Dye-based ink formulations

(54) Title: COLORING BASE INK FORMULATION AND METHOD FOR PREPARING A COLORING BASE INK FORMULATION (51) Int.CI .: C09D 11/00; B41J 2/01 (30) Unionist Priority: 23/04/2007 US 11 / 788,904 (73) Holder (s): HEWLETT-PACKARD DEVELOPMENT COMPANY, LP

(72) Inventor (s): ZIA UR REHMAN; MARY E. AUSTIN; SUKANYA RENGASWAMY

COLORING BASE INK FORMULATION AND METHOD FOR PREPARING A COLORING BASE INK FORMULATION.

Historic

The use of inkjet printing systems in offices and homes has grown dramatically in recent years. Growth can be attributed to drastic reductions in the cost of inkjet printers and substantial improvements in print resolution and overall print quality. Although print quality has improved dramatically, research and development efforts continue to improve the durability and permanence of inkjet images particularly in porous media because this property still lags behind the durability and permanence produced by other photographic techniques and Printing. A continuing demand for inkjet printing has resulted in the need to produce high quality images, high permanence and great durability, while maintaining a reasonable cost. In particular, there is a demand for inkjet printing that can produce documents and photographs that are resistant to water damage and that remain for long periods of time without losing their color due to ozone and / or light.

summary

Briefly described, embodiments of this disclosure include dye-based ink formulations and methods for preparing dye-based ink formulations. Among others, an exemplary dye-based ink formulation includes a dye and a solvent, in which the solvent is selected from: 1,2,4-butanotriol, 1,3-butylene glycol, N- (2hydroxyethyl) propanamide; 1,2-butylene glycol; 2,3 butanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; 2methyl-2,4-pentanediol; urea; hexylene glycol; betaine sulfolane; 1,2-hydroxyethyl-2P; sulfolane; 1,5-pentanediol; 2-pyridyl carbinol; 1,4-piperazine dicarboxaldehyde, N, N-dimethyl propionamide, 1,4-butanediol; dipropylene glycol,

N-acyl-L-cysteine; and combinations thereof, and the solvent being in an amount of about 5 to 30 weight percent of the dye-based ink formulation.

Among others, an exemplary method for preparing dye-based ink formulations includes: providing at least one dye from each of the following: a black dye, a yellow dye, a magenta dye, and a cyan dye; provide at least one solvent selected from: 1,2,4-butanotriol, 1,3-butylene glycol, N- (2hydroxyethyl) propanamide; 1,2-butylene glycol; 2,3 butanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; 2methyl-2,4-pentanediol; urea; hexylene glycol; betaine sulfolane; 1,2-hydroxyethyl-2P; sulfolane; 1,5-pentanediol; 2-pyridyl carbinol; 1,4-piperazine dicarboxaldehyde, N, N-dimethyl propionamide, 1,4-butanediol; dipropylene glycol, N-acyl-L-cysteine; and combinations thereof, and the solvent being in an amount of about 5 to 30 weight percent of the dye-based ink formulation; and forming the dye-based ink formulation.

Detailed Description

Incorporations of this disclosure will employ, unless otherwise indicated, techniques of synthetic organic chemistry, paint chemistry, media chemistry, and the like, which are within the limits of technical knowledge. Such techniques are fully explained in the literature.

The following examples are proposed in order to provide those with common experience in the art with a full disclosure and description of how to execute the methods and use the compositions disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (eg quantities, temperatures, etc.) but some errors and deviations must be taken into account. Unless otherwise stated, parts are by weight, temperatures are in ° C, and pressure is or is close to atmospheric. Standard temperature and pressure are defined as 20 ° C and 1 atmosphere.

Before the detailed description of the incorporations of this disclosure, it should be understood that, unless otherwise indicated, this disclosure is not limited to materials, reagents, reactive materials, particular manufacturing processes, or the like, as such may vary. It is also understood that the technology used here is only for the purpose of describing particular incorporations, and is not intended to be limiting. In the present disclosure, it is also possible that steps can be performed in a different sequence where this is logically possible.

It should be noted that when used in the specification and in the appended claims, the singular forms one, one, and the and include referents in the plural unless the context clearly shows otherwise. Thus, for example, the reference to a support includes a plurality of supports. In this specification and in the claims that follow it, reference will be made to a number of terms that will be defined to have the following meanings unless an opposite intention is obvious.

Light stability is defined based on exposure to nominal light behind glass before a failure condition is reached (loss of optical density and / or color change). Nominal light exposure is 450 lux 12 hours daily. The failure condition used is 25% dye loss to black, starting with an optical density black of only optical ink density 4 (CMYK) of 1.5 and / or color change over time. The gradual loss of light is marked on a scale of 1 to 4, where a score of 1 would mean 0-25 years of gradual loss of light, a score of 2 would mean 26-50 years of gradual loss of light, a score of 3 would mean 51-75 years of gradual light loss, and a score of 4 would mean more than 75 years of gradual light loss.

The gradual ozone loss test is performed in a Hampton 903 ozone chamber at a temperature of 25 ° C, 50% relative humidity and an ozone concentration of 1 ppm until a failure condition (loss of optical density and / or color change). The failure condition used is 25% dye loss to black, starting with an optical density black of only optical ink density 4 (CMYK) of 1.5 and / or color change over time. The gradual loss of ozone is marked on a scale of 1 to 4, where a score of 1 would mean 0-2 years of gradual ozone loss, a score of 2 would mean 3-5 years of gradual ozone loss, a score of 3 would mean 6-8 years of gradual ozone loss, and a score of 4 would mean more than 9 years of gradual ozone loss.

Water resistance is determined using the ISO / DIS 18935: 2004 (E) water resistance method. Water stability was scored on a scale of 0-6 where a score less than or equal to 2 would mean poor water resistance, a score of 3-4 would mean reasonably water resistant and a score of 5-6 would indicate good resistance to water. Water.

Discussion

Dye-based ink formulations are described. The dye-based ink formulation includes selected solvents that can be used with a dye or with a dye combination (e.g., a black dye, a yellow dye, a magenta dye, a cyan dye, and combinations thereof). The use of the dye-based ink formulation can produce improved water durability in print media, while at the same time it does not affect the efficiency of the products. For example, porous media printed with the dye-based ink formulation have improved water durability while retaining permanence compared to other dye-based formulations printed on the same type of porous media.

The dye-based ink formulation can be printed using an ink delivery system which includes, but is not limited to, inkjet technologies and coating technologies, which distribute ink over the media. Inkjet technology, such as continuous flow and ejection inkjet technologies when needed, can be used to distribute ink. 0 The ink delivery system can include at least one inkjet printer head system (for example, thermal inkjet printer head and / or piezo inkjet printer head) operating to deliver (e.g., jet) the inks through one or more of a plurality of nozzles on a print head. The printhead system incorporates an arrangement of discharge chambers that receive the ink dissolved or dispersed in a liquid vehicle, which are in fluid communication with one or more ink reservoirs.

The term printing media or printing medium may include, but is not limited to, a paper substrate, a photographic based substrate, greeting cards, film, coated paper, transparencies, brochure paper, cloth, and the like. In particular, the printing media includes porous printing media. Porous media includes, but is not limited to, HP ADVANCED glossy photo paper, HP photo quality inkjet paper, other inkjet paper, HP Semi-Gloss daily photo paper, HP photo paper and brochure HP TRI-FOLD, Brightness.

The dye-based ink formulation may include, but is not limited to, a dye and a vehicle. The dye-based ink formulation can include a single dye or a combination (mixture) of dyes. In an embodiment, the dye-based ink formulation includes, but is not limited to, a black dye, a yellow dye, a magenta dye, a cyan dye, and any combination thereof.

vehicle may include, but is not limited to, a solvent and optionally a surfactant and a buffer solution. Beyond

1,2,4Ν- (22,3 lithium hydroxide, potassium, and acid thereof, the dye formulation includes, but is not limited to, salts, biocides, an aqueous solution, and combinations thereof.

solvent may include, but is not limited to, butanotriol, 1,3-butylene glycol, hydroxyethyl) propanamide; 1,2-butylene glycol;

butanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; 2methyl-2,4-pentanediol; urea; hexylene glycol; betaine sulfolane; 1,2-hydroxyethyl-2P; sulfolane; 1,5-pentanediol; 2-pyridyl carbinol; 1,4-piperazine dicarboxaldehyde, Ν, Νdimethyl propionamide, 1,4-butanediol; dipropylene glycol, N-acyl-L-cysteine, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), 2-pyrrolidinone, and combinations thereof; in particular, the solvent can include 1,2,4-butanotriol, 1,3-butylene glycol, N- (2-hydroxyethyl) propanamide; 1,2butylene glycol; 2,3-butanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; 2-methyl-2,4-pentanediol; urea; hexylene glycol; betaine sulfolane; 1,2-hydroxyethyl-2-pyrrolidinone; sulfolane; 2-ethyl-2-hydroxymethyl-1, 3propanediol, and combinations thereof.

solvent can be about 5 to 30% by weight, about 10 to 25% by weight, about 15 to 25% by weight, about 18 to 22% by weight of the dye-based ink formulation.

Optionally, various buffers or pH adjusting agents can also be used in the ink formulation. The buffering agent may include, but is not limited to, alkali metal hydroxides (citric hydroxide);

triethanolamine, diethanolamine, hydrochloric acid; and other acidic or basic components that do not substantially interfere with drain control or optical density characteristics. In addition, commercially obtainable pH buffers can also be used and are obtainable from Sigma Aldrich (for example, MES, MOPs, Trizma, Bis-Tris, MOPSO, TES, TAPSO, TEA, TRICINE, BICINE, TAPS, and AMPSO, na form of acid or and amines (for example, sodium, amine hydroxide (for example, and dimethyl-ethanolamine);

lithium; triphosphates mixtures thereof

The surfactant can be about 0 to 3% by weight of the dye-based paint formulation.

The salt may include, but is not limited to, ammonium, potassium, or lithium benzoate salts; ammonium, potassium, or lithium acetates; xylene sulfonate salts of ammonium, potassium, or lithium; ammonium, sodium, potassium, and lithium nitrates; ammonium, potassium, or lithium lactates; ammonium, potassium, or lithium citrates; sodium, potassium, and lithium carbonates; sodium, potassium, and sodium, potassium, and lithium diphosphates; and In addition, the salt may include sodium, potassium, and lithium salts of compounds such as, but not limited to, citrate, succinate, lactate, formate, gluconate, tartrate, malonate, fumarate, malate, sebacate, laurate, glutarate, acetate, oxalate, adipate, pyelicate, subericate, azelaicate, and mixtures thereof.

The salt can be about 0 to 6% by weight of the dye-based ink formulation.

Various biocides can be used to inhibit the growth of undesirable microorganisms. Biocides may include, but are not limited to, sorbate salts, commercial products such as NUOSEPT¹Inc., a division of Huls America), UCARCIDE 'benzoates, salts (Nudex, (Union

Carbide)

VANCIDE¹ (RT Vanderbilt Co.), and PROXEL ™ (ICI by weight of

Americas), and other biocides.

Biocides can be about 0 to 3 dye-based ink formulation.

Dyes can be non-ionic, cationic, anionic, or mixtures thereof. Dyes for use in inkjet printing can be used in the practice of this disclosure. Dyes can include a large number of direct dyes and water-soluble acids. For the purpose of clarification only, and not for limitation, some exemplary dyes suitable for this purpose are shown below.

Specific examples of such dyes include the series of Pro-Jet dyes obtainable from Avecia Ltd., including Direct Yellow 86, Acid Red 249, Direct Blue 199, Direct Black 168, and Direct Yellow 132; Aminíla Brilliant Red FB (Sumitomo Chemical Co.); the Duasyn line of salt-free dyes obtainable from Hoechst, such as Reactive Black 31, Direct Yellow 157, Reactive Yellow 37, Acid Yellow 23, Reactive Red 180, Acid Red 52, and Acid Blue 9; mixtures thereof and the like.

Additional examples include Tricon 227 Direct Red and Tricon 17 Acid Yellow (Tricon Colors Incorporated), Bernacid 1BMN Red, Pontamine A Brilliant Binding Blue, BASF X-34, Pontamine 2 Food Black, FBL Supra Cone Catodirect Turquoise. (Carolina Color and Chemical), Direct Blue 86 (Mobay Chemical), Reactive Red 4 (Aldrich Chemical), Reactive Red 56 (Pylan, Inc.), Bright Red Levafix E-4B (Mobay Chemical), Bright Red Levafix E-6BA (Mobay Chemical), Red # 28 Pylam Certified D&C (Pyiam), Direct Shine Pink B ground (Crompton & Knowles), Cartasol Yellow GTF Presscacke (Sandoz, Inc.), Extra Cone, from Tartrazine (Sandoz, Inc.), Carolina and Chemical, Cartasol Yellow GTF Special Liquid (Sandoz, Inc.), D&C Yellow # 10 (Tricon), 16948 Dark Yellow (Tricon), Basacid X34 Black (BASF), Black 2GT Letter (Sandoz, Inc.), Neozapon 492 Red (BASF), Orasol G Red (CibaGeigy), Color Bright Pink B (Crompton-Knolls), Red Aizen Spilon C-BH (Hodagaya Chemical Company), Red Kayanol 3BL (Nippon Kayaku Company), Bright Red Levanol 3BW (Mobay Chemical Company), Lemon Yellow Levaderm (Mobay Chemical Company), Yellow Aizen Spilon C-GNH (Hodagaya Chemical Company), Yellow Spirit Fast 3G, Yellow Sirius Supra GD 167, Yellow Bright Cartasol 4GF (Sandoz), Yellow Pergasol CGP (Ciba-Geigy), Black Orasol RL (Ciba-Geigy), Black Orasol RLP (CibaGeigy), Black Savinyl RLS (Sandoz) , Dermacarbon 2GT (Sandoz), Black Pyrazole BG (ICI Americas), Black Morfast

Cone. A (Morton-Thiokol), Black Diazol RN Quad (ICI Americas), Blue Orasol GN (Ciba-Geigy), Blue Savinyl GLS (Sandoz, Inc.), Blue Luxol MBSN (Morton-Thiokol), Blue Sevron 5GMF (ICI Americas ), and Basacid 750 Blue (BASF); Bright Yellow Levafix E-GA, Yellow Levafix E2RA, Black Levafix EB, Black Levafix E-2G, Black Levafix P36A, Black Levafix PN-L, Bright Red Levafix E6BA, and Bright Blue Levafix EFFA, all obtainable from Bayer; Procion PA Turquoise, Procion HA Turquoise, Procion Ho5G Turquoise, Procion H-7G Turquoise, Procion MX5B Red, Procion H8B Red, Procion MX 8B GNS Red, Procion G Red, Procion MX-8G Yellow, Procion H-EXL Black, Procion Black PN, Blue Procion MX-R, Blue Procion MX-4GD, Blue Procion MX-G, and Blue Procion MX-2GN, all obtainable from ICI Americas; Red Cibacron FB, Black Cibacron BG, Black Lanasol B, Red Lanasol 5B, Red Lanasol B, and Yellow Lanasol 46, all obtainable from Ciba-Geigy; Black Baslien P-BR, Yellow Baslien EG, Bright Yellow Baslien P-3GN, Yellow Baslien M-6GD, Bright Red Baslien P-3B, Scarlet Baslien E-2G, Red Baslien EB, Red Baslien E7B, Red Baslien M-5B, Baslien ER Blue, Baslien P-3R Bright Blue, Baslien P-BR Black, Baslien P-GR Turquoise Blue, Baslien M-2G Turquoise, Baslien EG Turquoise, Baslien E-6B Green, all obtainable from BASF; Sumifix G Turquoise Blue, Sumifix H-GF Turquoise Blue, Sumifix B Black, Sumifix H-BG Black, Sumifix 2GC Yellow, Scarlet Sumifix Supra 2GF, and Sumifix 5BF Bright Red, all obtainable from Sumitomo Chemical Company; Intracon C-8G Yellow, Intracon C-8B Red, Intracon GE Turquoise Blue, Intracon HA Turquoise, and Intracon RL Black, all obtainable from Crompton & Knowles, Dyes & Chemicals Division; mixtures thereof, and the like. This relationship is intended to be merely exemplary, and should not be considered limiting.

The dye-based black ink formulation includes, but is not limited to, a black dye, a yellow dye, a magenta dye, and a cyan dye. In addition, the dye-based black ink formulation includes, but is not limited to, solvents, salts, buffers, biocides, binders, an aqueous solution, and combinations thereof.

The black dye may include, but is not limited to, 4 - [[6 [[4- [1,5-disulfo-2-naphthalenyl) azo] -2 1H-pyrazole-3-carboxylic acid -2 -methoxy-5methylphenyl] azo] -5-hydroxy-7-sulfo-2-naphthalenyl] azo] -4,5-hydroxy-5-oxo-l- (4-sulfo phenyl) - (Experimental Black 16), acid 2.7 -sulfonic naphthalene, 3- [[4 - [[4 - [[5- (aminocarbonyl) -1-ethyl-1,6-dihydro-2-hydroxy-4-methyl-6-oxo-3-pyridinyl] azo] potassium and sodium salt] -2-sulfo phenyl] azo] -2,5-bis (2-hydroxy ethoxy) phenyl] azo] -4,5-dihydroxy- (Experimental Black 10), cuprate (4-), tetrasodium (9C1) from [2 - (amino-κΝ) ethanol] [7 - [[3- (hydroxy-κθ) 4 - [[1— (hydroxy-κθ) -3-sulfo-7 - - [((2-sulfo ethyl) amino] -2naftalenyl]) azo-κΝΙ] phenyl] azo] -1,3-naphthalene disulfonate (6 -)] - (Experimental Black 11); 2,7naphthalene disulfonic acid, tetra-sodium salt (7C1) of 6 amino-4- hydroxy-3 - [[7-sulfo-4 - [(4-sulfo phenyl) azo] -1naphthalenyl] azo] - (Food Black 2) ; 1,3-benzene dicarboxylic acid, tetra-ammonium (9C1) salt of 5 - [[4— [7— amino-1-hydroxy-3-sulfο-2-naphthalenyl) azo] -6-sulfo-lnaphthalenyl] azo ] - (Project 286); and combinations thereof. In addition, it should be noted that the black dye may include, but is not limited to, tris azo dyes. In particular, the black dye can include compounds defined by Formula 1 below:

<img file="BRPI0809724B1_D0001.tif" />

Formula 1 in which X is SO3Q, where Q is a sodium ion, lithium ion, or a combination thereof, and where n is 1, 2 or 3.

Additional incorporations of tris azo dyes are described in US patent application No. 20070062409, which is incorporated herein by reference.

In addition, it should be noted that the black dye may include, but is not limited to, azocomposites. In particular, the azocomposite has the chemical structure of Formula 2:

<img file="BRPI0809724B1_D0002.tif" />

Formula 2 in which each of R¹ and R² independently represents a hydrogen, a halogen, a cyano group, a carboxy group, a sulfo group, a sulfamoyl group, an Nalkyl amino sulfonyl group, and an N-phenyl amino sulfonyl group; each of R³, R⁴, R⁵, R⁶, R⁷, and R⁸ independently represents a hydrogen, a halogen group, a hydroxy group, a cyano group, a carboxy group, a sulfo group, a sulfamoyl group, an N-alkyl amino sulfonyl group, an N-phenyl amino sulfonyl group; and n is 0 or 1.

The black dye can be about 0.5 to 5.0% by weight of the pigment-based black formulation.

The yellow dye may include, but is not limited to, 1,5-naphthalene disulfonic acid, tetra-sodium salt (9C1) of 3 - [[4 - [[4,6-bis [(3-sulfopropyl) thio] 1 , 3,5-triazin-2yl] amino] 5-methoxy-2-methyl phenyl] azo] - (Y104), 1,3naphthalene disulfonic acid, tetra-sodium (9C1) salt of 7— [[4 - [[4 , 6-bis [(3-sulfopropyl) thio] -1,3,5-triazin-2-yl] amino] 3-methoxyphenyl] azo] - (Y1189); benzenesulfonic acid, 2,5-dichloro-4- [4,5-dihydro-3-methyl-5oxo-4 - [(4-sulfophenyl) azo] -lH-pyrazol-l-yl] - disodium salt (9C1) (17-Na Acid Yellow); 1H-pyrazol-3-carboxylic acid, 4,5-dihydro-5-oxo-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] (Acid Yellow 23) tri13 sodium (9C1); 1,5-naphthalene disulfonic acid, 3,3 'sodium salt - [[6- [(2hydroxyethyl) amino] 1,3,5-triazine-2,4-diyl] bis [imino (2methyl-4,1 -phenylene) -2,1-diazanodyl]] bis- (1: 4) or TMA salt (Direct Yellow 86); and combinations thereof. The yellow dye can be about 0.1 to 4.0% by weight of the dye-based black ink formulation.

The magenta dye may include, but is not limited to, 6-benzothiazole sulfonic acid, 2- [4-cyano-3- (1,1-dimethylethyl) -5 - [[4-methyl-6 - [(6-sulfo -2-benzothiazolyl) (2,4,6-trimethyl-3-sulfo-phenyl) amino] -2 - [(2,4,6-trimethyl-3-sulfo-phenyl) amino] -3-pyridinyl] azo] -1H-pyrazole -l-il] (Magenta Experimental 1); 1,3-benzene disulfonic acid, 4- [[2,7-dihydro-3-methyl-2,7-dioxo-l- (3-benzoyl) -3H-naphtho [1,2,3 -of] quinolin-6-yl] amino] - (1: 3) (Experimental Magenta 2); 2,7-naphthalene disulfonic acid, 5- (benzoyl amino) -4-hydroxy-3 - [[1-sulfo-6 - [[2- (sulfo oxy) ethyl] sulfonyl] - tetra-sodium salt (9C1) 2-naphthalenyl] azo] (Reactive Red 180-Na); xanthyl, mono-sodium salt, 3 - [(2,6-dimethyl phenyl) amino] -6 - [(2,6-dimethyl sulfo phenyl) amino] -9- (2-phenyl sulfon) - (Acid Red 289 -At); xanthyl, sodium salt, 3,6-bis (diethylamino) -9- (2,4-phenyl disulfide) salt - (Acid Red 52); 2naphthalenesulfonic acid, disodium salt (9C1) of 6-amino-5 [[4 - [[4- [bis (2-hydroxyethyl) amino] -6 - [(2-sulfo ethyl) amino] -1,3,5- triazin-2-yl] amino] phenyl] azo] -4hydroxy- (Μ-377-Na); nickel, sodium 5 - [(2-hydroxy3,7-disulfo-1-naphthalenyl) azo] -1H-1,2,4-triazole-3carboxylate complexes (Magenta Experimental 7), and combinations thereof. The magenta dye can be about 0 to 3.5% by weight of the dye-based black ink formulation.

The cyan dye can include, but is not limited to, cuprate (3-), [[3,3 ', 3 - [[23 - [[3 - [[2-hydroxypropyl) amino] sulfonyl] propyl] sulfonyl] -29H , 31H-phthalocyanine-2,9,1614 triyl-KN29, KN30, KN31, KN32] tris (sulfonyl)] tris [1-propane sulfonate]] (5 -)] -, tri-lithium, (SP-4-2 ) - (9C1) (Cyan Experimental 1); copper, [29H, 31H-phthalocyaninate (2-) κΝ29, κΝ30, κΝ31, κΝ32] -, ammonium and sulfo sodium salts derived from amino sulfonyl [(2hydroxyethyl) amino] sulfonyl (Cyan Experimental 17i); copper, [29H, 31H-phthalocyaninate (2 -) - xN29, xN30, xN31, xN32] sulfo sodium salts derived from amino sulfonyl [(2hydroxyethyl) amino] sulfonyl (Cyano 485).

The cyan dye can be about 0 to 4.0% by weight of the dye-based black ink formulation.

Examples

In general, having now described the embodiments of the present disclosure, the following Examples describe some additional embodiments of the present disclosure. Although embodiments of the present disclosure are described together with the following examples and the corresponding figures and text, there is no intention to limit incorporations of the present disclosure to this description. On the contrary, the intention is to cover all alternatives, modifications, and equivalents included within the spirit and scope of incorporations of this disclosure.

Example 1

Table 1 shows examples of designed experiments where paints were prepared in paint vehicles containing 10.0% by weight of a single solvent (noted per sample # in (#)) in addition to a buffer, a surfactant and a biocide. Each ink had a constant supply of dye, so the observed differences in water resistance can be attributed to the effect of the solvent alone. As shown in Table 1, some of the solvents helped to improve the water resistance of the images.

Table 1

<td>Component</td><td>% by weight</td><td>Water resistance</td>

<td>TERGITOL 15-S-7</td><td> 0,2</td><td></td>

<td>SES sodium</td><td> 0,2</td><td></td>

<td>At₂ EDTA</td><td> 0,1</td><td></td>

<td>PROXEL GXL</td><td> 0,1</td><td></td>

<td>Samples (#)</td><td></td><td></td>

<td>1,2,4-butanotriol</td><td> 10(1)</td><td> 5</td>

<td>1,3-butylene glycol</td><td> 10 (2)</td><td> 5</td>

<td>1,5-pentanediol</td><td> 10(3)</td><td> 3</td>

<td>glycerol</td><td> 10(4)</td><td> 1</td>

<td>2-pyridyl carbonol</td><td> 10(5)</td><td> 3</td>

<td>3-methyl-1,3,5-pentanotriol</td><td> 10(6)</td><td> 1</td>

<td>N- (2-hydroxyethyl) propanamide</td><td> 10(7)</td><td> 5</td>

<td>1,2-butylene glycol</td><td> 10(8)</td><td> 5</td>

<td>N- (2-hydroxyethyl) acetamide</td><td> 10(9)</td><td> 1</td>

<td>4-pyridine propane</td><td> 10(10)</td><td> 1</td>

<td>3-morpholino-1,2-propanediol</td><td> 10(11)</td><td> 1</td>

<td>Piperazine</td><td> 10(12)</td><td> 1</td>

<td>1,4-piperazine dicarboxaldehyde</td><td> 10(13)</td><td> 3</td>

<td>Ν, Ν-dimethyl propionamide</td><td> 10(14)</td><td> 3</td>

<td>2,3-butanediol</td><td> 10 (15)</td><td> 5</td>

<td>3-methyl-1,5-pentanediol</td><td> 10(16)</td><td> 5</td>

<td>1,4-butanediol</td><td> 10(17)</td><td> 3</td>

<td>2-pyridyl carbinol</td><td> 10(18)</td><td> 3</td>

<td>1-methyl pyrazole</td><td> 10(19)</td><td> 1</td>

<td>1,2,3-trihydroxyhexane</td><td> 10 (20)</td><td> 1</td>

<td>Dipropylene glycol</td><td> 10 (21)</td><td> 3</td>

<td>N-acyl-L-cysteine</td><td> 10(22)</td><td> 3</td>

<td>l-ethyl-2P-4-carboxamide</td><td> 10(23)</td><td> 1</td>

<td>l-methyl-2P-4-carboxamide</td><td> 10 (24)</td><td> 1</td>

<td>1,6-hexanediol</td><td> 10 (25)</td><td> 5</td>

<td>Butiramide</td><td> 10 (26)</td><td> 1</td>

<td>N- (2-hydroxy-1-propyl) acetamide</td><td> 10(27)</td><td> 1</td>

<td>Urea</td><td> 10 (28)</td><td> 5</td>

<td>Hexylene glycol</td><td> 10 (29)</td><td> 5</td>

<td>Sulfolane</td><td> 10 (30)</td><td> 5</td>

<td>1,2-hydroxyethyl-2P</td><td> 10(31)</td><td> 5</td>

<td>Betaine sulfolane</td><td> 10 (32)</td><td> 5</td>

Example 2

Table 2a provides an illustrative embodiment of an ink formulation of the present disclosure. The black inks are prepared with 4.0% by weight of the Formula 2 dye and 3.0% by weight of Experimental Black 16 in a vehicle containing 10.9% EHPD had good color neutrality, but did not exhibit good water resistance. in the ISO water resistance test (Table 2b).

Table 2a

<td>Component</td><td>CAS #</td><td>Ink 1</td><td>Ink 2</td>

<td></td><td></td><td>% by weight</td><td>% by weight</td>

<td>1,2-hydroxyethyl 2P</td><td></td><td></td><td></td>

<td>EHPD</td><td> 77-99-6</td><td> 10,9</td><td> 10, 9</td>

<td>2-pyrrolidinone</td><td> 616-45-5</td><td> 6,5</td><td> 6, 5</td>

<td>1,5-pentanediol</td><td> 111-29-5</td><td> 2</td><td> 2</td>

<td>TERGITOL 15-S-7</td><td> 68131-40-8</td><td> 0,2</td><td> 0,2</td>

<td>SES sodium</td><td> 71119-23-8</td><td> 0,2</td><td> 0,2</td>

<td></td><td></td><td></td><td></td>

<td>DOWFAX 8390</td><td></td><td> 0,04</td><td> 0,04</td>

<td>At₂ EDTA</td><td> 6381-92-6</td><td> 0,0075</td><td> 0,0075</td>

<td>Betaine</td><td> 107-43-7</td><td> 3, 6</td><td> 3,6</td>

<td>2-methyl-2,4-pentanediol</td><td></td><td></td><td></td>

<td>PROXEL GXL</td><td></td><td> 0,1</td><td> 0,1</td>

<td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td>

<td>Dyes</td><td></td><td>% by weight</td><td>% by weight</td>

<td>Formula 2</td><td></td><td> 4</td><td></td>

<td>Experimental Black 16</td><td></td><td></td><td> 3</td>

<td>Balance with H₂0</td><td></td><td></td><td></td>

Table 2b

<td></td><td>Ink properties 1</td><td>Ink properties 2</td>

<td>Color</td><td>Bluish black</td><td>Neutral black</td>

<td>Gradual loss of ozone</td><td> 3</td><td> 2</td>

<td>Gradual loss of light</td><td> 4</td><td> 4</td>

<td>Water resistance</td><td> 1</td><td> 3</td>

<td>L * min</td><td> &gt;8</td><td> &lt;8</td>

<td>Saturation</td><td> &gt;8</td><td> &lt;8</td>

Example 3

Table 3a provides an illustrative embodiment of an ink formulation of the present disclosure. The removal of EHPD and betaine from ink vehicle components and the addition of 7% by weight of 1,2-hydroxyethyl-2P improved the water resistance of images printed with inks prepared with 4.0% by weight of Formula dye 2 and 3% by weight of Experimental Black 16 (Table 3b).

Table 3a

<td>Component</td><td>CAS #</td><td>Ink 3</td><td>Ink 4</td>

<td></td><td></td><td>% by weight</td><td>% by weight</td>

<td>1,2-hydroxyethyl 2P</td><td></td><td> 7</td><td> 7</td>

<td>EHPD</td><td> 77-99-6</td><td> -</td><td> -</td>

<td>2-pyrrolidinone</td><td> 616-45-5</td><td> 6,5</td><td> 6, 5</td>

<td>1,5-pentanediol</td><td> 111-29-5</td><td> 2</td><td> 2</td>

<td>TERGITOL 15-S-7</td><td> 68131-40-8</td><td> 0,2</td><td> 0,2</td>

<td>SES sodium</td><td> 71119-23-8</td><td> 0,2</td><td> 0,2</td>

<td>DOWFAX 8390</td><td></td><td> 0,04</td><td> 0, 04</td>

<td>At₂ EDTA</td><td> 6381-92-6</td><td> 0,0075</td><td> 0,0075</td>

<td>Betaine</td><td> 107-43-7</td><td> 3,6</td><td> 3,6</td>

<td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td>

<td>Dyes</td><td></td><td>% by weight</td><td>% by weight</td>

<td>Formula 2</td><td></td><td> 4</td><td></td>

<td>Experimental Black 16</td><td></td><td></td><td> 3</td>

<td>Balance with H₂O</td><td></td><td></td><td></td>

Table 3b

<td></td><td>Ink properties 3</td><td>Ink properties 4</td>

<td>Color</td><td>Bluish black</td><td>Neutral black</td>

<td>Gradual loss of ozone</td><td> 3</td><td> 2</td>

<td>Gradual loss of light</td><td> 4</td><td> 4</td>

<td>Water resistance</td><td> 3</td><td> 4</td>

<td>L * min</td><td> &gt;8</td><td> &lt;8</td>

<td>Saturation</td><td> &gt;8</td><td> &lt;8</td>

Example 4

Table 4a provides an illustrative embodiment of an ink formulation of the present disclosure. The addition of

7% by weight of 2-methyl-2,4-pentanediol in addition to 1,2hydroxyethyl-2P in the paint vehicle significantly improved the water resistance of black inks in the ISO water resistance test (Table 4b).

Table 4a

<td>Component</td><td>CAS #</td><td>Ink 5</td><td>Ink 6</td>

<td></td><td></td><td>% by weight</td><td>% by weight</td>

<td>1,2-hydroxyethyl 2P</td><td></td><td> 7</td><td> 7</td>

<td>EHPD</td><td> 77-99-6</td><td> -</td><td> -</td>

<td>2-pyrrolidinone</td><td> 616-45-5</td><td> 6,5</td><td> 6, 5</td>

<td>1,5-pentanediol</td><td> 111-29-5</td><td> 2</td><td> 2</td>

<td>TERGITOL 15-S-7</td><td> 68131-40-8</td><td> 0,1</td><td> 0,1</td>

<td>SES sodium</td><td> 71119-23-8</td><td> 0,2</td><td> 0,2</td>

<td>DOWFAX 8390</td><td></td><td> 0,04</td><td> 0,04</td>

<td>At₂ EDTA</td><td> 6381-92-6</td><td></td><td></td>

<td>Betaine</td><td> 107-43-7</td><td> 3,6</td><td> 3, 6</td>

<td>2-methyl1-2,4 pentanediol</td><td></td><td> 7</td><td> 7</td>

<td>PROXEL GXL</td><td></td><td> 0,1</td><td> 0,1</td>

<td>Dyes</td><td></td><td>% by weight</td><td>% by weight</td>

<td>Formula 2</td><td></td><td> 4</td><td></td>

<td>Experimental Black 16</td><td></td><td></td><td> 3</td>

<td>Balance with H₂0</td><td></td><td></td><td></td>

Table 4b

<td></td><td>Ink properties 5</td><td>Ink properties 6</td>

<td>Color</td><td>Bluish black</td><td>Neutral black</td>

<td>Gradual loss of ozone</td><td> 3</td><td> 2</td>

<td>Gradual loss of light</td><td> 4</td><td> 4</td>

<td>Water resistance</td><td> 4</td><td> 5</td>

<td>L * min</td><td> &gt;8</td><td> &lt;8</td>

<td>Saturation</td><td> &gt;8</td><td> &lt;8</td>

Example 5

Table 5a provides an illustrative embodiment of an ink formulation of the present disclosure. Inks prepared in an ink vehicle containing 7.0% by weight of each of the solvents, 1,2-butylene glycol and 1,6hexanediol resulted in printed images that had excellent water resistance from black inks in the ISO water resistance test ( Table 5b).

Table 5a

<td>Component</td><td>Ink 7</td>

<td></td><td>% by weight</td>

<td>1,2-butylene glycol</td><td> 7</td>

<td>1,6-hexanediol</td><td> 7</td>

<td>TERGITOL 15-S-7</td><td> 0,1</td>

<td>SES sodium</td><td> 0,2</td>

<td>At₂ EDTA</td><td> 0,1</td>

<td>PROXEL GXL</td><td> 0,1</td>

<td></td><td></td>

<td>Dyes</td><td>% by weight</td>

<td>Experimental Cyan 1</td><td> 1,59</td>

<td>Experimental Black 16</td><td> 1,71</td>

<td>Experimental Magenta 1</td><td> 1,9</td>

<td>Y104</td><td> 2,96</td>

Table 5b

<td></td><td>Ink properties 7</td>

<td>Color</td><td>Neutral black</td>

<td>Gradual loss of ozone</td><td> 4</td>

<td>Gradual loss of light</td><td> 4</td>

<td>Water resistance</td><td> 5</td>

<td>L * min</td><td> &lt;8</td>

<td>Saturation</td><td> &lt;8</td>

It should be noted that ratios, concentrations, quantities, and other numerical data can be expressed here in a range format. It should be understood that if its such a band format for convenience and brevity, and therefore, it should be interpreted in a flexible way to include not only the numerical values ​​explicitly mentioned as the limits of the band, but also to include all individual numeric values ​​or sub-bands covered within that range as if each value and sub-range is explicitly mentioned. To illustrate, a concentration range of about 0.1% to about 5% should be interpreted to include not only the explicitly mentioned concentration of about 0.1% by weight to about 5% by weight, but also to include individual concentrations (for example, 1%, 2%, 3%, and 4%) and the sub-ranges (for example, 0.5%, 1.1%, 2.2%, 3.3%, and 4.4 %) within the indicated range. The term about may include ± 1%, ± 2%, ± 3%, ± 4%, ± 5%, ± 6%, ± 7%, ± 8%, ± 9%, or ± 10%, or more of numeric values ​​being modified. In addition, the phrase about xay includes about x to about y.

Many variations and modifications can be made in the 5 incorporations described above. All such modifications and variations are intended to be included here within the scope of this disclosure and protected by the following claims.