# US 9,751,902 B2 · Organic titanium derivative and process for the preparation thereof, ink containing the derivative and ceramic digital printing method that uses the ink

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- Number: US 9,751,902 B2
- Document ID: US9751902B2
- Status: Granted
- Kind: B2
- Application number: 15/123,874
- Filed: 2015-07-23
- Published: 2017-01-19
- Granted: 2017-09-05
- Earliest claimed: 2014-07-24
- Assignees: Graziano Vignali
- Applicants: Graziano Vignali
- Inventors: Graziano Vignali; Fabrizio Guizzardi
- Web page: https://patentgrep.com/patent/US9751902B2

## CPC

- C07F 7/28: Titanium compounds
- B41J 2/01: Ink jet
- C04B 41/82: with organic materials
- C08G 83/001: {Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica}
- C08K 5/0091: {Complexes with metal-heteroatom-bonds}
- C09D 11/02: Printing inks (C09D11/30 takes precedence)
- C09D 11/033: characterised by the solvent
- C09D 11/322: Pigment inks
- C09D 11/38: characterised by non-macromolecular additives other than solvents, pigments or dyes
- C09D 11/40: Ink-sets specially adapted for multi-colour inkjet printing
- C04B 2235/3232: Titanium oxides or titanates, e.g. rutile or anatase
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B41J: TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

Described is a production process for the preparation of an organic titanium derivative useful for the preparation of yellow inks for digital printing on ceramics, comprising the following steps: (i) mixing an organic and/or inorganic compound of titanium (IV) and a 1,3-diol of formula: wherein R1, R2, R3 and R4 are independently selected from H and a linear or branched C1-C6 alkyl radical, in the presence of at least an organic solvent immiscible with water and subsequent removal of reaction by-products; (ii) adding water to the reaction mixture in a H2O:Ti≧2 molar ratio and subsequent removal of unreacted water and reaction by-products; (iii) maturing the reaction mixture at a temperature of 180-200° C. for 16-50 hours. Also described are the titanium derivative obtainable by means of the above-reported process, an ink that contains the derivative and a method of digital printing on ceramics that uses said ink.

## Claims

### Claim 1

A process for the preparation of an organic titanium derivative, comprising the following steps:
(i) mixing an organic and/or inorganic compound of titanium (IV) and a 1,3-diol of formula [1]:
wherein R1, R2, R3 and R4 are independently selected from H and a linear or branched C1-C6 alkyl radical,
in a Ti:diol molar ratio of between 1:0.85 and 1:1.20, in the presence of at least an organic solvent immiscible with water and subsequent removal of reaction by-products;
(ii) adding water to the reaction mixture in a H2O:Ti≧2 molar ratio and subsequent removal of unreacted water and reaction by-products;
(iii) maturing the reaction mixture at a temperature of 180-200° C. for 16-50 hours.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the organic and/or inorganic compound of titanium (IV) used in step (i) is selected from titanium halides, titanium sulphate, titanium hydroxide, chloro-isopropyl-titanate, titanium oxotitanates or titanium alkoxides of formula Ti(OR)4, wherein R is a linear or branched C1-C4 alkyl radical.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the 1,3-diol used in step (i) is 2-ethyl-1,3-hexanediol.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the organic solvent used in step (i) is selected from saturated or unsaturated, cyclic or acyclic, linear or branched, possibly halogenated aliphatic hydrocarbons; aromatic hydrocarbons; ethers; glycol ethers and mixtures thereof.

### Claim 5 (depends on 1)

A titanium derivative obtainable by the process according to claim 1, in the form of a titanium-containing organo-inorganic polymer characterized in that the polymeric fraction having Log M≧3 has an at least bimodal molecular weight distribution and represents at least 70% by weight of the derivative.

### Claim 6 (depends on 5)

An ink containing a titanium derivative of claim 5, comprising:
(A) 6.0-12.0% by weight of Ti in the form of said titanium derivative;
(B) 0.5-2.0% by weight of Cr in the form of an organic compound of Cr(III) and/or 1.0-3.0% by weight of Ni in the form of an organic compound of Ni;
(C) at least a organic solvent selected from saturated or unsaturated, cyclic or acyclic, linear or branched, possibly alogenated aliphatic hydrocarbons, aromatic hydrocarbons, ethers, glycol ethers, esters, carbonates, and mixtures thereof.

### Claim 7 (depends on 6)

The ink according to claim 6, further comprising as fourth component, (D), triphenylantimony, Sb(C6H5)3, in an amount such that the metal represents between 6.0 and 9.0% by weight of the ink.

### Claim 8 (depends on 6)

The ink according to claim 6, wherein the weight ratio of Ti to Cr is between 13:1 and 5:1.

### Claim 9 (depends on 6)

The ink according to claim 6, further comprising up to 10% by weight of the starting 1,3-diol.

### Claim 10 (depends on 6)

A ceramic printing method that uses the ink of any claim 6, comprising the following operational steps:
(a) preparing a ceramic material mixed with an additive comprising titanium dioxide (TiO2) and/or antimony trioxide (Sb2O3);
(b) applying said ink by means of digital printing on the ceramic material resulting from step (a);
(c) firing the ceramic material resulting from step (b) at a temperature of between 900° C. and 1300° C.

### Claim 11 (depends on 6)

An ink set comprising:
the ink according to claim 6;
a second ink (I2) comprising an organic solvent and at least an organic compound of cobalt; and
a third ink (I3) comprising an organic solvent and at least an organic compound of iron.

### Claim 12 (depends on 11)

The ink set according to claim 11, further comprising a fourth ink (I4) comprising an organic solvent and at least an organic compound of cobalt in combination with at least an organic compound of iron.