# US 11,993,723 B2 · Digital ceramic inkjet inks for glass and method for obtaining same

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- Number: US 11,993,723 B2
- Document ID: US11993723B2
- Status: Granted
- Kind: B2
- Application number: 17/272,310
- Filed: 2019-08-30
- Published: 2021-12-23
- Granted: 2024-05-28
- Earliest claimed: 2018-08-31
- Assignees: Tecglass Sl
- Applicants: Tecglass Sl
- Inventors: Javier Fernandez Vazquez; Tri Ratna Tuladhar
- Web page: https://patentgrep.com/patent/US11993723B2

## CPC

- C09D 11/322: Pigment inks
- B41J 2/21: for multi-colour printing
- B41J 2/2107: {characterised by the ink properties (supplying ink in a solid state B41J2/17593)}
- B41M 1/34: on glass or ceramic surfaces {(ink-jet printing on glass or ceramic surfaces B41M5/00)}
- B41M 5/007: {on glass, ceramic, tiles, concrete, stones, etc.}
- C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
- C09D 11/12: based on waxes or bitumen
- C09D 11/34: Hot-melt inks
- C09D 11/36: based on non-aqueous solvents
- 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)
- B41J: TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41M: PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING, (correction of typographical errors B41J; processes for applying transfer pictures or the like B44C1/16; fluid media for correction of typographical errors by coating C09D10/00; printing textiles D06P)

## Abstract

Ceramic inkjet inks for non-porous substrates (such as glass, metals) whereby the viscosity of the inks at the jetting temperature of 33-50° C. is 8-20 mPa·s and increase substantially to more than a factor of 5 (greater than 100 mPa·s) after landing on the substrate. The invention also relates to processing/formulating steps and tuning of the bulk and dynamic properties suitable for (i) inkjet printing in the printhead channel and (ii) desirable high viscosity after landing on the glass substrate. The ink comprises: Glass Frit composition which is in the form of particles having a volume particle size distribution Dv90 of less than 1.5 μm, carriers (30-50 wt %) and additives (0-10%). The ceramic ink mitigate ink splattering, spreading during and after landing, eliminate/reduce image defects because of dust contaminations from the environment on wet inks after printing.

## Claims

### Claim 1

Digital ceramic inject inks for glass comprising:
Glass Frit composition being present between 25 wt. % and 60 wt. % which is in the form of particles having a volume particle size distribution Dv90 of less than 1.5 μm, as measured by laser diffraction;
Inorganic pigments being present between 1 wt. % and 25 wt. % comprising oxides of metals and are heat resistant inorganic pigments having an average size of 2-3 microns, chemically inert and stable to ultraviolet light;
Carriers being present between 30 wt. % and 40 wt %, comprising mainly of polar, non-polar or Aqueous solvents;
Additives being present between 0 wt. % and 10 wt %;
wherein the solvents are also less than 10 wt. % mixtures of alkane waxes with a low melting point of 40-100° C., being solid at room temperature.

### Claim 2 (depends on 1)

The digital ceramic inject inks for glass according to claim 1, wherein
the glass Frit composition has in wt % weight percent of the total weight of the glass frit composition:
20-49 wt. % SiO2,
3-20 wt. % B2O3,
1-9 wt. % Na2O,
0.1-5 wt. % K2O,
1-7 wt. % TiO2,
0.01-1 wt. % Al2O3,
And the rest of the composition up to 100 wt % is either a combination of B2O3, Li2O and ZnO, or, B2O3 and ZnO or B2O3 and Li2O, or ZnO and Li2O
the oxides metals of the Inorganic pigments (1-25 Wt %) are such as chromium oxide, titanium dioxide (for white), or mixed oxides, iron oxide for different colours, are heat resistant inorganic pigments having an average size of 2-3 microns, chemically inert and stable to ultraviolet light,
the carriers (30-40 wt %), are additionally one of the following types:
Non polar inks;
Polar inks; or
Aqueous ink
the Additives, 0-10 wt % are one or a combination of:
Carriers, rheology agents, surfactants, anti-settling/static agents, flow and levelling agents, de-foaming/de-aeration agents, and resins; the additives can be in an amount up to 10 wt. %.

### Claim 3 (depends on 1)

The digital ceramic inject inks for glass according to claim 1, wherein the glass frit composition is one of the following:
glass Bismuth/Zinc frit composition Frit F1 including:
20-49 wt. % SiO2,
3-20 wt. % B2O3,
1-9 wt. % Na2O,
0.1-5 wt. % K2O,
1-7 wt. % TiO2,
0.01-1 wt. % Al2O3,
40-55 wt. % Bi2O3,
0.5-3 wt. % ZnO,
0.1-4 wt % Li2O,
mixture of other oxides such as CaO, BaO, MgO, P2O5, Fe2O3, SrO in an amount less than 10 wt %; or
Lithium free Bismuth/Zinc frit composition Frit F2 including:
20-49 wt. % SiO2,
3-20 wt. % B2O3,
1-9 wt. % Na2O,
0.1-5 wt. % K2O,
1-7 wt. % TiO2,
0.01-1 wt. % Al2O3,
50-60 wt. % Bi2O3,
7-12 wt. % ZnO,
mixture of other oxides such as CaO, BaO, MgO, P2O5, Fe2O3, SrO in an amount less than 10 wt %; or
Bismuth frit composition Frit F3 including:
20-49 wt. % SiO2,
3-20 wt. % B2O3,
1-9 wt. % Na2O,
0.1-5 wt. % K2O,
1-7 wt. % TiO2,
0.01-1 wt. % Al2O3,
45-55 wt. % Bi2O3,
0.1-4 wt. % Li2O
mixture of other oxides such as CaO, BaO, MgO, P2O5, Fe2O3, SrO in an amount less than 10 wt. %; or
Zn frit composition Frit F4 including:
20-49 wt. % SiO2,
3-20 wt. % B2O3,
1-9 wt. % Na2O,
0.1-5 wt. % K2O,
1-7 wt. % TiO2,
0.01-1 wt. % Al2O3,
7-15 wt. % ZnO,
1-5 wt % Li2O.

### Claim 4 (depends on 2)

The digital ceramic inject inks for glass according to claim 2, wherein the inorganic pigments are Cobalt chromite Blue green Spinel, Cobalt Aluminate Blue Spinel, Iron oxide red, Manganese Ferrite, Nickel Antimony Titanium Yellow Rutile, Copper Chromite Black Spinel, manganese ferrite, White titanium dioxide rutile and Anatase, Cobalt Titanate Green Spinel, Cobalt Chromite Blue Green Spinel; Brilliant bright colours yellow, oranges and red, which are capable of withstanding tempering conditions are cadmium range inorganic pigments such as Yellow 37 (Cadmium sulphide), Orange 20, Red 108 (Cadmium sulfoslenide) and Yellow 35 (Zinc cadmium Sulphide).

### Claim 5 (depends on 2)

The digital ceramic inject inks for glass according to claim 2, wherein the carriers are a mixture of linear C10-C24 alkanes, preferably linear C10-C22 alkanes, more preferably linear C12-C18 alkanes.

### Claim 6 (depends on 2)

The digital ceramic inject inks for glass according to claim 2, wherein the carriers are one or more alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohols, butyl alcohols; glycols, such as methyl glycol (MG), ethyl glycol, propyl glycol, butyl glycol (BG); glycol ethers, such as methoxy propanol (PM), ethoxy propanol (EP), diacetone propanol (DAA), methoxy butanol, dipropylene glycol monomethyl ether (DPM), tripropylene glycol methyl ether (TPM), propylene glycol mono methyl ether (PM), di or tri propylene glycol mono propyl ether (DPnP, TPnP), butyl diglycol (BDG); esters, such as methyl acetate, ethyl acetate (ETAC), propyl acetate(IPAC), butyl acetate (BUAC), methoxy propyl acetate (PMA), ethyl-3-ethoxy-propanol (EEP); ketones, such as acetone, methyl ethyl ketone (MEK), methyl butyl ketone, cyclohexanone.

### Claim 7 (depends on 2)

The digital ceramic inject inks for glass according to claim 2, wherein the carriers are water and mixture of one or more alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohols, butyl alcohols; glycols, such as methyl glycol (MG), ethyl glycol, propyl glycol, butyl glycol (BG); glycol ethers, such as methoxy propanol (PM), ethoxy propanol (EP), diacetone propanol (DAA), methoxy butanol, dipropylene glycol monomethyl ether (DPM), tripropylene glycol methyl ether (TPM), propylene glycol mono methyl ether (PM), di or tri propylene glycol mono propyl ether (DPnP, TPnP), butyl diglycol (BDG); esters, such as methyl acetate, ethyl acetate (ETAC), propyl acetate(IPAC), butyl acetate (BUAC), methoxy propyl acetate (PMA), ethyl-3-ethoxy-propanol (EEP), or a mixture thereof.

### Claim 8 (depends on 1)

A process for manufacturing the digital ceramic inks for glass according to claim 1, wherein the process comprises the following steps:
A. Preparing a glass frit paste (FP) by milling and grinding frit powder in the presence of a dispersant agent and a solvent to achieve a pigment volume particle size distribution Dv90 of less than 1.5 μm;
B. Preparing an inorganic pigment paste (PP) by milling and grinding pigment particles in the presence of a dispersant agent and a solvent to achieve a pigment volume particle size distribution Dv90 of less than 1 μm;
C. Mixing the frit paste of step (A) and pigment paste of step (B) in a high shear mixer or bead mixer;
D. Add a thinner constituting of mixture of solvents and additives to the concentrated ink of step (C) to achieve specific final formulations in the let-down medium, having a final solid content 30-60 wt. % on the total weight of the mixture and desired ink properties; and
E. Filtering the mixture of step (D) through a micrometer pore size filter, thereby obtaining a ceramic inkjet ink having a viscosity of 6-20 mPa·s at jetting temperature and jetting conditions.

### Claim 9 (depends on 7)

The process for manufacturing the digital ceramic inks according to claim 7, wherein in the milling for preparation of the frit paste is carried out by a mixing shear mixer of frit powder with dispersant, resins (such as polyacrylate, polyalkyd and polyamide resins) an a selection of solvents (non-polar aliphatic hydrocarbon, Polar glycol ether family, Aqueous water, thermoplastic paraffin wax, or mixture of one or many solvents), being followed by wet milling in a chamber component such as zirconia, silicon nitrite and/or silicon carbide and the final composition is dispersed frit paste with final particle size <1.5 μm.

### Claim 10 (depends on 9)

The process for manufacturing the digital ceramic inks according to claim 9, wherein the wet milled frit paste is one of the following table:
Bismuth-
Bismuth-
Zinc
Zinc
Zinc
Zinc
FP1-Non
FP2-
FP3-Non
FP4-
Components
polar
Polar
Polar
Polar
Bismuth/Zinc based
60-65%
60-65%
Frit F1
Zinc based Frit F4
60-65%
60-65%
C14-C18, n-alkanes
30-40%
30-40%
hydrocarbon
Dipropylene glycol
30-40%
30-40%
monomethyl ether
(DPM)
Polyamide resins
2-5%
Disperbyk 180
5-10%
Tego Dispers 656
5-10%

### Claim 11 (depends on 8)

The process for manufacturing the digital ceramic inks according to claim 8, wherein the inorganic pigment paste comprises 45-85 wt. % pigment, 2-20 wt. % dispersant agent and 10-55 wt. % solvent wherein the pigment is milled and grinded in the presence of a dispersant agent and a solvent, wherein the milling of the pigment powder (average particle size of 7-20 micron) is carried out by pre-mixing of pigment powder with specific dispersant, resins the selected choice of solvents (non-polar aliphatic hydrocarbon, Polar glycol ether family, Aqueous water, thermoplastic paraffin wax), this is then followed by wet milling using basket mill or a chamber components such as zirconia, silicon nitrite and/or silicon carbide.

### Claim 12 (depends on 11)

The process for manufacturing the digital ceramic inks according to claim 11, wherein the dispersant agent is a copolymer with acidic group Disperbyk 110, Disperbyk 111; alkylol ammonium salt of copolymer with acidic groups Disperbyk-180), solution of high molecular weight block copolymers with pigment affinic groups Disperbyk 182, Disperbyk 184, Disperbyk 190; copolymer with pigment affinic groups Disperbyk 191, Disperbyk 192, Disperbyk 194, Bykjet 9142Tego Dispers 7502, Tego Dispers 752W; block-copolymer with pigment affinic groups Disperbyk 2155; solution of alkylol ammonium salt of a higher molecular weight acidic polymer Anti-terra-250; structured acrylate copolymer with pigment affinic groups (Disperbyk 2010, Disperbyk 2015), polyvinylpyrrolidone, PVP K-15, PVP K-30, PVP K-60; polymeric hyperdispersant Solsperse J930, Solsperse J945, Solsperse J955, Solsperse J980, Solsperse J981, Solsperse J944, Solsperse J950, Solsperse J955: High molecular weight—polyurethane Efka PU 4009, EFKA PU 4010; high-molecular-weight carboxylic acid salts (Efka Fa4564) or a mixture thereof.