comprising:

a first grinding step of mixing and grinding oxide materials of La, Mn and Cu to obtain a first ground product with an average particle diameter of 5 μ

m or less, Mn being made from Mn₃O₄;

a first baking step of baking the first ground product at 700 to 1200°

C. to obtain the first baked product;

a second grinding step of grinding the first baked product to obtain a second ground product with an average particle diameter of 50 μ

m or less;

a second baking step of baking the second ground product at 600 to 1100°

C. to obtain a second baked product; and

a third grinding step of grinding the second baked product in an average particle diameter of 20 μ

m or less.

14. The method of manufacturing the black pigment according to claim 12, wherein

the black pigment further contains an oxide of Mo as the main component, and

in an oxide equivalent amount in which the total weight of three kinds of oxides that are La₂O₃ as an oxide of La, MnO₂ as an oxide of Mn, and CuO as an oxide of Cu is 100% by weight, the black pigment contains Mo as MoO₃ at a ratio of 5% by weight or less with respect to 100% by weight of the oxide equivalent amount.

15. An inorganic ceramic material containing a black pigment according to claim 1 and a ceramic agent.

16. An inorganic glass paste containing the black pigment according to claim 1 and a glass agent.

17. A baking product which is obtained by baking the inorganic glass paste according to claim 16 on a glass member, a metallic member, a china, or porcelain.

18. A resin paste containing the black pigment according to claim 1 and a resin agent.

19. A coated product which is obtained by coating the resin paste according to claim 18 to a base material.

20. The coated product according to claim 19, wherein the base material is a glass, a metal, a china, porcelain, a resin product, or a carbon material.

21. A resin member which contains the black pigment mixed according to claim 1 and a resin agent.

22. The black pigment according to claim 1, wherein the black pigment contains Si or Fe, or Si and Fe as accessary components in addition to the main components.

23. The method of manufacturing a black pigment according to claim 9, wherein the primary grinding step is performed by wet grinding.

24. The method of manufacturing a black pigment according to claim 9, wherein the primary grinding step is performed by wet grinding using water as a solvent.

25. The method of manufacturing a black pigment according to claim 12, wherein the primary grinding step is performed by wet grinding.

26. The method of manufacturing a black pigment according to claim 12, wherein the primary grinding step is performed by wet grinding using water as a solvent.

2-3. -3. (canceled)

6. (canceled)

10. (canceled)

13. (canceled)