Fluid set for ink-jet printers

The present invention relates to dyes, and more particularly, waterfast ink-jet ink compositions containing the same. The dyes of this invention, when interacted with a second reactive fluid or 5.sup.th pen fluid, provides permanence benefits, such as smearfastness, smudgefastness, and waterfastness.

FIELD OF INVENTION
 The present invention generally relates to dyes, and more particularly,
 waterfast ink-jet ink compositions containing the same. The dyes of this
 invention, when interacted with a second reactive fluid, provides
 permanence benefits, such as: smearfastness, smudgefastness, and
 waterfastness.
 BACKGROUND OF THE INVENTION
 The use of ink-jet printing systems has grown dramatically in recent years.
 This growth may be attributed to substantial improvements in print
 resolution and overall print quality, coupled with appreciable reduction
 in cost. Today's ink-jet printers offer acceptable print quality for many
 industrial, commercial, business and residential applications at costs
 fully an order of magnitude lower than comparable products available just
 a few years ago. Notwithstanding their recent success, intensive research
 and development efforts continue toward improving the permanence issues of
 ink-jet images.
 DETAILED DESCRIPTION OF THE INVENTION
 Definitions
 Fluid--includes either or both the reactant fluid and ink compositions.
 Reaction--means that the solubility or phase state of one or more
 components is changed as to immobilize the movement of at least one
 colorant on the print medium in the event that one fluid comes in contact
 with another fluid and interacts.
 Reactant Fluid--also known as a 5.sup.th pen fluid or fixer fluid. A fluid
 that is typically substantially devoid of color (i.e., the reactant fluid
 may contain no colorant (e.g., dye or pigment), or it may contain a
 colorant that does not absorb visible light but may absorb in either or
 both the IR or UV spectrums). The reactant fluid comprises a component (a
 molecule or complex, or a functional group in a molecule or complex) that
 is reactive with a component (a molecule or complex, or a functional group
 in a molecule or complex), including the colorant, in an ink thus
 providing for enhanced image integrity of printed areas created with the
 ink, such as, increased permanent (e.g. waterfastness, smearfastness,
 etc.) or bleed alleviation; improved color vibrancy, improved edge acuity,
 or reduced dry time; in the event that the reactant fluid and the ink are
 printed at least partially on a same pre-determined area on a print
 medium, or on pre-determined areas adjacent one another on a print medium.
 The reactive fluid is reactive with at least one ink formulated according
 to the present invention.
 Ink--a fluid containing at least one colorant, the ink absorbing in one or
 more regions (e.g., visible, IR, UV, etc.). Ink-jet printers typically
 contain an ink set with black, magenta, cyan, and yellow inks, commonly
 known as a 4-pen ink set. Additional pens with additional color inks may
 also be present.
 In the remainder of the disclosure, by way of example, unless stated
 otherwise, `image integrity` will be used to describe the desired effect
 obtained as the result of the reaction between reactive fluids, for
 example, between an ink reactive with the reactant fluid or between two
 inks reactive with one another. Furthermore, the term `image integrity`
 will encompass print attributes such as bleed alleviation, reduced dry
 time, smudgefastness, smearfastness, permanence, increased optical
 density, and waterfastness that may be affected as a result of the
 reaction between two reactive fluids. Additionally, when referring to an
 ink reaction with the reactant fluid, the ink may be also reactive with
 another, second ink.
 The present invention is directed to fluid sets, in particular for use in
 coloring applications, and more particularly for use in ink-jet printing.
 The present fluid set combines the benefits of interactive fluids while
 utilizing dyes providing enhanced image integrity to the ink-jet formula.
 The fluid set may be used in many applications of aqueous-based printing
 inks, in particular ink-jet inks for use in commercially available ink-jet
 printers such as DESKJET.RTM. printers, manufactured by Hewlett-Packard
 Company, of Delaware; and other commercially available home or office
 ink-jet printers.
 Aqueous inks of this invention comprise, by weight, from about 0.5 to about
 20 wt % colorant, preferably from about 1 to about 10%, and more
 preferably from about 1 to about 6 wt % colorant; from about 1 to about 40
 wt % of one or more organic solvents; and optionally up to about 20 wt %
 of an additive independently selected from the group consisting of
 immobilizing agents, surfactants, buffers, biocides, and mixtures thereof,
 with the proviso that at least one colorant in at least one ink is
 selected from dyes according to Formula I, II, III or IV.
 Colorants
 At least one of the inks of the present fluid set contains at least one
 colorant according to the present invention (i.e., `first colorant`), the
 colorant selected from the group consisting of dyes of Formula I, II, III
 and IV. Without being limited by theory, it is believed that the dyes of
 this invention interact with the reactive fluid, or 5.sup.th fluid, to
 form a gel or precipitate on the media which provides the benefits
 referred to above. It is believed that these dyes interact with the print
 media (cellulose fibers making up paper) through hydrogen bonding
 interactions and do not penetrate the paper as quickly as many other dyes.
 This allows time for the interaction between the dyes and the reactive
 fluid to form the gel or precipitate, thereby providing the benefit.
 For ease of reference, as used herein, the term `first colorant` refers to
 dyes of the present invention while the term `second colorant` refers to
 all other suitable colorants that may be used in conjunction with the
 first colorant of this invention in an inkset.
 Other colorants (`second colorants`) may be dye-based and/or pigments
 based. As used herein, the term `pigment` refers to a colorant that is
 insoluble in the aqueous vehicle, and includes disperse dyes as well as
 pigments that are either dispersed with the aid of a dispersant or those
 that are self-dispersed. The term `colorant` refers to either or both
 `first` and `second` colorant.
 The first colorants of the present invention are represented by any of the
 following structures:
 ##STR1##
 Wherein
 D is the chromophore;
 R.sub.1 is H or C.sub.1 -C.sub.5, preferably H or CH.sub.3, and more
 preferably H;
 R.sub.2 is a carbohydrate as defined by substructure A;
 R.sub.3 is C.sub.1 -C.sub.5, preferably CH.sub.3 ;
 R.sub.4 is a carbohydrate as defined by substructure B;
 R.sub.5 is defined by substructure C;
 R.sub.6 is selected from the group consisting of --OH, --R.sub.7 CO.sub.2 H
 wherein R.sub.7 is an aromatic or aliphatic moiety substituted with a
 CO.sub.2 H group, --R.sub.8 SO.sub.3 H wherein R.sub.8 is an aromatic or
 aliphatic moiety substituted with an --SO.sub.3 H group, NR.sub.1 R.sub.8
 wherein R.sub.8 is an aromatic moiety, --C.ident.N, --Cl, D wherein D is a
 chromophore as defined above; and NR.sub.2 R.sub.5 (amino carbohydrate)
 wherein R.sub.2 and R.sub.5 are as defined above.
 ##STR2##
 Wherein
 m is 1-5, preferably 1-2, and more preferably 1;
 n is 2-7, preferably 3-5, and more preferably 4;
 w is 0-4, preferably 0-1, and more preferably 0;
 x is 2-7, preferably 2-5, and more preferably 3;
 y is 0-1, preferably 1;
 z is 0-3, preferably 0-1, and more preferably 0.
 In the preferred embodiment, R.sub.6 is selected from the group consisting
 of --OH, --R.sub.7 CO.sub.2 H, --R.sub.8 SO.sub.3 H, and --NR.sub.1
 R.sub.8, and more preferably, R.sub.4 is --OH or R.sub.7 CO.sub.2 H;
 wherein R.sub.1, R.sub.7 and R.sub.8 are as defined above.
 The suitable starting dye (parent) for Formula I, Formula II and Formula
 III dyes contains a chromophore and has a primary or secondary amine
 functionality (i.e., --NHR.sub.1). The suitable starting dye (parent) for
 Formula IV contains a chromophore and has a primary or secondary amine
 functionality (i.e., --NHR.sub.1). Furthermore, the starting dye may be a
 commercial dye having a chloro-substituted triazabenzene reactive group
 (e.g., compound C1) or it may be a dye without such a reactive group
 (e.g., compound C2), in which case the latter dye may be reacted with a
 chloro-substituted triazabenzene ring (compound C3) to produce the former
 dye containing the reactive group (see Reaction Schemes 1-4) before the
 synthesis of the dyes of the present invention.
 ##STR3##
 Examples of suitable starting dyes include, but are not limited to: acid
 alizarin brown RP, acid blue 129, acid blue 25, acid blue 29, acid blue
 40, acid blue 41, acid yellow 66, acid yellow 69, acid yellow 9, basic
 blue 16, basic blue 11, basic blue 7, basic orange 2, basic red 2, basic
 red 5, basic red 9, basic violet 14, basic violet 2, cotton orange G,
 cresyl violet acetate, direct blue 1, direct blue 71, direct brown 191,
 Avecia 286/287 (also available under the trade name Projet Black 1/Projet
 Black 2), disperse black 1, disperse black 2, disperse black 3, and
 disperse black 4; dichlorotriazinyl dyes such as (i.e., dyes having two
 chlorines on the triazene ring to be substituted with one or two
 equivalents of amino carbohydrate (i.e., --NR.sub.2 R.sub.5) reactive
 yellow 3, reactive red 2, reactive red 5, reactive red 4 (available from
 Avecia); monochlorotriazinyl dyes, such as reactive yellow 127, reactive
 red 24, reactive blue 15, reactive violet 2 and reactive black 1.
 Reactions and Reactive Components or Reactive Agents
 The reactant fluids of this invention are preferably applied either or both
 under and over the ink layer in the printing process using methods known
 in the art for 5.sup.th pen applications.
 The present invention can be employed in any reactive system, regardless of
 the purpose for the reaction, where the reactant fluid is reactive with
 the ink comprising the dyes of the present invention, and in addition,
 also when an ink of the present invention and another ink react with one
 another. The one or more reactions can serve can serve to enhance any one
 of a number of desired image integrity attributes. Furthermore, the
 reaction scheme, between any two fluids reactive with one another may be
 the same or different than reaction scheme between any other two reactive
 fluids. Depending on the reaction mechanism employed, the reactive fluid
 is selected to interact with the ink formula containing the above inks.
 For example, when the reaction mechanism for reducing bleed is through
 precipitation of a pH-sensitive colorant, the fluid reactive with such ink
 comprises an acid in sufficient amount to render the pH-sensitive colorant
 of the ink insoluble upon contact, as disclosed in U.S. Pat. No.
 5,181,045, entitled "Bleed Alleviation using pH sensitive Dyes/Inks"; U.S.
 Pat. No. 5,785,743, entitled "Bleed Alleviation in Ink-Jet Inks using
 Organic Acids," filed by Adamic et al. On Dec. 6, 1995; and U.S. Pat. No.
 5,679,143, entitled "Bleed Alleviation in Ink-Jet inks Using Acids
 Containing a Basic Functional Group."
 Similarly, when the reaction mechanism is based on the use of a
 precipitating agent, such as multi-valent metal salts, as disclosed in the
 U.S. Pat. No. 5,428,383, the fluid reactive with such ink comprises a
 precipitating agent, e.g., multi-valent metal salt.
 Alternatively, the reaction between an ink and a reactant fluid may be
 based on the two fluids having components with opposite charges. For
 example, the ink may have a negatively charged colorant and the reactant
 fluid may contain a positively charged ingredient (or a component with a
 positively charged moiety), such that upon contact the colorant in the ink
 becomes immobilized. Examples of such positively charged components are
 polymers, dispersants on a pigment (in the case where the reactive fluid
 is another ink), self-dispersed pigments (in the case where the reactive
 fluid is another ink), and cationic surfactants.
 Similarly, when there are multiple reaction schemes, all desired reactive
 components compatible with one another in a given fluid composition may be
 present in the reactant fluid and any other reactive ink, such as those
 disclosed in, as for example, U.S. patent application Ser. No. 09/064,643,
 entitled "Ink Set for Improved Print Quality," by Ma et. al., filed Apr.
 22, 1998, and assigned to the same assignee as the present invention, and
 incorporated herein by reference in its entirety. For example, Ma
 discloses a set of printing liquids having multiple interactions:
 The reaction between the black and magenta inks is caused by the pH
 difference between the two inks and the excess hydrogen ions form the
 magenta ink. The black ink and the yellow ink react by virtue of the
 opposite charge between the dispersants for the black and the yellow
 pigments. The black ink and the cyan ink react due to the precipitation of
 the dispersed black pigment by the multi-valent metal ions (precipitating
 agent). Additionally, when the fourth ink (e.g., cyan) contains the
 optional acid, the pH difference between the cyan and the black ink
 further enhances the precipitation of the colorant in the black ink. The
 reaction between the magenta and the yellow inks is caused by the opposite
 charge between the dispersants for the magenta and the yellow pigments.
 The magenta and the cyan inks react by virtue of the multivalent metal
 precipitating the dispersed magenta pigment. And, finally, the yellow ink
 and the cyan ink react due to the opposite charge between the dispersed
 yellow pigment and the cyan dye.
 In the present invention, the reactant fluid may contain all of the
 aforementioned reactive components compatible with one another so as to
 provide for the proper reaction mechanisms between the reactant fluid and
 an ink reactive with the reactant fluid or between two inks reactive with
 one another.
 It is also within the scope of the present invention to have a fluid set
 wherein the reactant fluid may have to react with more than one ink to
 achieve the desired result (that is, the reactant fluid may provide a
 component such that in the event that the reactant fluid and two inks come
 into contact with one another on a print medium a desirable reaction
 occurs).
 Furthermore, the reactant fluid may contain polymeric or cross-linkable
 components for rendering the images more permanent. For example, the
 reactive fluids (e.g., the reactant fluid and an ink reactive with the
 reactant fluid) may each contain a component that will react with the
 component in the other reactive fluid such that upon reacting it will
 render the printed image more permanent.
 Preferably, the ink containing the dyes of the present invention is
 reactive with the reactant fluid, optionally it can also react with
 another ink. Preferably all of the inks selected for use in the ink set
 are reactive with the reactant fluid. The reactant fluid comprises at
 least one component for reactiving with at least one ink containing the
 above described dyes. Additionally, but optionally, the reactive fluid may
 comprise any other component which serves to aid the performance of the
 fluid in the inkjet printer. For example, water, solvents, surfactants,
 and biocides may be employed.
 The reaction between the reactive fluids may employ any one of several
 reactive mechanisms well-known in the art such as the use of a
 pH-sensitive colorant, or the use of a precipitating agent, as described
 in the aforementioned patents and applications. As stated earlier, the
 reaction between the reactive fluids can serve to enhance any one of a
 number of print system attributes. Furthermore, the reaction scheme,
 between the reactive fluid and one ink may be the same or different than
 reaction schemes between the reactive fluid and a second ink.
 Examples of immobilizing agents include: precipitating agents such as
 inorganic salts (preferably divalent or trivalent salts of chloride and/or
 nitrate such as Mg(NO.sub.3).sub.2, Ca(NO.sub.3).sub.2, CaCl.sub.2,
 MgCl.sub.2, AlCl.sub.3, Al(NO.sub.3).sub.3 and the hydrates of these
 agents, organic acids such as succinic acid, citric acid, glutaric acid,
 morpholinoethane sulfonic acid, boronic materials such as boric acid and
 the ammonium or sodium salts of borates, cationic surfactants such as
 Unamine O (available form Lonza) and dodecyltrimethylammonium chloride,
 and polymeric cationic reagents such as acidified PEI,
 poly(diallyldimethyl)ammonium chloride, and acidified poly(allylamine).
 The reactive fluid, in addition to water and the reactant agent described
 above, may also contain one or more of the same ingredients and in the
 same % amounts commonly formulated into inks. For instance, solvents,
 surfactants, amphiphiles, biocides, buffers may be present in the reactive
 fluids of this invention.
 Additional Colorants or Inks
 Examples of suitable second colorants herein include organic dyes having at
 least one and preferably two or more carboxyl and/or carboxylate groups,
 examples of which are listed in U.S. Pat. No. 4,963,189 (filed by
 Hindagolla and assigned to the same assignee as the present invention, and
 incorporated herein by reference), and carboxylated pigments dispersions
 having a water insoluble colorant (e.g., pigment) dispersed with a
 dispersant preferably containing carboxylate solubilizing groups, such as
 those disclosed in U.S. Pat. No. 5,085,698, and U.S. Pat. No. 5,555,008,
 both incorporated herein by reference, or self-dispersed pigments provided
 under the Trade name Cabojet.TM. by Cabot Company.
 The fluids of the present invention may comprise from about 1 to about 40
 wt % of at least one organic solvent. More preferably the fluids comprise
 from about 1 to about 25 wt % of at least one organic solvent with from
 about 5 to about 15 wt % being the more preferred. Optionally, one or more
 water-soluble surfactants/amphiphiles (0 to about 40 wt %, preferably
 about 0.1 to about 5 wt %) may be present. The inks of this invention have
 a pH in the range of from about 7 to about 11, preferably from about 8 to
 about 10, more preferably from about 8 to about 9. The 5.sup.th pen fluids
 of this invention have a pH in the range of from about 2.5 to about 7,
 preferably from about 3 to about 6, more preferably from about 4 to about
 5.
 Aqueous Vehicle
 All concentrations herein are expressed in weight percentages, unless
 otherwise indicated. The purity of all components is that employed in
 normal commercial practice for ink-jet inks. All cited documents and
 patents are hereby incorporated by reference.
 Other ingredients added to the inks of this invention should be compatible
 with the above colorants employed in this invention. Likewise, other
 ingredients added to the reaction fluids of this invention should be
 compatible with the above reactive agents employed in this invention.
 The aqueous vehicle is water or a mixture of water and at least one
 water-soluble organic solvent, as is well-known in the art. Selection of a
 suitable mixture depends on requirements of the specific application, such
 as the desired surface tension and viscosity, the selected colorant or
 reactive agent, drying time of the ink-jet fluid, and the type of print
 medium onto which the fluid will be printed. For a discussion of inks and
 their properties, see The Printing Manual, 5.sup.th Ed., Leach et al.
 (Chapman and Hall, 1993). See also U.S. Pat. Nos. 2,833,736; 3,607,813,;
 4,104,061; 4,770,706; and 5,026,755.
 The water soluble organic solvents suitably employed in the present ink-jet
 ink compositions include any of, or a mixture of two or more, of such
 compounds as nitrogen-containing ketones, such as 2-pyrrolidinone,
 N-methyl-2-pyrrolidinone (NMP), 1,3-dimethylimidazolid-2-one, and
 octyl-pyrrolidinone; diols such as ethanediols (e.g., 1,2-ethanediol),
 propanediols (e.g., 1,2-propanediol, 1,3-propanediol), butanediols (e.g.,
 1,2-butanediol, 1,3-butanediol, 1,4-butanediol), pentanediols (e.g.,
 1,2-pentanediol, 1,5-pentanediol), hexanediols (e.g., 1,2-hexanediol,
 1,6-hexandiol, 2,5-hexanediol), heptanediols (e.g., 1,2-heptanediol,
 1,7-heptanediol), octanediols (e.g., 1,2-octanediol, 1,8-octanediol);
 triolos such as 2-ethyl-2-hydroxymethyl-1,3-propanediol and
 ethylhydroxypropanediol (EHPD); and glycol ethers and thioglycol ethers,
 commonly employed in ink-jet inks such as polyalkylene glycols such as
 polyethylene glycols (e.g., diethylene glycol (DEG), triethylene glycol,
 tetraethylene glycol), polypropylene glycols (e.g., dipropylene glycol,
 tripropylene glycol, tetrapropylene glycol, polymeric glycols (e.g., PEG
 200, PEG 300, PEG 400, PPG 400) and thiodiglycol. Prefereably
 2-pyrrolidinone, NMP, DEG, EHPD and 1,5-pentanediol are employed in the
 practice of this invention with 2-pyrrolidinone, DEG and 1,5-pentanediol
 being the most preferred solvents.
 Suitable surfactants may be nonionic or anionic when used in the fluid
 vehicle. Examples of suitable nonionic surfactants include, secondary
 alcohol ethoxylates (e.g., Tergitol series available form Union Carbide
 Co.), nonionic fluoro surfactants (such as FC-170C available from 3M),
 nonionic fatty acid ethoxylate surfactants (e.g., Alkamul PSMO-20
 available from Rhone-Poulenc), fatty amide ethoxylate surfactants (e.g.,
 Aldamide L-203 available from Rhone-Poulenc), and acetylenic polyethylene
 oxide surfactants (e.g., Surfynol series, available from Air Products &
 Chemicals, Inc.). Examples of anionic surfactants include
 alkyldiphenyloxide surfactants (such as Calfax available from Pilot), and
 Dowfax (e.g., Dowfax 8390 available from Dow), and fluorinated surfactants
 (Fluorad series available form 3M). Cationic surfactants may be used in
 the reactive fluid which interacts with the ink vehicle and/or ink vehicle
 colorant. Cationic surfactants that may be used include betaines (e.g.,
 Hartofol CB-45 available from Hart Product Corp., Mackam OCT-50 available
 form McIntyre Group Ltd., Amisoft series available from Ajinomoto),
 quaternary ammonium compounds (e.g., Glucquat series available from
 Amerchol, Bardac and Barquat series available from Lonza), cationic amine
 oxides (e.g., Rhodamox series available form Rhone-Poulenc, Barlox series
 available from Lonza) and imidazoline surfactants (e.g., Miramine series
 available from Rhone-Poulenc, Unamine series available from Lonza).
 Buffers may be used to modulate pH and they can be organic based biological
 buffers or inorganic buffers such as sodium phosphate. Furthermore, the
 buffer employed should provide a pH ranging from about 4 to about 9 in the
 practice of the invention. Examples of preferably employed organic buffers
 include Trizma base, available from companies such as Aldrich Chemical
 (Milwaukee, Wis.), 4-morpholinoethanesulfonic acid (MES) and
 4-morpholinopropanesulfonic acid (MOPS).
 Any of the biocides commonly employed in ink-jet inks may be employed in
 the practice of the invention, such as NUOSEPT 95, available form Hals
 America (Piscataway, N.J.); Proxel GXL, available from Avecia (Wilmington,
 Del.); and glutaraldehyde, available from Union Carbide Company (Bound
 Brook, N.J.) under the trade designation UCARCIDEW 250. Proxel GXL is the
 preferred biocide.
 Printing Methods
 This invention also encompasses a method for inkjet printing with the
 colorants and 5.sup.th pen fluids discussed above.
 Ink containing one or more of the colorants having a structure selected
 from the group consisting of Formula I, Formula II, Formula III, or
 Formula IV is printed onto a substrate, such as paper, textile or
 transparency. Next, the ink is overprinted with a layer of 5.sup.th pen
 fluid such that the ink comes into contact with the reactive agent in the
 reactive fluid. The colorants in the ink then react with the reactive
 agent to form a gel or precipitate.
 Alternatively, the 5.sup.th pen fluid may be underprinted as a first layer
 on the substrate and then the ink is overlaid on top of the 5.sup.th pen
 fluid layer. And in another alternative, the 5.sup.th pen fluid is both
 underprinted and overprinted with the ink layer.
 Method of Synthesis
 The dyes of the present invention may be synthesized using the general
 procedures and conditions described below:
 Synthesis of Formula I
 Procedure 1: Dissolve one molar equivalent of the starting dye in deionized
 water with one molar equivalent of the carbohydrate (i.e., compound having
 R.sub.2 or R.sub.4 functionality). Add 2 molar equivalents of hydrochloric
 acid to the reaction mixture and stir vigorously. Slowly add a molar
 equivalent of sodium cyanoborohydride (dissolved in methanol) to the
 reaction mixture. After addition of the sodium cyanoborohydride, slowly
 warm the reaction mixture to reflux and continue refluxing for a period of
 4-8 hours. At the end of the reflux period, cool the reaction to room
 temperature, add enough hydrochloric acid to evolve hydrogen cyanide from
 the excess sodium cyanoborohydride. Concentrate the reaction mixture using
 reduced pressure and purify with the use of a silica gel column using
 acetonitrile and water as the eluent.
 Procedure 2: A second synthesis to form compounds of type Formula I may be
 performed on dyes of Formula III. Dissolve the Formula III compound in
 tetrahydrofuran, add 2 molar equivalent of acid (e.g.,
 2-naphthalenesulfonic acid) to the reaction mixture. Slowly add a 2 molar
 equivalent of sodium cyanoborohydride (dissolved in methanol) to the
 reaction mixture. After addition of the sodium cyanoborohydride, slowly
 warm the reaction mixture to reflux and continue refluxing for a period of
 4-8 hours. At the end of the reflux period, cool the reaction to room
 temperature. Concentrate the reaction mixture using reduced pressure and
 purify with the use of a silica gel column using acetonitrile and water as
 the eluent.
 Synthesis of Formula II or Formula III
 Dissolve one molar equivalent of the dye in acetonitrile along with a four
 molar equivalent of the carbohydrate. Add a catalytic amount of
 hydrochloric acid to the reaction mixture and stir vigorously while
 refluxing for a period of 2-4 hours. After refluxing, cool the reaction to
 room temperature and remove the solvent under reduced pressure. Purify the
 dye using a silica gel column and acetonitrile as the eluent.
 EXAMPLE #1
 Synthesis of Acid Blue TS-1
 ##STR4##
 In a 500 mL, 3-neck, round bottom flask 4.27 g. of Acid Blue 25 and 4.69 g.
 of D-glucose is added and dissolved in 150 mL of deionized water. The
 flask is fitted with a reflux condenser and an addition funnel and the
 reaction mixture stirred vigorously. The reaction mixture then has 2.00 g.
 of concentrated hydrochloric acid (36%) added, while in the addition
 funnel 1.60 g. of sodium cyanoborohydride is dissolved in methanol. After
 allowing the D-glucose and Acid Blue 25 to react for 30 minutes in the
 presence of hydrochloric acid, the sodium cyanoborohydride is slowly added
 to the reaction mixture. Upon complete addition of the sodium
 cyanoborohydride, the reaction is gently refluxed for 2 hours and then
 allowed to cool to room temperature. Additional hydrochloric acid is then
 added (to destroy excess sodium cyanoborohydride) and the reaction mixture
 concentrated under reduced pressure. The dye (acid blue TS-1) is then
 purified on a silica gel column using acetonitrile and water as the
 eluents.
 EXAMPLES #2
 Synthesis of Basic Red TS-2
 ##STR5##
 In a 500-mL, 3-neck, round bottom flask 4.49 g. of Basic Red 2 and 7.49 g.
 of D-glucose is added and dissolved in 150 mL of deionized water. The
 flask is fitted with a reflux condenser and an addition funnel and the
 reaction mixture stirred vigorously. The reaction mixture then has 4.90 g.
 of concentrated hydrochloric acid (36%) added, while in the addition
 funnel, 3.48 g. of sodium cyanoborohydride is dissolved in methanol. After
 allowing the D-glucose and Basic Red 2 react for 30 minutes in the
 presence of hydrochloric acid, the sodium cyanoborohydride is slowly added
 to the reaction mixture. Upon complete addition of the sodium
 cyanoborohydride, the reaction is gently refluxed for 2 hours and then
 allowed to cool to room temperature. Additional hydrochloric acid is then
 added (to ensure the solution is acidic to destroy any excess sodium
 cyanoborohydride) and the reaction mixture concentrated under reduced
 pressure. The dye (basic red TS-2) is then purified on a silica gel column
 using acetonitrile and water as the eluents.
 EXAMPLE #3
 Synthesis of Direct Blue TS-1
 ##STR6##
 In a 500 mL, 3-neck, round bottom flask 6.73 g. of Direct Blue 1 and 6.32
 g. of D-glucose is added and dissolved in 150 mL of deionized water. The
 flask is fitted with a reflux condenser and an addition funnel and the
 reaction mixture stirred vigorously. The reaction mixture then has 2.87 g.
 of concentrated hydrochloric acid (36%) added, while in the addition
 funnel 1.80 g. of sodium cyanoborohydride is dissolved in methanol. After
 allowing the D-glucose and Direct Blue 1 to react for 30 minutes in the
 presence of hydrochloric acid, the sodium cyanoborohydride is slowly added
 to the reaction mixture. Upon complete addition of the sodium
 cyanoborohydride, the reaction is gently refluxed for 2 hours and then
 allowed to cool to room temperature. Additional hydrochloric acid is then
 added (to ensure destruction of any excess sodium cyanoborohydride) and
 the reaction mixture concentrated under reduced pressure. The dye (direct
 blue TS-1) is then purified on a silica gel column using acetonitrile and
 water as the eluents.
 The dyes of Formula IV may be synthesized using standard procedures such as
 those described in U.S. Pat. No. 5,722,745, and the reactions described in
 Reaction Scheme 1-4.
 ##STR7##
 ##STR8##
 ##STR9##
 ##STR10##
 The following exemplify the typical reaction conditions designated as a, b,
 c or d in the Reaction Schemes 1-4:
 Reaction (a): Dissolve dye/chromophore (such as Compound C2 in synthesis
 Reaction Scheme 1) in water at neutral pH (pH.about.7) and add to an ice
 cold suspension of cyanuric chloride (ice bath made up from 1:1
 acetone:ice water) at a dye/chromophore to cyanuric chloride (Compound C3)
 molar ratio of about 1:1. Stir the reaction mixture for about 2 hours. The
 reaction product (such as Compound C1 in Reaction Scheme 1) may then be
 isolated through precipitation methods, rinsing with hexanes and followed
 by drying the precipitate.
 Reaction (b): Dissolve the dichlorotriazinyl compound (such as Compounds
 C1, C7 and C9 in Reaction Schemes 1, 2, or 3, respectively) in water at
 neutral pH (pH.about.7) and add a one molar equivalent of the reactive
 material (such as Compounds C2 and C4 in Reaction Schemes 1, 2 or 3,
 respectively) (dissolved in water at pH.about.7). Raise the temperature to
 35.degree. C. and allow reaction to proceed overnight. The reaction
 product (such as Compounds C5 and C8, in Reaction Schemes 1, 2 or 3,
 respectively) may then be isolated through precipitation methods, rinsing
 with hexanes and drying. If the reactive material is the amino
 carbohydrate (as in Compound C4 in Reaction Scheme 1) and R4 is an amino
 carbohydrate (as in Compound C8 in Reaction Scheme 2), then this reaction
 may be run at 70-75.degree. C. for 6 hours before isolating the final
 product.
 Conversely, an alternate procedure may be used to selectively generate the
 mono-substituted compound (such as Compound C5 in Reaction Scheme 1) when
 using a dichlorotriazinyl substituted dye (such as Compound C1 in Reaction
 Scheme 1) as the starting material. Into the reaction vessel, suspend the
 dichlorotriazinyl compound, 1 molar equivalent of the amino carbohydrate
 (an excess may be used with this process since only one equivalent will be
 placed on the triazo ring), and 1 molar equivalent of NaHCO.sub.3 (sodium
 bicarbonate) in acetonitrile (CH.sub.3 CN). Add to the reaction mixture a
 catalytic amount of DTAB (dodecyltrimethylammonium bromide). Allow the
 reaction to reflux for about 1 week, at which time the product may be
 isolated by removing the solvent and purifying the product through column
 chromatography using silica gel and acetonitrile/water as the eluent.
 Reaction (c): Dissolve the monochlorotriazinyl compound (such as Compound
 C1, C8 and C10 in Reaction Schemes 1 or 3, 2 and 4, respectively) in water
 along with the reactive material (such as Compound C6, C4, C2 in Reaction
 Schemes 1 or 3, 2, and 4, respectively). Dissolve two molar equivalents of
 NaHCO.sub.3 (sodium bicarbonate) in the reaction solution. Raise the
 temperature to about 70-75.degree. C. and maintain this temperature for
 about 6 hours. Isolate the final product (Formula IV) through
 precipitation methods and rinsing with hexanes and drying.
 Reaction (d): Dissolve the amino carbohydrate (such as Compound C4 in
 Reaction Scheme 3) in water at neutral pH (pH.about.7). Add to an ice cold
 suspension of cyanuric chloride (ice bath made up from 1:1 acetone:ice
 water) at a molar ratio of 1:1. Stir the reaction mixture for 2 hours
 before proceeding to the next step of the synthesis.
 EXAMPLE #4
 Synthesis of Acid Red SA-1
 ##STR11##
 5.01 g. of Reactive Red 2 (available from Aldrich Chemical Co.--also named
 Procion Red MX-3B) is placed in a 300 mL round bottom flask along with
 1.75 g. of D-glucosamine hydrochloride (slight excess), 1.40 g. of sodium
 bicarbonate (to neutralize two equivalents of HCl) and 0.20 g. of
 dodecyltrimethylammonium bromide (to act as a catalyst for the reaction).
 Approximately 150 mL of acetonitrile is added to this mixture. The new
 mixture is refluxed for about one week (with periodic TLC (thin layer
 chromatography) checks to assess the progress of the reaction) until the
 reaction has proceeded to completion. The acetonitrile is removed under
 reduced pressure and the resulting dye is purified via column
 chromatography and verified by LC/MS.
 EXAMPLE #5
 Synthesis of Acid Red SA-3
 ##STR12##
 5.0 g. of D-glucosamine hydrochloride is dissolved in approximately 150 mL
 of water and neutralized to pH 7 using 1.0 M NaOH (sodium hydroxide) in a
 300 mL round bottom flask. To this mixture is added a 50 mL solution
 containing 7.0 g. of Reactive Red 2 and 2.0 g. of sodium bicarbonate (to
 neutralize 2 equivalents of HCl) dissolved in water. The reaction vessel
 is fitted with a thermometer and the reaction is heated to about
 75-80.degree. C. for a period of 6 hours before cooling the reaction to
 room temperature. The dye is then concentrated under reduced pressure and
 then purified on a silica gel column.
 EXAMPLE #6
 Synthesis of Acid Blue SA-1
 ##STR13##

EXAMPLES
 Example I
 The following data represents the improvement that can be obtained with
 dyes of this invention in terms of waterfastness and smearfastness.
 Several different types of immobilizing fluids are used with these dyes,
 and improvements with various types of immobilizing fluids are observed
 with these of dyes.
 The recorded values as shown below are for the derivatized dyes AB SA-1, AB
 SA-2, AR SA-1, AR SA-2, AY SA-1, AR TS-1a, AR TS-1b, AR TS-2+ and AR
 TS-3+. These values are compared to the parent dyes (reactive blue 2,
 reactive blue 4, reactive red 2, S66895 (available from Avecia), acid
 yellow 127, S174216, S173946, S176831 and S 175567 (all available from
 Avecia), respectively).
 TABLE 1
 Underprinting/Overprinting Effects with Derivatized Dyes.
 Waterfastness Smearfastness
 Dye Parent Dye (% Improvement) (% Improvement)
 AB SA-1 Reactive Blue 2 24 8.6
 AB SA-2 Reactive Blue 4 13 6.4
 AR SA-1 Reactive Red 2 10 7.0
 AR SA-2 S66895 8 3.0
 AY SA-1 Acid Yellow 127 7 n/a
 AR TS-1a S174216 6 3.2
 AR TS-1b S173946 4 8.7
 AR TS-2+ S176831 8 4.6
 AR TS-3+ S175567 15 21.2
 The values obtained in this data is the average taken of several readings
 using `fixative` agents which include: cationic polymers (acidified PEI),
 cationic surfactants (dodecyltrimethylammonium chloride and Unamine O),
 inorganic salts (Ca.sup.2+ and Mg.sup.2+) as well as an organic acid
 (succinic acid). The underprinting/overprinting reactant fluids are made
 as described earlier in this invention and consist of the following:
 humectant (0-40 wt %, preferably 5-30 wt %, more preferably 5-20 wt %),
 surfactant (0-20 wt %, preferably 0.5-10 wt %, more preferably 0.5-5 wt
 %); fixative agent (either Ca.sup.2+, Mg.sup.2+ of 0-20 wt %, preferably
 5-15 wt %, more preferably 5-10 wt %; cationic polymer (PEI at pH 3-5,
 preferably pH=4), 0-20 wt %, preferably 1-10 wt %, more preferably 1-5 wt
 %; cationic surfactant of 0-20 wt %, preferably 1-10 wt %, more preferably
 1-5 wt %; and/or organic acid of 0-40 wt %, preferably 1-20 wt % more
 preferably 1-10 wt %); anti-cockle/anti-curl reagents (0-40 wt %,
 preferably 5-30 wt %, more preferably 5-20 wt %); a biocide of 0-5 wt %,
 preferably 0.1-2 wt %, and more preferably 0.1-0.5 wt %; and a tracer dye
 that can be tracked by either IR or UV and has no absorption in the
 visible spectrum (0-10 wt %, preferably 0-5%, more preferably 0.01-1 wt
 %).
 The ink vehicle, because it contains the carbohydrate substituted dyes, may
 be simplified from `normal` ink-jet vehicles in that it does not need to
 contain a humectant to keep the nozzle from clogging due to evaporation of
 the ink vehicle (primarily water). This is because of the strong hydrogen
 bonding promoted by the dye itself, with it being in sufficient quantities
 to prevent the excessive evaporation of water during the lifetime of the
 pen. Additionally, lower level of surfactants are needed to initiate paper
 penetration by the dye since the carbohydrate moiety on the dye also acts
 as a surfactant with increased wetting ability. However, this does not
 preclude the addition of surfactants to help maximize the efficiency of
 this operation.
 Example II
 The following are examples of reaction fluids or 5.sup.th pen fluids for
 use in inkjet printing.