Ink jet ink compositions

• US 9,796,861 B2
• Filed: 04/02/2015
• Issued: 10/24/2017
• Est. Priority Date: 04/08/2014
• Status: Active Grant

• Current Assignee: Lubrizol Advanced Materials Incorporated (Berkshire Hathaway Incorporated)
• Original Assignee: Lubrizol Advanced Materials Incorporated (Berkshire Hathaway Incorporated)
• Inventors: Cartridge, David, Coulbeck, Elliot, Furmston, Chris, Thetford, Dean
• Primary Examiner(s): SOLOMON, LISA
• Application Number:
  US15/302,013
• Publication Number:
  US 20170183518A1
• Time in Patent Office: 936 Days
• Field of Search: None
• CPC Class Codes: B41J 2/01 Ink jet
• CPC Class Codes: C04B 41/0072 Heat treatment
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/4896 Polyethers
• CPC Class Codes: C04B 41/83 Macromolecular compounds
• CPC Class Codes: C09B 67/0002 Grinding; Milling with solid grinding or milling assistants
• CPC Class Codes: C09B 67/0022 Wet grinding of pigments
• CPC Class Codes: C09B 67/009 polymeric dispersing agent
• CPC Class Codes: C09D 11/03 characterised by features other than the chemical nature of the binder
• CPC Class Codes: C09D 11/322 Pigment inks
• CPC Class Codes: C09D 11/326 characterised by the pigment dispersant
• CPC Class Codes: C09D 11/36 based on non-aqueous solvents
• CPC Class Codes: C09D 17/002 in organic medium C09D17/003, C09D17/004 take precedence
• CPC Class Codes: C09D 17/007 Metal oxide

Abstract

The invention provides dispersed inorganic mixed metal oxide pigment compositions utilizing a carboxylic acid, containing dispersant and a mixed metal oxide pigment. The metal oxide pigment is of the type used to color ceramic or glass articles. The dispersant, in addition to at least one carboxylic acid group, comprises at least one 300-3000 g/mole solubilizing chain of repeating units from hydrocarbylene or repeating units from C3 or C4 alkylene ethers or mixtures of said ethers. A milling process using beads is also described to reduce the mixed metal oxide particle size to the desired range. A method of using the mixed metal oxide dispersion to digitally print an image on a ceramic or glass article using the dispersion jetted through a nozzle and firing the colored article is also described.

Claims

1. A composition comprising a particulate solid, a non-polar medium and a dispersing agent of the formula (1)

[R—

X]_m-Q 

 

(1)

wherein R is

i) a C_20-200 hydrocarbylene chain linked to a terminal hydroxyl or amine group that reacts to form X, or

ii) a 300 to 3000 g/mole monosubstituted polyether chain obtained from poly(C_3-16-alkylene oxide) with a connecting group of 1 to 15 atoms to link to a terminal hydroxyl or amine group that reacts to form X where the alkylene oxide may be a mixture of C_3-16 alkylene oxide and wherein said polyether chain optionally includes up to 5 wt. %, based on the weight of the poly(alkylene oxide), of repeat units from ethylene oxide, or

iii) a combination of i) and ii) when m is greater than 1;

or

iv) a C_1-19 optionally substituted hydrocarbylene with heteroatoms, such as O and N, linked to a hydroxyl or amine that reacts with a carbonyl of Q to form X with a combination of i) or ii) or mixtures thereof, when m is greater than 1;

m is 1-3;

X is O, NG, N or mixtures thereof;

addition of an optionally substituted alkyl (meth)acrylate or (meth)acrylamide with X when it is an amine; and

Q is derived from a compound of 2 to 24 carbon atoms containing at least 2 or more carboxylic acids or derivatives thereof, such as 1 or more anhydride groups, where the linkage between X and Q is represented by an ester, amide or imide group from coupling the compound of Q through ester, amide or imide forming reactions with X, and Q contains at least one residual, free acidic carboxyl group and can optionally contain heteroatoms, such as O and N, and halogens such as Cl and Br or mixtures thereof, and wherein the particulate solid is a mixed metal oxide pigment that develops its color intensity and hue after firing at elevated temperatures.

2. The composition according to claim 1, wherein R is a polyisobutylene compound of 500 to 2800 g/mole molecular weight.

3. The composition according to claim 1, wherein R is a poly(alkylene oxide) compound of 500 to 2800 g/mole molecular weight and wherein the monosubstituted group on said polyether chain is a C₁-C₃₆ hydrocarbyl.

4. The composition according to claim 1, wherein X is an amide linkage.

5. The composition according to claim 1, wherein X is an imide linkage.

6. The composition according to claim 1, wherein X is an ester linkage.

7. The composition according to claim 1, wherein Q is derived from a polycarboxylic acid or an anhydride, thereof, having from 8 to 24 carbon atoms and optionally substituted with one or more halogen, oxygen, and/or nitrogen and having at least one aryl group and having from 2 to 6 carbonyl groups in the carboxylic acid, anhydrides thereof, or mixtures thereof.

8. The composition, according to claim 1, wherein Q is derived from an aliphatic polycarboxylic acid and/or an anhydride thereof having from 2 to 24 carbon atoms and optionally substituted with one or more halogen, oxygen, and/or nitrogen.

9. The composition as claimed in claim 1, wherein the particulate solid is at least one ceramic pigment of mixed metal oxides which contain a combination of two or more elements in cationic form selected from Al, Mg, Ca, Cd, Co, Cr, Fe, In, Mn, Ni, Pr, Sb, Se, Si, Sn, Ti, V, Zn and Zr.

10. The composition as claimed in claim 1, wherein the inorganic particulate is present from about 20 to about 60 wt. % of said composition.

11. A process for milling an inorganic particulate, having a dry powder volume average particle diameter D₅₀ in excess of 1 micron, in a non-polar solvent to a D₅₀ particle size of less than 600 nanometres, said process comprising;

a) blending a non-polar organic medium, said inorganic particulate material comprising a mixed metal oxide pigment, optionally including a vitreous glaze material, having a dry powder volume average particle diameter in excess of 1 micron, and a dispersing agent of the formula

[R—

X]_m-Q 

 

(1)

wherein R is

i) a C_20-200 hydrocarbylene chain linked to a terminal hydroxyl or amine group that reacts to form X, or

ii) a 300 to 3000 g/mole monosubstituted polyether chain obtained from poly(C_3-16-alkylene oxide) with a connecting group of 1 to 15 atoms to link to a terminal hydroxyl or amine group that reacts to form X where the alkylene oxide may be a mixture of C_3-16 alkylene oxide and wherein said polyether chain optionally includes up to 5 wt. %, based on the weight of the poly(alkylene oxide), of repeat units from ethylene oxide, or

iii) a combination of i) and ii) when m is greater than 1;

or

iv) a C_1-19 optionally substituted hydrocarbylene with heteroatoms, such as O and N, linked to a hydroxyl or amine that reacts with a carbonyl of Q to form X with a combination of i) or ii) or mixtures thereof, when m is greater than 1;

m is 1-3;

X is O, NG, N or mixtures thereof;

G is H or an optionally substituted C_1-36 hydrocarbylene group, or is the residue of a Michael addition of an optionally substituted alkyl (meth)acrylate or (meth)acrylamide with X when it is an amine; and

Q is derived from a compound of 2 to 24 carbon atoms containing at least 2 or more carboxylic acids or derivatives thereof, such as 1 or more anhydride groups, where the linkage between X and Q is represented by an ester, amide or imide group from coupling the compound of Q through ester, amide or imide forming reactions with X, and Q contains at least one residual, free acidic carboxyl group and can optionally contain heteroatoms, such as O and N, and halogens such as Cl and Br or mixtures thereof;

b) milling said mixed metal oxide pigment dispersed with said dispersing agent in said non-polar organic medium using a bead mill for 5 minutes to 60 hours; and

c) confirming the volume average particle diameter D₅₀ is less than 600 nanometres.

13. The process according to claim 11, wherein said metal oxide pigment contains a combination of two or more different elements in the form of cations selected from the group of Al, Mg, Ca, Cd, Co, Cr, Fe, In, Mn, Ni, Pr, Sb, Se, Si, Sn, Ti, V, Zn and Zr and wherein if R is a monosubstituted polyether chain, the monosubstituted group on said polyether chain is a C₁-C₃₆ hydrocarbyl.

12. A process for milling an inorganic particulate, having a dry powder volume average particle diameter D₅₀ in excess of 1 micron, in a non-polar solvent to a D₅₀ particle size of less than 600 nanometres, said process comprising;

a) blending a non-polar organic medium, said inorganic particulate material comprising a mixed metal oxide pigment, optionally including a vitreous glaze material, having a dry powder volume average particle diameter in excess of 1 micron, and a dispersing agent of the formula

[R—

X]_m-Q 

 

(1)

wherein R is

i) a C_20-200 hydrocarbylene chain linked to a terminal hydroxyl or amine group that reacts to form X, or

ii) a 300 to 3000 g/mole monosubstituted polyether chain obtained from poly(C_3-16-alkylene oxide) with a connecting group of 1 to 15 atoms to link to a terminal hydroxyl or amine group that reacts to form X where the alkylene oxide may be a mixture of C_3-16 alkylene oxide and wherein said polyether chain optionally includes up to 5 wt. %, based on the weight of the poly(alkylene oxide), of repeat units from ethylene oxide, or

iii) a combination of i) and ii) when m is greater than 1;

or

iv) a C_1-19 optionally substituted hydrocarbylene with heteroatoms, such as O and N, linked to a hydroxyl or amine that reacts with a carbonyl of Q to form X with a combination of i) or ii) or mixtures thereof, when m is greater than 1;

m is 1-3;

X is O, NG, N or mixtures thereof;

G is H or an optionally substituted C_1-36 hydrocarbylene group, or is the residue of a Michael addition of an optionally substituted alkyl (meth)acrylate or (meth)acrylamide with X when it is an amine; and

Q is derived from a compound of 2 to 24 carbon atoms containing at least 2 or more carboxylic acids or derivatives thereof, such as 1 or more anhydride groups, where the linkage between X and Q is represented by an ester, amide or imide group from coupling the compound of Q through ester, amide or imide forming reactions with X, and Q contains at least one residual, free acidic carboxyl group and can optionally contain heteroatoms, such as O and N, and halogens such as Cl and Br or mixtures thereof;

b) milling said mixed metal oxide pigment dispersed with said dispersing agent in said non-polar organic medium using a bead mill at a milling rate of 0.4 to 8 KWatt/hour per Kg of particulate; and

c) confirming the volume average particle diameter D₅₀ so is less than 600 nanometres.

20. The process according to claim 12, wherein said metal oxide pigment contains a combination of two or more different elements in the form of cations selected from the group of Al, Mg, Ca, Cd, Co, Cr, Fe, In, Mn, Ni, Pr, Sb, Se, Si, Sn, Ti, V, Zn and Zr and wherein if R is a monosubstituted polyether chain the monosubstituted group on said polyether chain is a C₁-C₃₆ hydrocarbyl.

14. A process for digitally printing on ceramic article or glass article substrate using an ink jetted through a nozzle,

a) providing a mixed metal oxide dispersed in a non-polar organic medium with a dispersing agent of the formula

[R—

X]_m-Q 

 

(1)

wherein R is

i) a C_20-200 hydrocarbylene chain linked to a terminal hydroxyl or amine group that reacts to form X, or

ii) a 300 to 3000 g/mole monosubstituted polyether chain obtained from poly(C_3-16-alkylene oxide) with a connecting group of 1 to 15 atoms to link to a terminal hydroxyl or amine group that reacts to form X where the alkylene oxide may be a mixture of C_3-16 alkylene oxide and wherein said polyether chain optionally includes up to 5 wt. %, based on the weight of the poly(alkylene oxide), of repeat units from ethylene oxide, or

iii) a combination of i) and ii) when m is greater than 1;

or

iv) a C_1-19 optionally substituted hydrocarbylene with heteroatoms, such as O and N, linked to a hydroxyl or amine that reacts with a carbonyl of Q to form X with a combination of i) or ii) or mixtures thereof, when m is greater than 1;

m is 1-3;

X is O, NG, N or mixtures thereof;

G is H or an optionally substituted C_1-36 hydrocarbylene group, or is the residue of a Michael addition of an optionally substituted alkyl (meth)acrylate or (meth)acrylamide with X when it is an amine; and

Q is derived from a compound of 2 to 24 carbon atoms containing at least 2 or more carboxylic acids or derivatives thereof, such as 1 or more anhydride groups, where the linkage between X and Q is represented by an ester, amide or imide group from coupling the compound of Q through ester, amide or imide forming reactions with X, and Q contains at least one residual, free acidic carboxyl group and can optionally contain heteroatoms, such as O and N, and halogens such as Cl and Br or mixtures thereof;

b) jetting said mixed metal oxide dispersed in said non-polar organic medium using said dispersing agent onto said substrate, optionally where said substrate has had one or more layers of glaze applied thereon, to form a pigmented digital image on said substrate wherein said image develops into a colored image upon firing said ceramic substrate or heating said glass substrate to provide tempering or annealing;

c) optionally applying a glaze over said digital image; and

d) heating said ceramic article at an elevated temperature or heating said glass article to anneal or temper it, wherein said image from metal oxide develops optimal color intensity upon heating to its color.

15. The process of claim 14, wherein the mixed metal oxide pigment that develops its color intensity and hue after firing at 600°

C. or above for a ceramic substrate or 400°

C. or above for a glass substrate and wherein if R is a monosubstituted polyether chain the monosubstituted group on said polyether chain is a C₁-C₃₆ hydrocarbyl.

16. The process of claim 14, wherein said metal oxide is at least one ceramic pigment of mixed metal oxides which contain a combination of two or more elements in cationic form selected from the group of Al, Mg, Ca, Cd, Co, Cr, Fe, In, Mn, Ni, Pr, Sb, Se, Si, Sn, Ti, V, Zn and Zr.

17. The process of claim 14, wherein said metal oxide is present in said dispersion of metal oxide in non-polar organic medium at a concentration of from about 20 to about 60 wt. %.

18. The process of claim 14, wherein R is a mono substituted polyether chain and said nonpolar organic medium is selected from petroleum distillate, octyl octonoate, 2-ethylhexyl-stearate, 2-ethylhexyl-cocoate, di-octyl adipate, isopropyl laurate, ethylhexyl cocoate, propylene glycol dicaprylate, tripropylene glycol bis-2-ethylhexanoate, tripropylene glycol mono-2-ethylhexanoate, tripropylene glycol (methyl ether), dipropylene glycol (methyl ether), di- propylene glycol (n-butyl ether), and isopropyl bisphenols such as 2,2-bis(4-hydroxy-3-isopropyl-phenyl)propane and mixtures thereof.

19. The process of claim 14, wherein R is a polyisobutylene and said nonpolar organic medium is selected from petroleum distillate, octyl octonoate, 2-ethylhexyl-stearate, 2-ethyl-hexyl-cocoate, di-octyl adipate, isopropyl laurate, ethylhexyl cocoate, propylene glycol dicaprylate, tripropylene glycol bis-2-ethylhexanoate, tripropylene glycol mono-2-ethylhexanoate, and isopropyl bisphenols such as 2,2-bis(4-hydroxy-3-isopropyl-phenyl)propane, and mixtures thereof.