# Patent

## Title
Thermal ink jet ink composition

## Abstract

Disclosed are ink jet ink compositions suitable for use in thermal ink jet printers. The ink jet ink compositions contain one or more volatile organic solvents, one or more humectants, one or more binder resins, and one or more colorants. The ink jet ink compositions may also contain additives such as a plasticizer and/or a surfactant. Embodiments of the ink jet ink compositions have short dry times, good adhesion to a variety of substrates, and/or long decap times.

## Background
BACKGROUND OF THE INVENTION
Thermal ink jet (TIJ) print heads produce ink droplets from thermal vaporization of the ink solvent. In the jetting process, a resistor is heated rapidly to produce a vapor bubble which subsequently ejects a droplet from the orifice. This process is extremely efficient and reproducible. Modem TIJ print heads for industrial graphics applications are capable of generating uniform drops of 4 pL or smaller in volume at frequencies of 36 kHz or greater. Typical commercial TIJ devices are specifically designed to vaporize water or solvents that have physical properties close to those of water (e.g. high boiling point, large heat capacity, low molecular weight).
Although TIJ printing systems have been available for over 30 years, nearly all of the commercial inks available for thermal ink jet systems have been water-based, i.e. they contain more than 50% water. Such aqueous inks have one or more drawbacks such as long ink dry times or poor adhesion to semi-porous or non-porous substrates.
There is a desire for inks with attractive performance characteristics such as short dry times, long decap times and good adhesion when using a TIJ system to print onto semi-porous and non-porous substrates.
BRIEF SUMMARY OF THE INVENTION
The invention provides a thermal ink jet ink composition comprising one or more volatile organic solvents, one or more humectants, one or more binder resins, and one or more dyes. In an embodiment, the humectants are present in an amount not more than 30% by weight of the ink jet ink composition.
In another embodiment, the invention provides a thermal ink jet ink composition comprising one or more alcohols, one or more humectants, one or more binder resins, one or more colorants, and one or more plasticizers. In a specific embodiment, the plasticizers are present in an amount not more than 5% by weight of the ink jet ink composition.
In yet another embodiment, the invention provides a thermal ink jet ink composition comprising one or more volatile organic solvents, one or more humectants, one or more binder resins, and one or more pigments. In a specific embodiment, the humectants are present in an amount not more than 30% by weight of the ink jet ink composition. In a further specific embodiment, the ink jet ink composition is free or substantially free of a polymeric surfactant.
The invention also provides a method for printing images on a substrate in a thermal ink jet printer comprising directing a stream of droplets of the thermal ink jet ink composition of the invention to a substrate and allowing the ink droplets to dry, thereby printing images on a substrate.
The thermal ink jet ink composition of the invention has one or more of the following features: short dry times, long decap times, good adhesion to substrates, safety, and material compatibility. Decap time is defined as the amount of time a nozzle can remain dormant and then be fired again without detrimental effect on the droplet velocity, weight or direction. Fluids with good material compatibility are defined as those which do not degrade the ability of the TIJ cartridge to fire for some reasonable length of time. The thermal ink jet ink composition does not require heat assist (e.g., thermal driers) when printed on semi-porous and non-porous substrates.


DETAILED DESCRIPTION OF THE INVENTION
The invention provides a thermal ink jet ink composition comprising one or more volatile organic solvents, one or more humectants, one or more binder resins, and one or more colorants.
In an embodiment, the invention provides a thermal ink jet ink composition comprising one or more volatile organic solvents, one or more humectants, one or more binder resins, and one or more dyes, wherein the humectants are present in an amount not more than 30% by weight of the ink jet ink composition, wherein the one or more volatile organic solvents are selected from the group consisting of C1-C4 alcohols, C4-C8 ethers, C3-C6 ketones, C3-C6 esters, and mixtures thereof.
In another embodiment, the invention provides a thermal ink jet ink composition comprising one or more C1-C4 alcohols, one or more humectants, one or more binder resins, one or more colorants, and one or more plasticizers, wherein the plasticizers are present in an amount not more than 5% by weight of the ink jet ink composition and are selected from the group consisting of butyl benzyl phthalate, n-ethyl op-toluene sulfonamide, and mixtures thereof.
In yet another embodiment, the invention provides a thermal ink jet ink composition comprising one or more volatile organic solvents, one or more humectants, one or more binder resins, one or more pigments, wherein the humectants are present in an amount not more than 30% by weight of the ink jet ink composition and the ink jet ink composition is free or substantially free of a polymeric surfactant, wherein the one or more volatile organic solvents are selected from the group consisting of C1-C4 alcohols, C4-C8 ethers, C3-C6 ketones, C3-C6 esters, and mixtures thereof.
In accordance with an embodiment, the volatile organic solvents are selected from the group consisting of C1-C4 alcohols, C4-C8 ethers, C3-C6 ketones, C3-C6 esters, and mixtures thereof. Examples of C1-C4 alcohols include methanol, ethanol, 1-propanol, and 2-propanol. Examples of C4-C8 ethers include diethyl ether, dipropyl ether, dibutyl ether and tetrahydrofuran. Examples of C3-C6 ketones include acetone, methyl ethyl ketone and cyclohexanone. Examples of C3-C6 esters include methyl acetate, ethyl acetate and n-butyl acetate. The organic solvents, particularly alcohols, ketones, and esters, have an attractive feature that they penetrate semi- and non-porous substrate surfaces more readily than water based inks, thus reducing dry time and improving adhesion.
The one or more volatile organic solvents can be present in any suitable amount, for example, in an amount 50% or more, about 60% or more, about 70% or more, about 80% or more, or about 90% or more by weight of the ink jet ink composition. In an embodiment, the one or more volatile organic solvents can be present in an amount from 50 to about 99%, preferably from about 60 to about 97%, and more preferably from about 80 to about 95% of the ink jet ink composition. The thermal ink jet ink composition of the invention can optionally include water in a suitable amount, e.g., up to 49% by weight, up to about 25% by weight, or up to about 10% by weight, up to about 5% by weight, or up to about 2% by weight of the ink jet ink composition.
The thermal ink jet ink composition of the invention can include any suitable colorant or colorants, which may be dye or pigment. In an embodiment of the invention, one or more dyes are employed as the colorant, wherein the one or more dyes are selected from the group consisting of acid dyes, basic dyes, solvent dyes, disperse dyes, mordant dyes and any combination thereof. Examples of solvent dyes include naphthol dyes, azo dyes, metal complex dyes, anthraquinone dyes, quinoimine dyes, indigoid dyes, benzoquinone dyes, carbonium dyes, naphthoquinone dyes, naphthalimide dyes, phthalocyanine dyes, and perylene dyes.
For example, the thermal ink jet ink composition can include one or more dyes are selected from the group consisting of C.I. Solvent Yellow 19, C.I. Solvent Yellow 21, C.I. Solvent Yellow 61, C.I. Solvent Yellow 80, C.I. Solvent Orange 1, C.I. Orange 37, C.I. Orange 40, C.I. Solvent Orange 54, C.I. Solvent Orange 63, C.I. Solvent Red 8, Solvent Red 49, C.I. Solvent Red 81, C.I. Solvent Red 82, C.I. Solvent Red 84, C.I. Solvent Red 100, C.I. Acid Red 92, C. I. Reactive red 31, Orient Pink 312, C.I. Basic Violet 3, C.I. Basic Violet 4, C.I. Solvent Violet 8, C.I. Solvent Violet 21, C.I. Solvent Blue 2, C.I. Solvent Blue 5, C.I. Solvent Blue 11, C.I. Solvent Blue 25, C.I. Solvent Blue 36, C.I. Solvent Blue 38, C.I. Solvent Blue 55; C.I. Solvent Blue 70, C.I. Solvent Green 3, C.I. Solvent Black 3, C.I. Solvent Black 5, C.I. Solvent Black 7, C.I. Solvent Black 22, Solvent Black 26, C.I. Solvent Black 27 (MORFAST BLACK 101), C.I. Solvent Black 29 (VALIFAST BLACK 3808), C.I. Acid Black 123, C.I. Solvent Black 48, C.I. Oil Blue 613, and any combination thereof, and preferably one or more dyes selected from the group consisting of C.I. Solvent Black 29 (ORASOL BLACK RLITM), C.I. Solvent Black 26, C.I. Solvent Black 48, C.I. Solvent Black 3 (Oil Black 860), C.I. Basic Violet 3, C.I. Solvent Blue 38, C.I. Solvent Blue 70, C.I. Oil Blue 613, C.I. Solvent Red 49 (ORIENT PINKTM 312), C.I. Solvent Orange 54 (VALIFAST ORANGETM 3210), and any combination thereof.
Any suitable pigment can be used, for example, one or more pigments selected from the group consisting of phthalocyanine blue, carbon black, mars black, quinacridone magenta, ivory black, prussian blue, cobalt blue, ultramarine blue, manganese blue, cerulean blue, indathrone blue, chromium oxide, viridian, cobalt green, terre verte, nickel azo yellow, light green oxide, phthalocyanine green-chlorinated copper phthalocyanine, burnt sienna, perinone orange, irgazin orange, quinacridone magenta, cobalt violet, ultramarine violet, manganese violet, dioxazine violet, zinc white, titanium white, flake white, aluminum hydrate, blanc fixe, china clay, lithophone, arylide yellow G, arylide yellow 10 G, barium chromate, chrome yellow, chrome lemon, zinc yellow, cadmium yellow, aureolin, naples yellow, nickel titanate, arylide yellow GX, isoindolinone yellow, flavanthrone yellow, yellow ochre, chromophthal yellow 8GN, toluidine red, quinacridone red, permanent crimson, rose madder, alizarin crimson, vermilion, cadmium red, permanent red FRG, brominated anthranthrone, naphthol carbamide, perylene red, quinacridone red, chromophthal red BRN, chromophthal scarlet R, aluminum oxide, barium oxide, bismuth oxide, boric oxide, cadmium oxide, calcium oxide, cerium oxide, chromium oxide, cobalt oxide, copper oxide, iridium oxide, lead oxide, magnesium oxide, manganese oxide, nickel oxide, phosphorus oxide, potassium oxide, rutile, silicon oxide, silver oxide, sodium oxide, strontium oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, and any combination thereof.
In embodiments, the pigments are selected from the group consisting of azo pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, metal oxide pigments, carbon black, and any combination thereof.
The pigments can have any suitable particle size, for example, from about 0.005 micron to about 15 microns, preferably from about 0.005 to about 1 micron, and more preferably from about 0.01 to about 0.3 micron.
In any of the embodiments above, the colorant, dye or pigment, can be present in an amount from about 0.01% to about 10%, preferably from about 0.5% to about 7%, and more preferably from about 1% to about 5% by weight of the ink jet ink composition.
In any of the embodiments above, any suitable humectant can be used. Preferably, humectants have a boiling point greater than 150° C., greater than 200° C., or greater than 250° C., and/or a relative evaporation rate less than 1.0, less than 0.9, less than 0.7, less than 0.4, less than 0.1, or less than 0.01. The humectants typically are solvents having one or more polar functional groups such as hydroxyl, ether, amide, ester, ketone, and carbonate, for example, two functional groups, which may be the same or different, such as two hydroxyl groups or one hydroxyl group and one ether group. In an embodiment, the one or more humectants are selected from the group consisting of polyol, glycol ether, diacetone alcohol, 2-pyrrolidinone, N-methylpyrrolidinone, ethyl lactate, propylene carbonate, 1,3-dimethyl-2-imidazolidindione, and alkyl esters, and any combination thereof.
For example, the polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(ethylene-co-propylene glycol), polyvinyl alcohol, trimethylol propane, ethylene glycol, glycerin, diethylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, pentaethylene glycol, 1,2-propylene glycol, 1,3-propanediol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, bis-2-hydroxyethyl ether, 1,4-butanediol, 1,2-butenediol, 1,4-butenediol, 1,3-butenediol, 1,5-pentanediol, 2,4-pentanediol, 2,4-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, pentaerythritol, sorbitol, mannitol, and any combination thereof, and preferably the polyol is selected from the group consisting of polyethylene glycol, trimethylol propane, ethylene glycol, glycerin, diethylene glycol, tripropylene glycol, and any combination thereof,
A preferred humectant is glycol ether, for example, a glycol ether selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-propyl ether, tripropylene glycol t-butyl ether, tripropylene glycol n-butyl ether, ethyl cellosolve, methyl cellosolve, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, and any combination thereof, and preferably, the glycol ether is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and any combination thereof In embodiments of the invention, propylene glycol monomethyl ether is a preferred humectant.
Humectants contribute, at least in part, to a feature of the thermal ink jet ink composition. Thus, humectants can lengthen decap times; however, excessive amounts of humectants could increase the dry time of the ink jet ink composition. In any of the embodiments, the one or more humectants can be present in any suitable amount, for example, in an amount about 50% by weight or less, about 40% by weight or less, preferably about 30% by weight or less, about 25% by weight or less, about 20% by weight or less, about 15% by weight or less, or about 10% by weight or less. In an embodiment, the one or more humectants can be present in an amount from about 1% to about 30%, preferably from about 2% to about 15%, and more preferably from about 3% to about 10% of the ink jet ink composition.
As discussed, the thermal ink jet ink composition of the invention includes one or more binder resins. Any suitable binder resin, soluble or dispersible, can be employed, preferably a solvent soluble binder resin. In an embodiment, the thermal ink jet ink composition of the invention includes one or more binder resins selected from the group consisting of polyamide resins, polyurethane resins, rosin ester resins, acrylic resins, polyvinyl butyral resins, polyesters, polyurethanes, phenolic resins, polyimides, vinyl resins, ethylene vinyl acetate resins, polystyrene/acrylates, cellulose ethers, cellulose nitrate resins, polymaleic anhydrides, acetal polymers, polystyrene/butadienes, polystyrene/methacrylates, sulfonated polyesters, aldehyde resins, and polyketone resins, and any combination thereof, and preferably one or more binder resins selected from the group consisting of polyamide resins, rosin ester resins, acrylic resins, polyketone resins, and any combination thereof. An example of a suitable polyamide resin is ARIZONA 201-150TM available from Arizona Chemical Company, Jacksonville, Fla., or COGNIS VERSAMID 756TM, available from Cognis GmbH, Monheim am Rhein, Germany, both of which are alcohol-soluble polyamide resins. Examples of wood rosin ester resins include UNIREZTM 8115, available as a 40% solution in ethanol from Penn Color, Doylestown, Pa., which is a hydrogenated wood rosin ester, and STAYBELITETM ESTER 10, available from Chem Central Corporation. Examples of cellulose nitrate resins are NOBELTM DLX 3-5 or NOBELTM DHX 5-8, available from Nobel Enterprises. Examples of polyvinyl butyral resins are PIOLOFORMTM BN18, available from Wacker Chemie AG, and MOWITALTM B20H available from Kuraray America, Inc.
The binder resin can be present in any suitable amount, for example, in an amount from about 0.1 to about 30%, preferably from about 0.2 to about 15%, and more preferably from about 0.3 to about 8% of the ink jet ink composition.
In a particular embodiment of the thermal ink jet ink composition of the invention, the volatile organic solvent or solvents can be present in an amount from about 50% to about 95% by weight, the colorant(s) (dyes, pigments, or a combination thereof), can be present in amount from about 1% to about 8% by weight, the glycol ether can be present in an amount from about 3% to 30% by weight, and the binder resin can be present in an amount from about 1% to about 15% by weight of the ink jet ink composition.
The thermal ink jet ink composition of the invention can further include one or more additives such as surfactants, plasticizers, or conductive salts. Preferably, a polymeric surfactant is employed. Examples of surfactants include siloxanes, silicones, silanols, polyoxyalkyleneamines, propoxylated (poly(oxypropylene)) diamines, alkyl ether amines, nonyl phenol ethoxylates, ethoxylated fatty amines, quaternized copolymers of vinylpyrrolidone and dimethyl aminoethyl methacrylate, fluorinated organic acid diethanolamine salts, alkoxylated ethylenediamines, polyethylene oxides, polyoxyalkylene polyalkylene polyamines amines, polyoxyalkylene polyalkylene polyimines, alkyl phosphate ethoxylate mixtures, polyoxyalkylene derivatives of propylene glycol, and polyoxyethylated fatty alcohols. A specific example of a suitable polymeric surfactant, e.g., Silicone Fluid SF-69, available from Dow Corning Co, Midland, Mich., which is a blend of silanols and cyclic silicones. Additional examples of polymeric surfactants include DISPERSYBYKTM (BYK-Chemie, USA), SOLSPERSETM (e.g., SOLSPERSE 13940 which is a polymer/fatty acid condensation polymer) and EFKATM (EFKA Chemicals) polymeric dispersants.
In any of the embodiments of the invention, the surfactant can be present in an amount from about 0.01 to about 1.0%, preferably from about 0.01 to about 0.5%, and more preferably from about 0.01 to about 0.1% of the ink jet ink composition.
Examples of suitable plasticizers include phthalate plasticizers, e.g., alkyl benzyl phthalates, butyl benzyl phthalate, dioctyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, diethyl phthalate, dimethyl isophthalate, dibutyl phthalate, and dimethyl phthalate, esters such as di-(2-ethylhexy)-adipate, diisobutyl adipate, glycerol tribenzoate, sucrose benzoate, polypropylene glycol dibenzoate, neopentyl glycol dibenzoate, dibutyl sebacate, and tri-n-hexyltrimellitate, and sulfonamide plasticizers such as Plasticizer 8, available from Monsanto Co., St. Louis, Mo., which is n-ethyl o,p-toluene sulfonamide.
In embodiments of the invention, the plasticizer can be present in an amount from about 0.1 to about 5.0%, preferably from about 0.3 to about 3.0%, and more preferably from about 0.5 to about 2.0% of the ink jet ink composition.
The thermal ink jet ink composition of the invention may include additional ingredients such as surfactants, bactericides, fungicides, algicides, sequestering agents, buffering agents, corrosion inhibitors, antioxidants, light stabilizers, anti-curl agents, thickeners, and other agents known in the relevant art. In an embodiment, the ink composition of the invention is free or substantially free of antioxidants.
The thermal ink jet ink composition of the invention has one or more attractive features such as short unassisted dry times of printed alphanumeric or graphic images, long decap times, good adhesion to semi-porous and non-porous substrates, and safety or material compatibility with one or more components of a thermal ink jet printer. For example, embodiments of the thermal ink jet ink composition of the invention have a dry time of about 10 seconds or less, such as 7 seconds or less, 4 seconds or less, or 2 seconds or less, under ambient conditions. On porous substrates, the dry times are shorter than in semi- or non-porous substrates. For example, embodiments of the thermal ink jet ink composition of the invention have a dry time of about 1 second on porous substrates and less than about 5 seconds, preferably less than about 2 seconds, and more preferably less than about 1 second on semi-porous substrates.
The thermal ink jet ink composition of the invention can have any suitable viscosity or surface tension. In embodiments of the invention, the thermal ink jet ink composition has a viscosity of less than about 10 cPs, preferably less than about 5 cPs, and more preferably less than about 3 cPs, for example, a viscosity from about 1 to 4 or from about 1 to about 3 cPs at 25° C.
In embodiments of the invention, the thermal ink jet ink composition has a surface tension from about 20 to about 50 mN/m, from about 21 to about 40 mN/m, or from about 22 to about 30 mN/m at 25° C.
The thermal ink jet ink composition of the invention can be prepared by any suitable method. For example, the chosen ingredients can be combined and mixed with adequate stirring and the resulting fluid filtered to remove any undissolved impurities.
The present invention further provides a method for printing images on a substrate in a thermal ink jet printer comprising directing a stream of droplets of any of the embodiments of the thermal ink jet ink composition of the invention to a substrate and allowing the ink droplets to dry, thereby printing images on a substrate. Any suitable substrate can be printed in accordance with the invention. Examples of suitable substrates include porous substrates such as uncoated paper, semi-porous substrates such as aqueous coated paper, clay coated paper, silica coated paper, UV overcoated paper, polymer overcoated paper, and varnish overcoated paper, and non-porous substrates such as hard plastics, polymer films, metals, glass, and ceramics. The paper substrates can be thin sheets of paper, rolls of paper, or cardboard. Plastics, metals, glass, and ceramic substrates can be in any suitable form such as in the form of bottles or containers, plates, rods, cylinders, etc.
Examples of polymer coating include a coating of polystyrene, polyvinyl alcohol, polyacryate, polymethacrylate, polystryrene or polyvinyl chloride. Examples of polymer film substrates include polyvinyl butyrals, polyolefins, polyvinyl chloride, polyethylene terephthalate, PETG, polybutylene terephthalate (PBT), polyester, polycarbonate, acrylonitrile-butadiene-styrene (ABS) copolymer, polyvinyl fluoride polymer, polyamides, polyimides, and cellulose. Plastics can be treated plastics (e.g. chemical etch, corona discharge, flame plasma, etc.) or untreated plastics. Examples of metals include aluminum, copper, stainless steel, and metal alloys. Examples of ceramics include oxides, nitrides, and carbides of metals.
The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.
EXAMPLE 1
This example illustrates embodiments of the thermal ink jet ink composition of the invention. The materials employed in preparing the ink jet ink composition, their amounts, and the formulation numbers are set forth in Table 1 below.







TABLE 1







Ink formulations in accordance with embodiments of the invention


















Material
2520
2538
5521
5678
5745
5750
5762
5798
5815
5817
5818





















ethanol



86.55
45.35
45.49
25.00
85.49
41.50
86.00
86.00


isopropanol
73.45


1-propanol

79.00


1-butanol


82.28


methanol








41.00


glycol ether PM
10.50
5.00
3.15
3.50
45.10
40.00
50.00
10.00
10.00
10.00
10.00


Valifast Black 3808
4.00
4.00



4.00
4.00
4.00
4.00
4.00


Orasol Black RLI




5.00


Valifast Orange 3210


1.06
1.00
1.00
1.00


Orient Oil Pink 312


1.38
1.40


40% Unirez 8115 in EtOH
12.00
12.00
12.08


20% Arizona 201-150 in EtOH






20.00


40% Cognis Versamid 756 in EtOH



7.50


Nobel DLX 3-5








3.00


Piloform LL 4140




3.00


Joncryl 682





6.00


K-Plast 1022





3.00


Silicone fluid SF69
0.05

0.05
0.05
0.05
0.01

0.01
0.01
0.01
0.01


Plasticizer 8




0.50
0.50
1.00
0.50
0.50









EXAMPLE 2
This Example illustrates the ink dry times of embodiments of the thermal ink jet ink composition of the invention.







TABLE 2







Ink dry times of embodiments of the ink composition on


various substrates










Formulation


Unassisted Dry


Number
Substrate
Type
Time, sec





5678
Clay Coat
semi-porous
1



Aqueous Coat
semi-porous
2



Varnish Coat
semi-porous
2



UV Coat
semi-porous
3



HDPE
non-porous
1



Polypropylene
non-porous
2



PET
non-porous
1



PVC
non-porous
2



Glass
non-porous
2



Aluminum
non-porous
1


5750
Clay Coat
semi-porous
1



Aqueous Coat
semi-porous
1



Varnish Coat
semi-porous
1



UV Coat
semi-porous
2



HDPE
non-porous
2



Polypropylene
non-porous
3



PET
non-porous
2



PVC
non-porous
2



Glass
non-porous
2



Aluminum
non-porous
2


5798
Clay Coat
semi-porous
1



Aqueous Coat
semi-porous
1



Varnish Coat
semi-porous
1



UV Coat
semi-porous
2



HDPE
non-porous
2



Polypropylene
non-porous
3



PET
non-porous
2



PVC
non-porous
2



Glass
non-porous
1



Aluminum
non-porous
1









EXAMPLE 3
This Example illustrates some of the properties of embodiments of the ink jet ink composition of the invention.







TABLE 3







Properties of embodiments of the thermal ink jet ink


composition of the invention









Formulation
Viscosity
Surface Tension


No.
(cPs)
(mN/m)





5521
3.42
24.1


5678
1.71
22.6


5745
3.10
24.4


5750
3.28
25.0


2520
3.03
22.0


5798
1.50
22.6


5815
2.31
20.2









EXAMPLE 4
This Example illustrates the adhesion of the printed images obtained from embodiments of the ink jet ink composition of the invention. The ink jet ink composition Nos. 2520, 5745, 5750 and 5815 produce images on clay coat substrates having aqueous overcoat, UV overcoat, or varnish overcoat, as well as on polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, glass and aluminum substrates, that pass a 1 minute rub resistance test as well as a 24 hour scratch adhesion test
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

## Claims

1. A thermal ink jet ink composition comprising one or more volatile organic solvents, one or more humectants, one or more binder resins, one or more dyes, and a polymeric surfactant comprising a blend of silanols and cyclic silicones, wherein the one or more humectants are present in an amount from about 1% to about 30% by weight of the ink jet ink composition, wherein the one or more volatile organic solvents are selected from the group consisting of C1-C4 alcohols, C4-C8 ethers, C3-C6 ketones, C3-C6 esters, and mixtures thereof, wherein the thermal ink jet ink composition optionally includes water up to about 10% by weight of the ink jet ink composition and wherein the thermal ink jet ink composition is suitable for use in thermal ink jet printers.

2. The thermal ink jet ink composition of claim 1, wherein the one or more volatile organic solvents comprise methanol, ethanol, 1-propanol, or isopropanol, or a mixture thereof.

3. The thermal ink jet ink composition of claim 1, wherein the one or more humectants are selected from the group consisting of polyol, glycol ether, diacetone alcohol, 2-pyrrolidinone, N-methylpyrrolidinone, ethyl lactate, 1,3-dimethyl-2-imidazolidindione, propylene carbonate, alkyl esters, and mixtures thereof.

4. The thermal ink jet ink composition of claim 3, wherein the polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(ethylene-co-propylene glycol), polyvinyl alcohol, trimethylol propane, ethylene glycol, glycerin, diethylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, pentaethylene glycol, 1,2-propylene glycol, 1,3-propanediol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, bis-2-hydroxyethyl ether, 1,4-butanediol, 1,2-butenediol, 1,4-butenediol, 1,3-butenediol, 1,5-pentanediol, 2,4-pentanediol, 2,4-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, pentaerythritol, sorbitol, mannitol, and mixtures thereof.

5. The thermal ink jet ink composition of claim 4, wherein the polyol is selected from the group consisting of polyethylene glycol, trimethylol propane, ethylene glycol, glycerin, diethylene glycol, tripropylene glycol, and mixtures thereof.

6. The thermal ink jet ink composition of claim 1, wherein the humectant is a glycol ether.

7. The thermal ink jet ink composition of claim 3, wherein the glycol ether is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-propyl ether, tripropylene glycol t-butyl ether, tripropylene glycol n-butyl ether, ethyl cellosolve, methyl cellosolve, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, and mixtures thereof.

8. The thermal ink jet ink composition of claim 7, wherein the glycol ether is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and mixtures thereof.

9. The thermal ink jet ink composition of claim 1, wherein the one or more binder resins are selected from the group consisting of polyamide resins, rosin ester resins, acrylic resins, polyketone resins, cellulose nitrate resins, polyvinyl butyral resins, and mixtures thereof.

10. The thermal ink jet ink composition of claim 1, wherein the one or more dyes are selected from the group consisting of C.I. Solvent Yellow 19, C.I. Solvent Yellow 21, C.I. Solvent Yellow 61, C.I. Solvent Yellow 80, C.I. Solvent Orange 1, C.I. Orange 37, C.I. Orange 40, C.I. Solvent Orange 54, C.I. Solvent Orange 63, C.I. Solvent Red 8, Solvent Red 49, C.I. Solvent Red 81, C.I. Solvent Red 82, C.I. Solvent Red 84, C.I. Solvent Red 100, C. I. Acid Red 92, C.I. Reactive red 31, C.I. Basic Violet 3, C.I. Basic Violet 4, C.I. Solvent Violet 8, C.I. Solvent Violet 21, C.I. Solvent Blue 2, C.I. Solvent Blue 5, C.I. Solvent Blue 11, C.I. Solvent Blue 25, C.I. Solvent Blue 36, C.I. Solvent Blue 38, C.I. Solvent Blue 55; C.I. Solvent Blue 70, C.I. Solvent Green 3, C.I. Solvent Black 3, C.I. Solvent Black 5, C.I. Solvent Black 7, C.I. Solvent Black 22, Solvent Black 26, C.I. Solvent Black 27, C.I. Solvent Black 29, Acid Black 123, C.I. Solvent Black 48, C.I. Oil Blue 613, and mixtures thereof.

11. The thermal ink jet ink composition of claim 10, wherein the one or more dyes are selected from the group consisting of C.I. Solvent Black 29, C.I. Solvent Black 26, C.I. Solvent Black 48, C.I. Solvent Black 3, C.I. Basic Violet 3, C.I. Solvent Blue 38, C.I. Solvent Blue 70, C.I. Oil Blue 613, C.I. Solvent Red 49, C.I. Solvent Orange 54, and mixtures thereof.

12. The thermal ink jet ink composition of claim 6, wherein the one or more volatile organic solvents are present in an amount from 50% to about 95% by weight, the one or more dyes are present in amount from about 1% to about 8% by weight, the glycol ether is present in an amount from about 3% to 30% by weight, the one or more binder resins are present in an amount from about 1% to about 15% by weight of the ink jet ink composition.

13. The thermal ink jet ink composition of claim 12, wherein one or more volatile organic solvents comprise methanol, ethanol, or isopropanol.

14. The thermal ink jet ink composition of claim 12, wherein the glycol ether is propylene glycol monomethyl ether.

15. The thermal ink jet ink composition of claim 12, wherein the one or more binder resins comprise a polyamide resin, a polyurethane resin, a cellulose nitrate resin, a polyvinyl butyral resin, or a rosin ester resin.

16. The thermal ink jet ink composition of claim 1, further including a plasticizer.

17. A thermal ink jet ink composition comprising one or more C1-C4 alcohols, one or more humectants, one or more binder resins, one or more colorants, and one or more plasticizers, wherein the one or more plasticizers are present in an amount not more than 5% by weight of the ink jet ink composition and are selected from the group consisting of butyl benzyl phthalate, n-ethyl o,p-toluene sulfonamide, and mixtures thereof, and wherein the thermal ink jet ink composition is suitable for use in thermal ink jet printers.

18. The thermal ink jet ink composition of claim 17, wherein the one or more C1-C4 alcohols are selected from the group consisting of methanol, ethanol, 1-propanol, and isopropanol.

19. The thermal ink jet ink composition of claim 17, wherein the one or more humectants are selected from the group consisting of polyol, glycol ether, diacetone alcohol, 2-pyrrolidinone, N-methylpyrrolidinone, ethyl lactate, 1,3-dimethyl-2-imidazolidindione, propylene carbonate, alkyl esters, and mixtures thereof.

20. The thermal ink jet ink composition of claim 19, wherein the humectant is a glycol ether.

21. The thermal ink jet ink composition of claim 17, wherein the one or more binder resins are selected from the group consisting of polyamide resins, polyurethane resins, rosin ester resins, acrylic resins, polyvinyl butyral resins, polyesters, polyurethanes, phenolic resins, polyimides, vinyl resins, ethylene vinyl acetate resins, polystyrene/acrylates, cellulose ethers, cellulose nitrate resins, polymaleic anhydrides, acetal polymers, polystyrene/butadienes, polystyrene/methacrylates, sulfonated polyesters, aldehyde resins, polyketone resins, and mixtures thereof.

22. The thermal ink jet ink composition of claim 17, wherein the one or more colorants are one or more pigments.

23. The thermal ink jet ink composition of claim 22, wherein the one or more pigments are selected from the group consisting of azo pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, metal oxide pigments, carbon black, and mixtures thereof.

24. The thermal ink jet ink composition of claim 17, which optionally includes water up to about 25% by weight of the ink jet ink composition.

25. The thermal ink jet ink composition of claim 20, wherein the one or more C1-C4 alcohols are present in an amount from 50% to about 95% by weight, the one or more colorants are present in an amount from about 1% to about 8% by weight, the glycol ether is present in an amount from about 3% to 30% by weight, and the one or more binder resins are present in an amount from about 1% to about 15% by weight of the ink jet ink composition.

26. The thermal ink jet ink composition of claim 25, wherein the one or more binder resins comprise a polyamide resin, a polyurethane resin, a cellulose nitrate resin, a polyvinyl butyral resin, or a rosin ester resin.

27. A method for printing images on a substrate in a thermal ink jet printer comprising directing a stream of droplets of a thermal ink jet ink composition to a substrate, wherein the thermal ink jet ink composition comprises:
one or more C1-C4 alcohols
one or more humectants,
one or more binder resins,
one or more colorants, and
one or more plasticizers, wherein the one or more plasticizers are present in an amount not more than 5% by weight of the ink jet ink composition and are selected from the group consisting of butyl benzyl phthalate, n-ethyl o,p-toluene sulfonamide, and mixtures thereof, and wherein the thermal ink jet ink composition is suitable for use in thermal ink jet printers; and
allowing the ink droplets to dry, thereby printing images on a substrate, wherein the thermal ink jet ink composition has a dry time of 7 seconds or less.

28. The thermal ink jet ink composition of claim 1, wherein the one or more volatile organic solvents comprise acetone, methyl ethyl ketone, or cyclohexanone, or a mixture thereof.

29. The thermal ink jet ink composition of claim 1, wherein the one or more volatile organic solvents comprise is methyl acetate, ethyl acetate, or n-butyl acetate, or a mixture thereof.

30. The thermal ink jet ink composition of claim 1, wherein the one or more volatile organic solvents comprise methyl ethyl ketone.

31. The thermal ink jet ink composition of claim 1, wherein the one or more volatile organic solvents comprise is ethanol.

32. The thermal ink jet ink composition of claim 17, further comprising acetone, methyl ethyl ketone, or cyclohexanone, or a mixture thereof.

33. The thermal ink jet ink composition of claim 17, further comprising methyl acetate, ethyl acetate, or n-butyl acetate, or a mixture thereof.

34. The thermal ink jet ink composition of claim 17, further comprising methyl ethyl ketone.

35. The thermal ink jet ink composition of claim 17, wherein the one or more C1-C4 comprise alcohols ethanol.

36. The method of claim 27, wherein the dry time is 4 seconds or less.

37. The method of claim 27, wherein the dry time is 2 seconds or less.

38. The method of claim 27, wherein the one or more binder resins are selected from the group consisting of polyamide resins, rosin ester resins, acrylic resins, polyketone resins, cellulose nitrate resins, polyvinyl butyral resins, and mixtures thereof.

39. The method of claim 27, wherein the binder resin is a polyamide resin, a polyurethane resin, a cellulose nitrate resin, a polyvinyl butyral resin, or a rosin ester resin.

40. The method of claim 27, further comprising methanol, ethanol, or isopropanol.

41. The method of claim 27, further comprising acetone, methyl ethyl ketone, or cyclohexanone, or a mixture thereof.

42. The method of claim 27, further comprising methyl acetate, ethyl acetate, or n-butyl acetate, or a mixture thereof.

43. The method of claim 27, further comprising methyl ethyl ketone.

44. The method of claim 27, wherein the one or more C1-C4 alcohols comprise ethanol.

45. The method of claim 27, wherein the one or more humectants are selected from the group consisting of polyol, glycol ether, diacetone alcohol, 2-pyrrolidinone, N-methylpyrrolidinone, ethyl lactate, 1,3-dimethyl-2-imidazolidindione, propylene carbonate, alkyl esters, and mixtures thereof.

46. The method of claim 27, wherein the humectant is a glycol ether.

47. The method of claim 27, wherein the glycol ether is propylene glycol monomethyl ether.

48. The thermal ink jet ink composition of claim 17, which further includes a surfactant.

49. The thermal ink jet ink composition of claim 48, wherein the surfactant is a polymeric surfactant.

50. The thermal ink jet ink composition of claim 49, wherein the polymeric surfactant is a blend of silanols and cyclic silicones.