Subpigmentary titanium dioxide with improved photostability

• US 5,451,252 A
• Filed: 11/03/1994
• Issued: 09/19/1995
• Est. Priority Date: 07/11/1992
• Status: Expired due to Fees

• Current Assignee: Kronos Incorporated (Seahawk Acquisition Corp.)
• Original Assignee: Kronos Incorporated (Seahawk Acquisition Corp.)
• Inventors: Schwindt, Rolf, Kluwig, Manfred, Elfenthal, Lothar
• Primary Examiner(s): BOS, STEVEN J
• Application Number:
  US08/333,689
• Time in Patent Office: 320 Days
• Field of Search: 106/436, 106/441, 106/439, 106/430, 106/440, 423/266
• US Class Current: 106/436
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/10 extending in one dimension, e.g. needle-like
• CPC Class Codes: C01P 2004/32 Spheres
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C09C 1/3607 Titanium dioxide

Abstract

Subpigmentary titanium dioxide with decreased photoactivity is produced if known ions for increasing photostability in titanium dioxide pigments are not deposited on the surface of the subpigmentary particles, but instead are included intracrystallinely in the pigment particle (i.e., doped). In a preferred process for preparation of doped subpigmentary titanium dioxide particles, an acid solution containing the dopant is added in two stages to a suspension of subpigmentary titanium dioxide.

Claims

1. A process for preparing metal ion-doped subpigmentary titanium dioxide particles having improved photostability wherein the metal ion-dopant is homogeneously intracrystalline-distributed internally in the subpigmentary titanium dioxide particles, said process comprising the steps of:

(a) providing a suspension of subpigmentary titanium dioxide;

(b) introducing a first portion of a metal ion-dopant into the suspension;

(c) maturing the suspension for a first period of time;

(d) introducing the remainder of the metal ion-dopant into the suspension;

(e) maturing said suspension for a second period of time;

(f) recovering subpigmentary titanium dioxide from said suspension;

thereby producing metal ion-doped subpigmentary titanium dioxide particles with the dopant distributed intracrystallinely throughout the particles.

2. A process according to claim 1, further comprising subjecting the subpigmentary titanium dioxide particles to a posttreatment consisting of precipitating inorganic oxides on the subpigmentary titanium dioxide particles.

3. A process according to claim 1, wherein the dopant comprises at least one metal ion selected from the group consisting of ions of iron, antimony, zinc, manganese, niobium, vanadium, nickel, copper and tantalum.

4. A process according to claim 1, further comprising introducing a solution or suspension of colloidal tin oxide particles having an average particle size in the range from 1 to 10 nm into the suspension of titanium dioxide after introducing the first portion of the dopant.

5. A process according to claim 4, wherein the suspension of titanium dioxide and the first portion of dopant is heated to a temperature of about 60°

C. for a period of at least about 30 minutes prior to introdution of the remainder of the dopant.

6. A process according to claim 1, wherein the subpigmentary titanium dioxide is prepared by hydrolysis of a titanyl sulfate solution.

7. A process according to claim 4, wherein the solution containing colloidal tin oxide has an average particle size of less than 4 nm and is introduced into said suspension to limit the particle size of the subpigmentary titanium dioxide produced.

8. A process according to claim 1, wherein said metal ion-doped subpigmentary titanium dioxide particles are recovered by filtering.

9. A process according to claim 1, wherein said metal ion, doped subpigmentary titanium dioxide particles are subjected to at least one post-treatment step selected from the group consisting of washing, drying, tempering, grinding, inorganic post treatment and final milling.

10. A process according to claim 1, further comprising subjecting the metal ion-doped subpigmentary titanium dioxide particles to a tempering treatment to increase at least one of (1) the degree of rutilization of the particles and (2) rounding of the particles.

11. Subpigmentary titanium dioxide particles, wherein said particles comprise a crystalline lattice with a metal ion-dopant for improving photostability distributed intracrystallinely throughout said lattice.

12. Subpigmentary titanium dioxide particles according to claim 11, wherein the dopant comprises at least one metal ion selected from the group consisting of ions of iron, antimony, zinc, manganese, niobium, vanadim, nickel, copper and tantalum.

13. Subpigmentary titanium dioxide particles according to claim 11, wherein the particles are spherical and have an average particle size in the range from about from 10 to 100 nm.

14. Subpigmentary titanium dioxide particles according to claim 13, wherein the particles have an average particle size in the range from about 20 to 80 nm.

15. Subpigmentary titanium dioxide particles according to claim 11, wherein the particles are acicular.

16. Subpigmentary titanium dioxide particles according to claim 11, wherein the particles contain from 0.1 to 5 atom-% of the dopant.