Title of Invention

MAGENTA INK-JET INKS

Abstract The present invention is drawn to magenta dye blends and magenta ink-jet inks that can be used in ink sets for creating photo quality images. The dye blend can comprise a nickel chromophore-containing azo dye blended with a rhodamine dye at a 1:80 to 125:4 weight ratio. The dye blend can be incorporated into an ink vehicle to form magenta ink-jet inks that exhibit good lightfastness, airfastness, and chroma.
Full Text

MAGENTA INK-JET INKS
FIELD OF THE INVENTION
The present invention is drawn to the area of ink-jet imaging. More specifically, the present invention is drawn to magenta ink-jet inks that can be used in magenta-cyan-yellow ink sets.
BACKGROUND OF THE INVENTION
In general, ink-jet inks are either dye- or pigment-based inks. Both are typically prepared in an ink vehicle that contains the dye and/or the pigment. Dye-based ink-jet inks generally use a liquid colorant that is usually water-based to turn the media a specific color. Conversely, pigmented inks typically use a solid or dispersed colorant to achieve color.
Color characteristics of dye-containing inks play an important role in the quality of the printed ink-jet image. Perceived color quality can be characterized using any one of several color space systems, such as CIELAB or Munsell, as is well known in the art. With respect to Munsell color space, a given color is defined using three terms, namely Hue, Value, and Chroma. With respect to CIELAB color space, a color is defined using three terms L*, a*, and b*. With this system, L* defines the lightness of a color, and it ranges from 0 to 100 (with 100 being white). Additionally, the terms a* and b*, together, define the hue, where a* ranges from a negative number (green) to a positive number (red), and b* ranges from a negative number (blue) to a positive number (yellow). Alternate terms such as h° (hue angle) and C* (chroma) can be used to further describe a given color, as is known to those skilled in the art.

There is a need to improve permanence of ink-jet produced photographs, while preserving their color vividness. There are several failure mechanisms by which ink-jet produced images can undesirably change color over time. Photographs can fade under the action of light or an atmospheric gas, or as a result of trace impurities in the air. Another failure mechanism is due to humidity causing humid color change. Prior solutions have used multiple dyes in a single ink wherein one provides good lightfastness and the other provides good chroma. Such systems in the prior art have lead to images having bright chroma and mediocre to good lightfastness on swellable photo media. Alternative, single bright dyes have been used that provide good humidfastness and airfastness, but relatively poor lightfastness, or vice versa.
Accordingly, investigations continue into developing ink formulations that have improved properties and that do not improve one property at the significant expense of others. Many challenges still remain to further improve the image quality and lightfastness of ink-jet prints without sacrificing pen performance and reliability.
SUMMARY OF THE INVENTION
It has been recognized that it would be advantageous to develop magenta dye blends as well as magenta ink-jet inks for use with dye sets and ink-jet ink sets, respectively, that exhibit good gamut, lightfastness, airfastness, and chroma. As such, magenta dye blends and magenta ink-jet inks are provided that meet these criterion.
In one embodiment, a magenta dye blend for formulating an ink-jet ink can comprise a nickel -containing azo dye blended with a rhodamine dye. The nickel -containing azo dye to rhodamine dye weight ratio can be from 1:80 to 125:4.
Alternatively, a magenta ink-jet ink for ink-jet printing can comprise an effective amount of an ink vehicle and from 0.9 wt% to 10.5 wt% of a magenta dye blend admixed in the ink vehicle. Again, the magenta dye blend can

comprise a nickel -containing azo dye and a rhodamine dye at a weight ratio from 1:80 to 125:4.
Additional features and advantages of the invention will be apparent from the detailed description which illustrates, byway of example, features of the
invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
Before the present invention is disclosed and described, it is to be understood that this invention is not limited to the particular process steps and materials disclosed herein because such process steps and materials may vary somewhat. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only. The terms are not intended to be limiting because the scope of the present invention is intended to be limited only by the appended claims and equivalents thereof.
It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.
Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or subranges encompassed within that range as if each numerical value and subrange is explicitly recited. To illustrate, a concentration range of "about 0.1 wt% to about 5 wt%" should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations and the sub-ranges within the indicated range. Thus, included in this numerical range are individual concentrations such as 1 wt%, 2 wt%, 3 wt%, and 4 wt%, and sub-ranges such as from 0.1 wt% to 1.5 wt%, 1 wt% to 3 wt%, from 2 wt% to 4 wt%, from 3 wt% to 5 wt%, etc. This same principle applies to ranges reciting only one numerical value. For example, a range recited as "less

than about 5 wt%" should be interpreted to include all values and sub-ranges between 0 wt% and 5 wt%. Furthermore, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.
As used herein, "effective amount" refers to at least the minimal amount of a substance or agent, which is sufficient to achieve a desire effect. For example, an effective amount of an "ink vehicle" is the minimum amount required in order to create an ink composition, while maintaining properties necessary for effective ink-jetting.
As used herein, "liquid vehicle" or "ink vehicle" refers to the liquid fluid in which colorant is placed to form an ink. Ink vehicles are well known in the art, and a wide variety of ink vehicles may be used with the systems and methods of the present invention. Such ink vehicles may include a mixture of a variety of different agents, including, surfactants, solvents, co-solvents, buffers, biocides, sequestering agents, viscosity modifiers, surface- active agents, water, etc.
The term "substantially" when used with another term shall include from mostly to completely.
With this in mind, the present invention is drawn to the area of ink-jet imaging. More specifically, the present is drawn to magenta dye blends and magenta ink-jet inks for ink-jet imaging.
The magenta dye blend for formulating an ink-jet ink can comprise a nickel -containing azo dye blended with a rhodamine dye. The nickel -containing azo dye to rhodamine dye weight ratio can be from 1:80 to 125:4.
Additionally, a magenta ink-jet ink for ink-jet printing can comprise an effective amount of an ink vehicle and from 0.9 wt% to 10.5 wt% of a magenta dye blend admixed in the ink vehicle. The magenta dye blend of the ink-jet ink can comprise a nickel -containing azo dye and a rhodamine dye at a weight ratio from 1:80 to 125:4.
With respect to either the dye blend or the ink-jet ink, the nickel -containing azo dye can be any functional dye that meets these criterion set forth above. Specific examples, which are not intended to be limiting, are the dyes having a structure according to Formula 1 below:


Formula 1
In such a dye the nickel to dye molecule ratio can 1:1, 1:2 or 2:2. Ri can be N or C. Furthermore, R2, R3, R4, R5 and R6 can be CN, COOM, SO3M, H, and S02NH2. M can be H Na, Li, K, NH4, ammonium substituted alkyl and combinations thereof. The nickel -containing azo dye can be a single nickel -containing azo dye, or can be two or more nickel -containing azo dyes blended together.
One preferred embodiment of the above Formula 1 is Formula 2, which has a 1:2 nickel to dye ratio and is shown below.


Furthermore, in Formula 2, Ri is C; R2 and R3 are CN; R5 is S03M; and R4 and R6 are H.
Another preferred embodiment of Formula 1 is Formula 3, which has a 1:1 nickel to dye ratio and is shown below.

Furthermore, in Formula 3, R^ is N; R2 is H; R3 is COOH; R4 is S03; R5 is H and R6 is S03.
With respect to either the dye blend or the ink-jet ink, any functional rhodamine dye can be used. The rhodamine dye can be a single rhodamine dye, or can be two or more rhodamine dyes blended together. Without limitation, examples include Acid Red 52, Acid Red 289, Acid Red 388, and mixtures thereof.
The dye blends can be used to formulate magenta ink-jet inks, which can be used with commercially available ink-jet printers, such as DESKJET™ and other similar printers manufactured by Hewlett-Packard Company. In one embodiment, if the dye blend is used to formulate a magenta ink-jet ink, then the rhodamine dye can be present in the magenta ink-jet ink at from 0.1 wt% to 2.5 wt%, and the nickel -containing azo dye is present in the magenta ink-jet ink at from 0.8 wt% to 8 wt%. These and other magenta ink-jet inks can be used with three, four, five, or six pen ink sets for producing true colors on a variety of

media, including uncoated media, clay coated media, inorganic porous media, and gelatin coated media, each with improved lightfastness and gamut.
It should be noted that embodiments above and hereafter are merely provided to set forth some examples. Those skilled in the art will appreciate modifications that are also within the scope of the present invention.
A typical ink vehicle formulation that can be used with a dye set of the present invention can include one or more solvent or co-solvents, present in total at from 5.0% to 50.0% by weight, and one or more non-ionic, cationic, and/or anionic surfactant, present in total at from 0.01% to 10.0% by weight. The balance of the formulation can be purified water, and/or other vehicle components known in the art such as biocides, viscosity modifiers, materials for pH adjustment, sequestering agents, preservatives, and the like.
Classes of solvents or co-solvents that can be used can include aliphatic alcohols, aromatic alcohols, diols, glycol ethers, polyglycol ethers, caprolactams, formamides, acetamides, and long chain alcohols. Examples of such compounds include primary aliphatic alcohols, secondary aliphatic alcohols, 1,2-alcohols, 1,3-alcohols, 1,5-alcohols, ethylene glycol alkyl ethers, propylene glycol alkyl ethers, higher homologs of polyethylene glycol alkyl ethers, N-alkyl caprolactams, unsubstituted caprolactams, both substituted and unsubstituted formamides, both substituted and unsubstituted acetamides, and the like. Specific examples of solvents that can be used include trimethylolpropane, 2-pyrrolidinone, and 1,5-pentanediol.
One or more of many surfactants can also be used as are known by those skilled in the art of ink formulation and may be alkyl polyethylene oxides, alkyl phenyl polyethylene oxides, polyethylene oxide block copolymers, acetylenic polyethylene oxides, polyethylene oxide (di)esters, polyethylene oxide amines, protonated polyethylene oxide amines, protonated polyethylene oxide amides, dimethicone copolyols, substituted amine oxides, and the like. The amount of surfactant added to the formulation of this invention may range from 0.01% to 10.0% by weight
Consistent with the formulation of this invention, various other additives may be employed to optimize the properties of the ink composition for specific

applications. Examples of these additives are those added to inhibit the growth of harmful microorganisms. These additives may be biocides, fungicides, and other microbial agents, which are routinely used in ink formulations. Examples of suitable microbial agents include, but are not limited to, Nuosept (Nudex, Inc.), Ucarcide (Union carbide Corp.), Vancide (R.T. Vanderbilt Co.), Proxel (ICI America), and combinations thereof.
Sequestering agents such as EDTA (ethylene diamine tetra acetic acid) may be included to eliminate the deleterious effects of heavy metal impurities, and buffer solutions may be used to control the pH of the ink. From 0.001% to 2.0% by weight, for example, can be used. Viscosity modifiers and buffers may also be present, as well as other additives known to those skilled in the art to modify properties of the ink as desired. Such additives can be present at from 0.01% to 20% by weight.
Though weight percent ranges various ink vehicle components are provided, this must not imply that a particular component is an essential element. In other words, the weight percent ranges provided are meant to state that if the component is present, the weight percent range can be used.
EXAMPLES
The following examples illustrate the embodiments of the invention that are presently best known. However, it is to be understood that the following are only exemplary or illustrative of the application of the principles of the present invention. Numerous modifications and alternative compositions, methods, and systems may be devised by those skilled in the art without departing from the spirit and scope of the present invention. The appended claims are intended to cover such modifications and arrangements. Thus, while the present invention has been described above with particularity, the following Examples provide further detail in connection with what are presently deemed to be the most practical and preferred embodiments of the invention.






The "years to failure" for lightfastness was tested using the Wilhelm procedure as described in: The Permanence and Care of Color Photographs" by Henry Wilhelm, Preservation Publishing Co., Grinell, Iowa. The inks were printed at an optical density of 0.5, and then exposed to cool white fluorescent light at intensity of 70 kLux using an Atlas HPUV fadeometer. To correct for the paper background, the background corrections with the power of 1.5 were introduced. The time to failure was estimated based on the assumption of 450 Lux exposure per 12-hour day, that is? 1971 kLux-hour per year. The time to failure was defined as the time at which 25% optical density loss was observed.
"Days to failure" for airfastness was determined using atmospheric air in Corvallis, Oregon USA, which was blown over printed color palettes and the fade of images was monitored overtime using the Wilhelm failure criteria (as used in lightfastness described above). The time to failure in hours was defined as the time at which 25% optical density loss was observed.
All of the samples were tested side-by-side. No acceleration factor due to increased air flow was introduced, and thus, the time to failure is regarded as relative, rather than as an absolute measurement.
As can be seen from Table 3 above, nickel -containing azo dyes alone (M1 and M4) have good lightfastness and airfastness, but are not bright enough when compared to the HP970C benchmark. The HP970 magenta, though bright enough to act as a benchmark with respect to chroma, is less than

desirable with respect to lightfastness on swellable media and airfastness on porous media. Conversely, inks M2, M3, M5, M6, and M7, all of which include a nickel -containing azo dye blended with a rhodamine dye, provided better chroma than the benchmark HP970C, as well as provided significantly better lighfastess on swellable media and airfastness on porous media. Only ink M7 performed below the lighfastness benchmark Kodak Edge 8 AgX, though ink M7 still exhibited an improvement over the HP970C magenta ink with respect to lightfastness. Ink M8, which contained the H-acid dye blended with a nickel -containing azo dye, performed poorly with respect to lightfastness.
While the invention has been described with reference to certain preferred embodiments, those skilled in the art will appreciate that various modifications, changes, omissions, and substitutions can be made without departing from the spirit of the invention. For example, though a specific vehicle is shown for use in Example 1, other vehicles can also be used. Additionally, other inks can be used with the ink sets of the present invention for alternative applications. It is intended, therefore, that the invention be limited only by the scope of the following claims.
What is claimed is:








CLAIMS
1. A magenta dye blend for formulating an ink-jet ink, comprising:
(a) a nickel chromophore-containing azo dye, blended with
(b) a rhodamine dye,
said nickel chromophore-containing azo dye to rhodamine dye weight ratio being from 1:80 to 125:4.
2. A magenta dye blend as in claim 1 admixed with an effective amount
of an ink vehicle.
3. The magenta dye blend of claim 1 or 2, wherein the nickel
chromophore-containing azo dye comprises a nickel metalized napthol azo
triazole.


o. A magenta dye blend as in claim 1 or 2, wherein the rhodamine dye comprises a member selected from the group consisting of Acid Red 52, Acid Red 289, Acid Red 388, and mixtures thereof.
6. A magenta dye blend as in claim 1 or 2, wherein the nickel
chromophore-containing azo dye is a single nickel chromophore-containing azo
dye.
7. A magenta dye blend as in claim 1 or 2, wherein the nick nickel chromophore-containing azo dye is at least two nickel chromophore-containing azo dyes blended together.
8. A magenta dye blend as in claim 1 or 2, wherein the rhodamine dye is a single rhodamine dye.
9. A magenta dye blend as in claim 1 or 2, wherein the rhodamine dye is
at least two rhodamine dyes blended together.
10. A magenta ink-jet ink as in claim 2, wherein the ink vehicle
comprises from 5.0% to 50.0% by weight of solvent, from 0.01% to 10.0% of
surfactant, and water.



Documents:

166-chenp-2006 amended claims 02-03-2011.pdf

166-CHENP-2006 AMENDED CLAIMS 04-10-2010.pdf

166-CHENP-2006 AMENDED PAGES OF SPECIFICATION 04-10-2010.pdf

166-CHENP-2006 EXAMINATION REPORT REPLY RECEIVED 04-10-2010.pdf

166-chenp-2006 form-3 04-10-2010.pdf

166-chenp-2006 form-5 04-10-2010.pdf

166-CHENP-2006 OTHER PATENT DOCUMENT 04-10-2010.pdf

166-chenp-2006 power of attorney 02-03-2011.pdf

166-CHENP-2006 POWER OF ATTORNEY 04-10-2010.pdf

166-chenp-2006 correspondence others 02-03-2011.pdf

166-chenp-2006-abstract.pdf

166-chenp-2006-assignement.pdf

166-chenp-2006-claims.pdf

166-chenp-2006-correspondnece-others.pdf

166-chenp-2006-description(complete).pdf

166-chenp-2006-form 1.pdf

166-chenp-2006-form 26.pdf

166-chenp-2006-form 3.pdf

166-chenp-2006-form 5.pdf

166-chenp-2006-pct.pdf


Patent Number 246734
Indian Patent Application Number 166/CHENP/2006
PG Journal Number 11/2011
Publication Date 18-Mar-2011
Grant Date 14-Mar-2011
Date of Filing 12-Jan-2006
Name of Patentee HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P
Applicant Address 20555 S.H 249 HOUSTON TEXAS 77070
Inventors:
# Inventor's Name Inventor's Address
1 KABALNOV, ALEXEY, S 2900 HIGHLAND DRIVE CORVALLIS OR 97330
2 DUPUY, CHARLES, G 4515 NORTHWEST ELMWOOD DRIVE CORVALLIS OR 97330
3 WANG, PATRICIA, A 5541 SPRINGWOOD AVE SE SALEM OR 97306
PCT International Classification Number C09D 11/00
PCT International Application Number PCT/US2004/022806
PCT International Filing date 2004-07-16
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/622,985 2003-07-18 U.S.A.