RADIATION CURABLE POLYURETHANE-BASED BINDER DISPERSION

• US 20180179325A1
• Filed: 10/28/2015
• Published: 06/28/2018
• Est. Priority Date: 10/28/2015
• Status: Active Grant

• Current Assignee: Hewlett-Packard Development Company, L.P. (HP Inc.)
• Original Assignee: Hewlett-Packard Development Company, L.P. (HP Inc.)
• Inventors: Chen, Tienteh, Huang, Bin, Abelovski, Benjamin, Sarkisian, George
• Granted Patent: US 10,829,583 B2
• Time in Patent Office: Days
• CPC Class Codes: B41M 5/0017 Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
• CPC Class Codes: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/0828 containing sulfonate groups or groups forming them
• CPC Class Codes: C08G 18/0866 the dispersing or dispersed phase being an aqueous medium
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/246 containing also tin-carbon bonds
• CPC Class Codes: C08G 18/2865 Compounds having only one primary or secondary amino group; Ammonia
• CPC Class Codes: C08G 18/288 Compounds containing at least one heteroatom other than oxygen or nitrogen
• CPC Class Codes: C08G 18/3215 containing aromatic groups or benzoquinone groups
• CPC Class Codes: C08G 18/348 Hydroxycarboxylic acids
• CPC Class Codes: C08G 18/3872 the sulfur atom belonging to a sulfoxide or sulfone group
• CPC Class Codes: C08G 18/4833 Polyethers containing oxyethylene units
• CPC Class Codes: C08G 18/62 Polymers of compounds having carbon-to-carbon double bonds
• CPC Class Codes: C08G 18/6225 Polymers of esters of acrylic or methacrylic acid
• CPC Class Codes: C08G 18/6541 the low-molecular compounds being compounds of group C08G18/34
• CPC Class Codes: C08G 18/6692 with compounds of group C08G18/34
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/673 containing two or more acrylate or alkylacrylate ester groups
• CPC Class Codes: C08G 18/675 Low-molecular-weight compounds
• CPC Class Codes: C08G 18/73 : acyclic
• CPC Class Codes: C08G 18/755 : and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 18/758 : containing two or more cycloaliphatic rings
• CPC Class Codes: C08L 2201/54 : Aqueous solutions or dispersions
• CPC Class Codes: C08L 2203/16 : used for films
• CPC Class Codes: C08L 75/00 : Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
• CPC Class Codes: 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
• CPC Class Codes: C09D 11/102 : containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C09D 11/30 : Inkjet printing inks
• CPC Class Codes: C09D 11/54 : Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
• CPC Class Codes: C09D 175/14 : Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 175/16 : having terminal carbon-to-carbon unsaturated bonds

Abstract

A radiation curable polyurethane-based binder dispersion includes water and a radiation curable polyurethane dispersed in the water. The polyurethane is formed from: a polyisocyanate; a polyol having a chain with two hydroxyl functional groups at one end of the chain and no hydroxyl groups at an opposed end of the chain, and having a number average molecular weight ranging from about 500 to about 5,000; an acrylate or methacrylate, the acrylate or methacrylate having at least one hydroxyl functional group and having an acrylate functional group or a methacrylate functional group; an alcohol or a diol or an amine having a number average molecular weight less than 600; and a sulfonate or sulfonic acid having one or two amino functional groups.

Claims

1. A radiation curable polyurethane-based binder dispersion, comprising:

water; and

a radiation curable polyurethane dispersed in the water, the polyurethane having been formed from;

a polyisocyanate;

a polyol having a chain with two hydroxyl functional groups at one end of the chain and no hydroxyl groups at an opposed end of the chain, and having a number average molecular weight ranging from about 500 to about 5,000;

an acrylate or methacrylate, the acrylate or methacrylate having at least one hydroxyl functional group and having an acrylate functional group or a methacrylate functional group;

an alcohol or a diol or an amine having a number average molecular weight less than 600; and

a sulfonate or sulfonic acid having one or two amino functional groups.

2. The radiation curable polyurethane-based binder dispersion as defined in claim 1, the radiation curable polyurethane having further been formed from:

i) a carboxylic acid having two or more hydroxyl functional groups;

or

ii) a homopolymer or copolymer of poly(ethylene glycol) having one or two hydroxyl functional groups or one or two amino functional groups at one end of its chain;

or

iii) a combination of i and ii.

3. The radiation curable polyurethane-based binder dispersion as defined in claim 1 wherein the sulfonate or sulfonic acid is selected from the group consisting of taurine, 4-aminotoluene-3-sulfonic acid, aniline-2-sulfonic acid, sulfanilic acid, 4-amino-1-naphthalenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 2-amino-1-naphthalenesulfonic acid, 5-amino-2-methoxybenzenesulfonic acid, 2-(cyclohexylamino)ethanesulfonic acid, 3-amino-1-propanesulfonic acid, 2-2-(aminoethyl)aminoethanesulfonic acid, 3-2-(aminoethyl)aminopropanesulfonic acid, N,N-Bis(2-hydroxyethyl)taurine, 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid, and N-(2-acetamido)-2-aminoethanesulfonic acid.

4. The radiation curable polyurethane-based binder dispersion as defined in claim 1 wherein:

the polyol is formed from a free radical polymerization of a monomer in the presence of a mercaptan including two hydroxyl functional groups or two carboxylic functional groups;

the monomer is selected from the group consisting of an alkylester of acrylic acid, an alkylester of methacrylic acid, an acid group containing monomer, acrylamide, an acrylamide derivative, methacrylamide, a methacrylamide derivative, styrene, a styrene derivative, acrylonitrile, vinylidene chloride, a fluorine containing acrylate, a fluorine containing methacrylate, a siloxane containing acrylate, a siloxane containing methacrylate, vinyl acetate, N-vinylpyrrolidone, and combinations thereof; and

the mercaptan is selected from the group consisting of thioglycerol, 1-mercapto-1,1-ethanediol, 2-mercapto-1,3-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,3-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and thioglycolic acid.

5. The radiation curable polyurethane-based binder dispersion as defined in claim 4 wherein:

the alkylester of acrylic acid or the alkylester of methacrylic acid is selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, trifluoroethyl (meth)acrylate, t-butyl (meth)acrylate, t-butyl acrylate, n-butyl acrylate 2-ethylhexyl (meth)acrylate, 2-ethylhexyl acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, allyl (meth)acrylate, isobornyl (meth)acrylate, isobornyl acrylate, polyester (meth)acrylate, polycarbonate (meth)acrylate, 2-aziridinylethyl (meth)acrylate, aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth)acrylate, amino-n-butyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate;

or

the acid group containing monomer is selected from the group consisting of acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, 2-(meth)acryloyl propionic acid, crotonic acid, and itaconic acid;

or

the acrylamide derivative or the methacrylamide derivative is selected from the group consisting of hydroxyethylacrylamide, N,N-methylol(meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone acrylamide, and N-isobutoxymethyl (meth)acrylamide;

or

the styrene derivative is selected from the group consisting of alpha-methyl styrene, p-aminostyrene, and 2-vinylpyridine.

6. The radiation curable polyurethane-based binder dispersion as defined in claim 4 wherein one of:

the monomer includes methyl methacrylate and n-butyl acrylate in a ratio of 1;

1 and the mercaptan includes 10 wt % thioglycerol;

the monomer includes methyl methacrylate and 2-ethylhexyl acrylate in a ratio of 3;

1 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes methyl methacrylate and 2-ethylhexyl acrylate in a ratio of 1;

1 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes methyl methacrylate and 2-ethylhexyl acrylate in a ratio of 9;

1 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes methyl methacrylate, 2-ethylhexyl acrylate, and methacrylic acid in a ratio of 5;

4;

1 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes allyl methacrylate and 2-ethylhexyl acrylate in a ratio of 7;

3 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes acrylonitrile and n-butyl acrylate in a ratio of 6;

4 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes benzyl methacrylate and 2-ethylhexyl acrylate in a ratio of 8;

2 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes cyclohexyl methacrylate and 2-ethylhexyl acrylate in a ratio of 66;

34 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes methyl methacrylate, 2-ethylhexyl acrylate, and diacetone acrylamide in a ratio of 50;

45;

5 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes isobornyl acrylate, methyl methacrylate and n-butylacrylate in a ratio of 20;

57;

23 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes isobornyl methacrylate and n-butyl acrylate in a ratio of 65;

35 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes cyclohexyl methacrylate and 2-ethylhexyl acrylate in a ratio of 8;

2 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes benzyl methacrylate and 2-ethylhexyl acrylate in a ratio of 19;

1 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes t-butyl acrylate and n-butyl methacrylate in a ratio of 8;

2 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes benzyl methacrylate, methyl methacrylate and n-butyl acrylate in a ratio of 2;

6;

2 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes cyclohexyl methacrylate, methyl methacrylate, and n-butyl acrylate in a ratio of 20;

57;

23 and the mercaptan includes 5 wt % thioglycerol;

the monomer includes isobornyl acrylate, methyl methacrylate and 2-ethylhexyl acrylate in a ratio of 20;

57;

23 and the mercaptan includes 5 wt % thioglycerol;

or

the monomer includes styrene and n-butyl methacrylate in a ratio of 4;

6 and the mercaptan includes 5 wt % thioglycerol.

7. The radiation curable polyurethane-based binder dispersion as defined in claim 1 wherein the acrylate or methacrylate is chosen from:

aliphatic diglycidyl compounds selected from the group consisting of 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (BGDA or BADGE), hydrogenated bisphenol F diglycidyl ether, and 1,6-hexanediylbis[oxy(2-hydroxy-3,1-propanediyl)] bisacrylate;

or

aromatic diglycidyl compounds selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, ethoxylated or propoxylated equivalents of bisphenol A diglycidyl ether;

ethoxylated or propoxylated equivalents of bisphenol F diglycidyl ether, diglycidyl phthalate, N,N-diglycidyl aniline, N,N-diglycidyl-4-glycidyloxyaniline, a diacrylate ester of bisphenol A diglycidyl ether (BGDA), and a dimethacrylate ester of bisphenol A diglycidyl ether (BGDM);

or

acrylates or methacrylates having one hydroxyl functional group selected from the group consisting of hydroxyethylacrylate (HEA), hydroxyethylmethacrylate (HEMA), hydroxybutylacrylate (HBA), hydroxybutylmethacrylate (HBMA), (3-(acryloxy)-2-hydroxypropyl methacrylate) (AHPMA), glycerol diacrylate, trimethylolpropane diacrylate, pentaerythritoltriacrylate (PETA), ditrimethylolpropane triacrylate (DTPTA), dipentaerythritol pentaacrylate (DPPA), and (poly)ethoxylated or (poly)propoxylated equivalents of glycerol diacrylate, trimethylolpropane diacrylate, PETA, DTPTA, or DPPA;

or

combinations thereof.

8. The radiation curable polyurethane-based binder dispersion as defined in claim 2 wherein the carboxylic acid having two or more hydroxyl functional groups is selected from the group consisting of dimethylol propionic acid (DMPA), dimethylol butanoic acid (DMBA), alanine, citric acid, tartaric acid, glycolic acid, lactic acid, malic acid, dihydroxymaleic acid, dihydroxytartaric acid, and mixtures thereof.

9. The radiation curable polyurethane-based binder dispersion as defined in claim 8 wherein the homopolymer or copolymer of poly(ethylene glycol) has a number average molecular weight (M_n) ranging from about 500 to about 3000 and a water solubility greater than 30% v/v, and wherein the homopolymer or copolymer of poly(ethylene glycol) is one of:

a poly(ethylene glycol) copolymer selected from the group consisting of a copolymer of poly(ethylene) and poly(ethylene glycol) with the one hydroxyl functional group, a copolymer of poly(propylene glycol) and poly(ethylene glycol) with the one hydroxyl functional group, and a copolymer of poly(ethylene glycol) and poly(propylene glycol) with the one amino functional group;

or

a poly(ethylene glycol) homopolymer selected from the group consisting of monoamine terminated poly(ethylene glycol), poly(ethylene glycol) monoethyl ether, poly(ethylene glycol) monopropyl ether, poly(ethylene glycol) monobutyl ether, poly(ethylene glycol) monomethyl ether, and two hydroxyl terminated at one end poly(ethylene glycol).

10. The radiation curable polyurethane-based binder dispersion as defined in claim 2 wherein:

the polyisocyanate is present in an amount ranging from about 20 wt % to about 50 wt % based on a total wt % of the radiation curable polyurethane;

the polyol having the chain with two hydroxyl functional groups at the one end of the chain and no hydroxyl groups at the opposed end of the chain is present in an amount ranging from about 10 wt % to about 70 wt % based on the total wt % of the radiation curable polyurethane;

the acrylate or methacrylate having the at least two hydroxyl functional groups and having the acrylate functional group or the methacrylate functional group is present in an amount ranging from about 5 wt % to about 40 wt % based on the total wt % of the radiation curable polyurethane;

the alcohol or diol or amine having the number average molecular weight less than 600 is present in an amount ranging from greater than 0 wt % to about 20 wt % based on the total wt % of the radiation curable polyurethane;

the sulfonate or sulfonic acid is present in an amount ranging from about 5 wt % to about 20 wt % based on the total wt % of the radiation curable polyurethane; and

when included;

the carboxylic acid is present in an amount ranging from greater than 0 wt % to about 10 wt % based on the total wt % of the radiation curable polyurethane; and

the homopolymer or copolymer of poly(ethylene glycol) is present in an amount ranging from greater than 0 wt % to about 20 wt % based on the total wt % of the radiation curable polyurethane.

11. The radiation curable polyurethane-based binder dispersion as defined in claim 1 wherein the alcohol or the diol or the amine having the number average molecular weight less than 600 is selected from the group consisting of 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, Bisphenol A ethoxylate, Bisphenol A propoxylate, and polycarbonate diol.

12. An inkjet ink, comprising:

water;

a colorant;

a co-solvent;

a surfactant; and

a radiation curable polyurethane binder, the radiation curable polyurethane binder having been formed from;

a polyisocyanate;

a polyol having a chain with two hydroxyl functional groups at one end of the chain and no hydroxyl groups at an opposed end of the chain and having a number average molecular weight ranging from about 500 to about 5,000;

an acrylate or methacrylate, the acrylate or methacrylate having at least one hydroxyl functional group and having an acrylate functional group or a methacrylate functional group;

an alcohol or a diol or an amine having a number average molecular weight less than 600; and

a sulfonate or sulfonic acid having one or two amino functional groups.

13. The inkjet ink as defined in claim 12, the radiation curable polyurethane binder having further been formed from:

i) a carboxylic acid having two or more hydroxyl functional groups;

or

ii) a homopolymer or copolymer of poly(ethylene glycol) having one or two hydroxyl functional groups or one or two amino functional groups at one end of its chain;

or

iii) a combination of i and ii.

14. The inkjet ink as defined in claim 12 wherein:

the polyol is formed from a free radical polymerization of a monomer in the presence of a mercaptan including two hydroxyl functional groups or two carboxylic functional groups;

the monomer is selected from the group consisting of an alkylester of acrylic acid, an alkylester of methacrylic acid, an acid group containing monomer, acrylamide, an acrylamide derivative, methacrylamide, a methacrylamide derivative, styrene, a styrene derivative, acrylonitrile, vinylidene chloride, a fluorine containing acrylate, a fluorine containing methacrylate, a siloxane containing acrylate, a siloxane containing methacrylate, vinyl acetate, N-vinylpyrrolidone, and combinations thereof; and

the mercaptan is selected from the group consisting of thioglycerol, 1-mercapto-1,1-ethanediol, 2-mercapto-1,3-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,3-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and thioglycolic acid.

15. An inkjet ink set, comprising:

a pre-treatment fixing fluid, including;

calcium propionate present in an amount ranging from greater than 4.5 to about 8.0 wt % based on a total wt % of the pre-treatment fixing fluid;

calcium pantothenate present in an amount ranging from about 2.0 wt % to equal to or less than 15 wt % based on the total wt % of the pre-treatment fixing fluid;

tetraethylene glycol;

a surfactant;

an acid present in an amount sufficient to render a pH of the pre-treatment fixing fluid from about 4.0 to about 7.0; and

a balance of water; and

an inkjet ink, including;

water;

a colorant;

a co-solvent;

a surfactant; and

a radiation curable polyurethane binder, the radiation curable polyurethane binder having been formed from;

a polyisocyanate;

a polyol having a chain with two hydroxyl functional groups at one end of the chain and no hydroxyl groups at an opposed end of the chain and having a number average molecular weight ranging from about 500 to about 5,000;

an acrylate or methacrylate, the acrylate or methacrylate having at least one hydroxyl functional group and having an acrylate functional group or a methacrylate functional group;

an alcohol or a diol or an amine having a number average molecular weight less than 600;

a sulfonate or sulfonic acid having one or two amino functional groups; and

one of;

i) a carboxylic acid having two or more hydroxyl functional groups;

or

ii) a homopolymer or copolymer of poly(ethylene glycol) having one or two hydroxyl functional groups or one or two amino functional groups at one end of its chain;

or

iii) a combination of i and ii.