CA2060598C - Bleed alleviation in ink-jet inks - Google Patents
Bleed alleviation in ink-jet inks Download PDFInfo
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- CA2060598C CA2060598C CA002060598A CA2060598A CA2060598C CA 2060598 C CA2060598 C CA 2060598C CA 002060598 A CA002060598 A CA 002060598A CA 2060598 A CA2060598 A CA 2060598A CA 2060598 C CA2060598 C CA 2060598C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
Abstract
Color bleed (the invasion of one color into another on the surface of the print medium) using ink-jet inks is al-leviated by employing zwitterionic surfactants (ph-sensi-tive or pH-insensitive) or ionic or non-ionic amphiphiles.
The inks of the invention comprise a vehicle and a dye.
The vehicle typically comprises a low viscosity, high boil-ing point solvent, one or two amphiphiles at concentrations above their critical micelle concentration (cmc), while the dye typically comprises any of the dyes commonly employed in ink-jet printing. The amount of surfactant/amphiphile is described in terms of its critical micelle concentration (cmc), which is a unique value for each amphiphile. Above the cmc, micelles form, which attract the dye molecule and thus control the color bleed. Below the cmc, there is no micelle formation, and thus no control of the color bleed.
The inks of the invention comprise a vehicle and a dye.
The vehicle typically comprises a low viscosity, high boil-ing point solvent, one or two amphiphiles at concentrations above their critical micelle concentration (cmc), while the dye typically comprises any of the dyes commonly employed in ink-jet printing. The amount of surfactant/amphiphile is described in terms of its critical micelle concentration (cmc), which is a unique value for each amphiphile. Above the cmc, micelles form, which attract the dye molecule and thus control the color bleed. Below the cmc, there is no micelle formation, and thus no control of the color bleed.
Description
2~~a~9~
PATENT
BLEED ALLEVIATION IN INK-JET INKS
TECHNICAL FIELD
The present invention relates to inks employed in ink-jet printing, especially in thermal ink-jet printing, and, more particularly, to colored ink compositions in which color bleed is substantially reduced or even eliminated.
BACKGROUND ART
Heavy dye loads on bond paper of various colored inks can lead to bleed and reduction of waterfastness. Bleed, as used herein, is the invasion of one color into another color on paper, which is a surface phenomenon. This is in contradistinction to uses of the term in the prior art, which tend to define "bleed" in the context of ink of a single color following the fibers of the paper; this is a sub-surface phenomenon.
Surfactants have been used as anti-clogging agents in Japanese Laid-Open Patent Application No. 63-165465 for use in ink-jet recording inks. The surfactants used in that application are limited to those having a surface tension between 20 and 50 dyne/cm. The amount of surfactant ranges from about 0.5 to 25 wt%. Specific examples disclosed in-clude sodium dodecyl benzene sulfonate, sodium laurate, and polyethylene glycol monooleyl ether.
Japanese Laid-Open Patent Application No. 01-203,483 is directed to ink-jet recording compositions. Bleed re duction is mentioned in connection with printing using the Case 189534 inks. However, the compositions require pectin (0.01 to 2 wt%), which is probably being used as a thickener. Howev er, pectin is not useful in inks used in thermal ink-jet printers, due to its thermal instability (it gels at higher temperatures).
Japanese Patent JO 1215-875-A is directed to inks suitable for ink-jet printing, evidencing good recording with fast drying without bleeding. The compositions ahl require triglycerides. Such compounds, however, are not stable to extended shelf life necessary for commercial inks.
Japanese Patent JO 1230-685-A is directed to inks suitable for ink-jet printing, evidencing quick absorption on the surface of conventional office paper without smear or blotting. The compositions comprise colorants and liq-uid solvents and/or dispersants and are characterized by the presence of a copolymer of ethylene oxide and propylene oxide of the formula HO ( C,H,O ) ,-C,H60 ( C,H,O ) bFI, where a+b is up to 50 and b is optionally 0. These copolymers are re-ferred to as "PLURONICS".~ For the most part, they have not been found to stop bleed.
Thermal ink-jet printers offer a low cost, high quali-ty, and comparatively noise-free option to other types of printers commonly used with computers. Such printers em-ploy a resistor element in a chamber provided with an egress for ink to enter from a plenum. The plenum is con-nected to a reservoir for storing the ink. A plurality of such resistor elements are arranged in a particular pat-tern, called a primitive, in a printhead. Each resistor element is associated with a nozzle in a nozzle plate, through which ink is expelled toward a print medium. The entire assembly of printhead and reservoir comprise an ink-jet pen.
In operation, each resistor element is connected via a conductive trace to microprocessor, where current-carry-* Trade-mark ~~~0~~~
PATENT
BLEED ALLEVIATION IN INK-JET INKS
TECHNICAL FIELD
The present invention relates to inks employed in ink-jet printing, especially in thermal ink-jet printing, and, more particularly, to colored ink compositions in which color bleed is substantially reduced or even eliminated.
BACKGROUND ART
Heavy dye loads on bond paper of various colored inks can lead to bleed and reduction of waterfastness. Bleed, as used herein, is the invasion of one color into another color on paper, which is a surface phenomenon. This is in contradistinction to uses of the term in the prior art, which tend to define "bleed" in the context of ink of a single color following the fibers of the paper; this is a sub-surface phenomenon.
Surfactants have been used as anti-clogging agents in Japanese Laid-Open Patent Application No. 63-165465 for use in ink-jet recording inks. The surfactants used in that application are limited to those having a surface tension between 20 and 50 dyne/cm. The amount of surfactant ranges from about 0.5 to 25 wt%. Specific examples disclosed in-clude sodium dodecyl benzene sulfonate, sodium laurate, and polyethylene glycol monooleyl ether.
Japanese Laid-Open Patent Application No. 01-203,483 is directed to ink-jet recording compositions. Bleed re duction is mentioned in connection with printing using the Case 189534 inks. However, the compositions require pectin (0.01 to 2 wt%), which is probably being used as a thickener. Howev er, pectin is not useful in inks used in thermal ink-jet printers, due to its thermal instability (it gels at higher temperatures).
Japanese Patent JO 1215-875-A is directed to inks suitable for ink-jet printing, evidencing good recording with fast drying without bleeding. The compositions ahl require triglycerides. Such compounds, however, are not stable to extended shelf life necessary for commercial inks.
Japanese Patent JO 1230-685-A is directed to inks suitable for ink-jet printing, evidencing quick absorption on the surface of conventional office paper without smear or blotting. The compositions comprise colorants and liq-uid solvents and/or dispersants and are characterized by the presence of a copolymer of ethylene oxide and propylene oxide of the formula HO ( C,H,O ) ,-C,H60 ( C,H,O ) bFI, where a+b is up to 50 and b is optionally 0. These copolymers are re-ferred to as "PLURONICS".~ For the most part, they have not been found to stop bleed.
Thermal ink-jet printers offer a low cost, high quali-ty, and comparatively noise-free option to other types of printers commonly used with computers. Such printers em-ploy a resistor element in a chamber provided with an egress for ink to enter from a plenum. The plenum is con-nected to a reservoir for storing the ink. A plurality of such resistor elements are arranged in a particular pat-tern, called a primitive, in a printhead. Each resistor element is associated with a nozzle in a nozzle plate, through which ink is expelled toward a print medium. The entire assembly of printhead and reservoir comprise an ink-jet pen.
In operation, each resistor element is connected via a conductive trace to microprocessor, where current-carry-* Trade-mark ~~~0~~~
ing signals cause one or more selected elements to heat up.
The heating creates a bubble of ink in the chamber, which is expelled through the nozzle toward the print medium. In this way, firing of a plurality of such resistor elements in a particular order in a given primitive forms alphanu-meric characters, performs area-fill, and provides other print capabilities on the medium.
Many inks that are described for use in ink-jet print ing are usually associated with non-thermal ink-jet print ing. An example of such non-thermal ink-jet printing is piezoelectric ink-jet printing, which employs a piezoelec-tric element to expel droplets of ink to the medium. Inks suitably employed in such non-thermal applications often cannot be used in thermal ink-jet printing, due to the ef-fect of heating on the ink composition.
A need remains for ink compositions for use in ink-jet printing, particularly thermal ink-jet printing, which do not evidence bleed, as defined herein, and yet which pos sess relatively long shelf life and other desirable proper ties of such inks.
DTSCLOSURE OF INVENTION
In accordance with the invention, color bleed on paper media printed by ink-jet is alleviated by employing non-ionic, pH-sensitive or insensitive zwitterionic (amphoter-ic) surfactants, or ionic surfactants (amphiphiles or de-tergents). The ink comprises (a) 0 to about 20 wt% of one or more low vapor pressure solvents (b) one or more water-soluble dyes, ( c ) one or more self-aggregating or preformed micellar, vesicular-like components (particular examples and concentrations to be specified below), and (d) a filler such as water and a biocide, fungicide, and/or slimicide.
As used herein, the term "low vapor pressure solvent" re-fers to a solvent having a vapor pressure that is lower Case 189534 than that of water and the term "water-soluble dye" refers to a dye whose solubility in water exceeds 2 wt%.
Low vapor pressure solvents can include, but are not restricted to, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and de-rivatives thereof; diols such as butanediol, pentanediol, hexanediol, and homologous diols; glycol esters such as propylene glycol laurate; mono and di glycol ethers such as l0 cellusolves, including ethylene glycol monobutyl ether, di-ethylene glycol ethers such as the carbitols, diethylene glycol mono ethyl, butyl, hexyl ethers, propylene glycol ether, dipropylene glycol ether, and triethylene glycol ether; long chain alcohols such as butyl alcohol, pentyl alcohol, and homologous alcohols: and other solvents such as sulfolane, esters, ketones, lactones such as y-butyro-lactone, lactams such as N-pyrrolidone and N-(2-hydroxyeth-yl)pyrrolidone, and glycerols and their derivatives.
Microbial reagents include, but are not limited to, NUOSEPT*(Nudex, Inc., a division of Huls Americal, UCARCIDE*
(Union Carbide), VANCIDE*(RT Vanderbilt Co.), and PROXEL*
(ICI Americas).
Dyes include, but are not limited to, anionic water soluble types such as C.I. Acid Blue 9 042090), C.I. Acid Red 18 (#18), C.I. Acid Red 27 016185), C.I. Acid Red 52 (#45100), C.I. Acid Yellow 23 019140), C.I. Direct Blue 199 ( #74190 ) , C. I . Direct Yellow 029325 ) and their monova lent alkali earth ions such as Na+, Li', Cs+, NH,+, and sub stituted ammonium salts. The dyes) is present from about 0.1 to 10 wt% of the ink.
It is important to note that some ingredients have du-al functions. For example, n-butyl carbitol can function as a low vapor pressure solvent and as a self-aggregating component. Further discussion concerning the critical role of aggregation and concentration of surfactants in allevi-* Trade-marks sting bleed is provided below. It is sufficient to state here that critical concentrations of surfactant are necessary to efficiently and completely prevent bleed in 5 double dot mode printing used to generate the print samples herein.
Other aspects of this invention are as follows:
A process for reducing color bleed in inks employed in thermal ink-jet printing, comprising printing on a l0 medium with an ink having the following composition:
(a) a vehicle; and (b) about 0.1 to 10 wt% of at least one water-soluble dye dissolved therein, wherein said vehicle comprises (1) at least one member selected from the group consisting of zwitterionic surfactants and non-ionic amphiphiles, present in an amount that is at least equal to its critical micelle concentration; (2) 0 to about 20 wt% of at least one organic solvent which supports the micelle formation of said at least one member; and (3) the balance water.
A process for reducing color bleed in inks employed in thermal ink-jet printing, comprising printing on a medium with an ink having the following composition:
(a) a vehicle; and (b) 0.1 to about 10 wt% of at least one water-soluble dye dissolved therein, wherein said vehicle comprises (1) at least one member selected from the group consisting of N,N-dimethyl-N-dodecyl amine oxide, N,N-dimethyl-N-hexadecyl 3o amine oxide, N,N-dimethyl-N-octadecyl amine oxide, N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide, present in an amount that is at least equal to its critical micelle concentration; (2) 0 to about 20 wt% of at least one organic solvent selected from the group consisting of pentanediol, pentanol, and butanol; and (3) the balance water.
. .. ~oso5go 5a BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows bleed reference patterns where higher bleed indices reflect unacceptable bleed (a bleed score of s2.5 is considered to be acceptable for high quality text output);
FIG. 2, on coordinates of text print quality (left abscissa) or bleed (right abscissa) and surfactant concentration, shows the qualitative effect on print quality and bleed as a function of concentration of a surfactant; and FIGS. 3a-b, on coordinates of dye concentration and total detergent (surfactant) concentration ([D]T), are plots of dye adsorption to micelles, with FIG. 3a showing the effect of weak absorption of dye to micelle and with FIG. 3b showing the effect of strong adsorption of dye to micelle, where [D]m is the detergent (surfactant) concentration in micelles and [D]W is the detergent (surfactant) concentration in water.
BEST MODES FOR CARRYING OUT THE INVENTION
In the practice of the invention, color bleed resulting from the use of ink-jet inks in thermal ink-jet printers is alleviated by employing either zwitterionic surfactants or non-ionic amphiphiles. The zwitterionic surfactants employed in the practice of the invention may be pH-sensitive or pH-insensitive.
All concentrations herein are in weight percent, unless otherwise indicated. The purity of all components is that employed in normal commercial practice for thermal ink-jet inks.
For convenience, examples of bleed alleviating surfac tants are divided into two categories: (1) non-ionic and amphoteric and (2) ionic. The former class is further sub divided into three classes: (a) water-soluble amphiphile mimetics, such as STARBURST~dendrimers, which are branched polyethylene amines available from Polysciences, Inc., and the like, (b) polyethers, such as ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol n-hexyl ether, triethylene glycol n-butyl ether, propylene glycol isobutyl ether, the TRITONS, which are nonyl phenyl polyethylene oxide surfactants available from Rohm & Haas Co., the PLURONICS~~and PLURAFACS, which are polyethylene oxide and polypropylene oxide block copolymers available from BASF, and the SURFYNOLS; which are acetylenic polyeth-ylene oxide surfactants available from Air Products & Chem-icals, Inc., and (c) amphoteric molecules, such as NDAO, NTAO, NHAO, OOAO, NOAO, and SH3-16; further information re-lating to these compounds is presented below. The ionic class, which comprises both cationic arid anionic surfac-tants, also is represented by bile salts (sodium, lithium, ammonium, or substituted-ammonium cholate) and water-solu-ble dyes.
An example of a pH-sensitive zwitterionic surfactant is N,N-dimethyl-N-dodecyl amine oxide (NDAO), which has a pka in water of about 2.3:
CH, CH, /
CizHzs-N+-CH ø CizHzs'N+-C- + H+
CH, CH3 * Trade-marks ~05i~~98~
The heating creates a bubble of ink in the chamber, which is expelled through the nozzle toward the print medium. In this way, firing of a plurality of such resistor elements in a particular order in a given primitive forms alphanu-meric characters, performs area-fill, and provides other print capabilities on the medium.
Many inks that are described for use in ink-jet print ing are usually associated with non-thermal ink-jet print ing. An example of such non-thermal ink-jet printing is piezoelectric ink-jet printing, which employs a piezoelec-tric element to expel droplets of ink to the medium. Inks suitably employed in such non-thermal applications often cannot be used in thermal ink-jet printing, due to the ef-fect of heating on the ink composition.
A need remains for ink compositions for use in ink-jet printing, particularly thermal ink-jet printing, which do not evidence bleed, as defined herein, and yet which pos sess relatively long shelf life and other desirable proper ties of such inks.
DTSCLOSURE OF INVENTION
In accordance with the invention, color bleed on paper media printed by ink-jet is alleviated by employing non-ionic, pH-sensitive or insensitive zwitterionic (amphoter-ic) surfactants, or ionic surfactants (amphiphiles or de-tergents). The ink comprises (a) 0 to about 20 wt% of one or more low vapor pressure solvents (b) one or more water-soluble dyes, ( c ) one or more self-aggregating or preformed micellar, vesicular-like components (particular examples and concentrations to be specified below), and (d) a filler such as water and a biocide, fungicide, and/or slimicide.
As used herein, the term "low vapor pressure solvent" re-fers to a solvent having a vapor pressure that is lower Case 189534 than that of water and the term "water-soluble dye" refers to a dye whose solubility in water exceeds 2 wt%.
Low vapor pressure solvents can include, but are not restricted to, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and de-rivatives thereof; diols such as butanediol, pentanediol, hexanediol, and homologous diols; glycol esters such as propylene glycol laurate; mono and di glycol ethers such as l0 cellusolves, including ethylene glycol monobutyl ether, di-ethylene glycol ethers such as the carbitols, diethylene glycol mono ethyl, butyl, hexyl ethers, propylene glycol ether, dipropylene glycol ether, and triethylene glycol ether; long chain alcohols such as butyl alcohol, pentyl alcohol, and homologous alcohols: and other solvents such as sulfolane, esters, ketones, lactones such as y-butyro-lactone, lactams such as N-pyrrolidone and N-(2-hydroxyeth-yl)pyrrolidone, and glycerols and their derivatives.
Microbial reagents include, but are not limited to, NUOSEPT*(Nudex, Inc., a division of Huls Americal, UCARCIDE*
(Union Carbide), VANCIDE*(RT Vanderbilt Co.), and PROXEL*
(ICI Americas).
Dyes include, but are not limited to, anionic water soluble types such as C.I. Acid Blue 9 042090), C.I. Acid Red 18 (#18), C.I. Acid Red 27 016185), C.I. Acid Red 52 (#45100), C.I. Acid Yellow 23 019140), C.I. Direct Blue 199 ( #74190 ) , C. I . Direct Yellow 029325 ) and their monova lent alkali earth ions such as Na+, Li', Cs+, NH,+, and sub stituted ammonium salts. The dyes) is present from about 0.1 to 10 wt% of the ink.
It is important to note that some ingredients have du-al functions. For example, n-butyl carbitol can function as a low vapor pressure solvent and as a self-aggregating component. Further discussion concerning the critical role of aggregation and concentration of surfactants in allevi-* Trade-marks sting bleed is provided below. It is sufficient to state here that critical concentrations of surfactant are necessary to efficiently and completely prevent bleed in 5 double dot mode printing used to generate the print samples herein.
Other aspects of this invention are as follows:
A process for reducing color bleed in inks employed in thermal ink-jet printing, comprising printing on a l0 medium with an ink having the following composition:
(a) a vehicle; and (b) about 0.1 to 10 wt% of at least one water-soluble dye dissolved therein, wherein said vehicle comprises (1) at least one member selected from the group consisting of zwitterionic surfactants and non-ionic amphiphiles, present in an amount that is at least equal to its critical micelle concentration; (2) 0 to about 20 wt% of at least one organic solvent which supports the micelle formation of said at least one member; and (3) the balance water.
A process for reducing color bleed in inks employed in thermal ink-jet printing, comprising printing on a medium with an ink having the following composition:
(a) a vehicle; and (b) 0.1 to about 10 wt% of at least one water-soluble dye dissolved therein, wherein said vehicle comprises (1) at least one member selected from the group consisting of N,N-dimethyl-N-dodecyl amine oxide, N,N-dimethyl-N-hexadecyl 3o amine oxide, N,N-dimethyl-N-octadecyl amine oxide, N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide, present in an amount that is at least equal to its critical micelle concentration; (2) 0 to about 20 wt% of at least one organic solvent selected from the group consisting of pentanediol, pentanol, and butanol; and (3) the balance water.
. .. ~oso5go 5a BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows bleed reference patterns where higher bleed indices reflect unacceptable bleed (a bleed score of s2.5 is considered to be acceptable for high quality text output);
FIG. 2, on coordinates of text print quality (left abscissa) or bleed (right abscissa) and surfactant concentration, shows the qualitative effect on print quality and bleed as a function of concentration of a surfactant; and FIGS. 3a-b, on coordinates of dye concentration and total detergent (surfactant) concentration ([D]T), are plots of dye adsorption to micelles, with FIG. 3a showing the effect of weak absorption of dye to micelle and with FIG. 3b showing the effect of strong adsorption of dye to micelle, where [D]m is the detergent (surfactant) concentration in micelles and [D]W is the detergent (surfactant) concentration in water.
BEST MODES FOR CARRYING OUT THE INVENTION
In the practice of the invention, color bleed resulting from the use of ink-jet inks in thermal ink-jet printers is alleviated by employing either zwitterionic surfactants or non-ionic amphiphiles. The zwitterionic surfactants employed in the practice of the invention may be pH-sensitive or pH-insensitive.
All concentrations herein are in weight percent, unless otherwise indicated. The purity of all components is that employed in normal commercial practice for thermal ink-jet inks.
For convenience, examples of bleed alleviating surfac tants are divided into two categories: (1) non-ionic and amphoteric and (2) ionic. The former class is further sub divided into three classes: (a) water-soluble amphiphile mimetics, such as STARBURST~dendrimers, which are branched polyethylene amines available from Polysciences, Inc., and the like, (b) polyethers, such as ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol n-hexyl ether, triethylene glycol n-butyl ether, propylene glycol isobutyl ether, the TRITONS, which are nonyl phenyl polyethylene oxide surfactants available from Rohm & Haas Co., the PLURONICS~~and PLURAFACS, which are polyethylene oxide and polypropylene oxide block copolymers available from BASF, and the SURFYNOLS; which are acetylenic polyeth-ylene oxide surfactants available from Air Products & Chem-icals, Inc., and (c) amphoteric molecules, such as NDAO, NTAO, NHAO, OOAO, NOAO, and SH3-16; further information re-lating to these compounds is presented below. The ionic class, which comprises both cationic arid anionic surfac-tants, also is represented by bile salts (sodium, lithium, ammonium, or substituted-ammonium cholate) and water-solu-ble dyes.
An example of a pH-sensitive zwitterionic surfactant is N,N-dimethyl-N-dodecyl amine oxide (NDAO), which has a pka in water of about 2.3:
CH, CH, /
CizHzs-N+-CH ø CizHzs'N+-C- + H+
CH, CH3 * Trade-marks ~05i~~98~
This compound has a molecular weight of 229, and a critical micelle concentration (cmc: to be discussed in greater de-tail below) of 13 mM.
Also, in place of the Ci2H25 moiety, any R moiety may be used. The following moieties, their name, abbreviation, molecular weight (mw), and cmc are useful in the practice of the invention N,N-dimethyl-N-tetradecyl amine oxide (NTAO);
mw = 257; cmc = 6-8 mM:
N,N-dimethyl-N-hexadecyl amine oxide (NHAO);
mw = 285: cmc = 0.8 mM;
N,N-dimethyl-N-octadecyl amine oxide (NOAO);
mw = 313; cmc = small;
N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide (OOAO): mw = 311: cmc = small.
Another example is N-dodecyl-N,N-dimethyl glycine, which has a pka of about 5 in water:
CH, CH, C12ia25 N+-CHz-COOH ~ C12HZ5-N/ CHZCOO' + H+
2 5 CH, CH, Yet other examples include phosphates, phosphites, phosphonates, lecithins or the like, and phosphate esters such as phosgomyelin which has a pk, of about 2 to 3 in water:
o O
3 5 R- ( O ) - IP-OCHZ CH2 N/ ~ R- ( O ) -P-OCH2-CHz N/ + H' OH
Case 189534 Other similar compounds include phosphoglycerides, such as phosphatidylethanolamines,phosphatidylcholines,phosphati-dyl serines, phosphatidylinositols, and H'-O-lysylphospha-tidylglycerols.
Additional examples of compounds that are useful in the practice of the invention include the sulfobetaines, which are zwitterionic, but pH-insensitive:
CH, /
CH,- ( CHI ) "-N'- ( CHz ),-SO;
CH, Where n=11, the compound is denoted S83-12 : where n=15 , the compound is denoted SB3-16.
Examples of ionic surfactants that are suitably em ployed in the practice of the invention include such cat ionic compounds as CHs /
CH,- ( CH= ) "-N'-CH, Br \
CH, cetyl trimethylammonium bromide (CTABr), and such anionic surfactants as CH3- ( CHZ ) ll-O-SO,- Na' sodium dodecyl sulfate (SDS) CH3- ( CHz .) r-SO,' Na' sodium sulfonates Examples of non-ionic, non-amphoteric surfactants use-ful in the practice of the invention include compounds available under the tradenames TERGITOL, which are alkyl polyethylene oxides available from Union Carbide, and BRIJ;
* Trade-marks ~o~o~~~
Also, in place of the Ci2H25 moiety, any R moiety may be used. The following moieties, their name, abbreviation, molecular weight (mw), and cmc are useful in the practice of the invention N,N-dimethyl-N-tetradecyl amine oxide (NTAO);
mw = 257; cmc = 6-8 mM:
N,N-dimethyl-N-hexadecyl amine oxide (NHAO);
mw = 285: cmc = 0.8 mM;
N,N-dimethyl-N-octadecyl amine oxide (NOAO);
mw = 313; cmc = small;
N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide (OOAO): mw = 311: cmc = small.
Another example is N-dodecyl-N,N-dimethyl glycine, which has a pka of about 5 in water:
CH, CH, C12ia25 N+-CHz-COOH ~ C12HZ5-N/ CHZCOO' + H+
2 5 CH, CH, Yet other examples include phosphates, phosphites, phosphonates, lecithins or the like, and phosphate esters such as phosgomyelin which has a pk, of about 2 to 3 in water:
o O
3 5 R- ( O ) - IP-OCHZ CH2 N/ ~ R- ( O ) -P-OCH2-CHz N/ + H' OH
Case 189534 Other similar compounds include phosphoglycerides, such as phosphatidylethanolamines,phosphatidylcholines,phosphati-dyl serines, phosphatidylinositols, and H'-O-lysylphospha-tidylglycerols.
Additional examples of compounds that are useful in the practice of the invention include the sulfobetaines, which are zwitterionic, but pH-insensitive:
CH, /
CH,- ( CHI ) "-N'- ( CHz ),-SO;
CH, Where n=11, the compound is denoted S83-12 : where n=15 , the compound is denoted SB3-16.
Examples of ionic surfactants that are suitably em ployed in the practice of the invention include such cat ionic compounds as CHs /
CH,- ( CH= ) "-N'-CH, Br \
CH, cetyl trimethylammonium bromide (CTABr), and such anionic surfactants as CH3- ( CHZ ) ll-O-SO,- Na' sodium dodecyl sulfate (SDS) CH3- ( CHz .) r-SO,' Na' sodium sulfonates Examples of non-ionic, non-amphoteric surfactants use-ful in the practice of the invention include compounds available under the tradenames TERGITOL, which are alkyl polyethylene oxides available from Union Carbide, and BRIJ;
* Trade-marks ~o~o~~~
which are also alkyl polyethylene oxides available from ICI
Americas, having the formula:
CH,- ( CH2 ) "- ( -O-CH2-CH2- ) m-OH
(where n=3 and m=2, this is n-butyl carbitol, a cellu-solve).
Also included in this category are the PLURONICS and the PLURAFACS (BASF) having the general formula:
HO- ( -CHZ-CH2-O- ) n- ( -CHZ-CH ( CH, ) -O- ) m CHZ-CH2-OH
The TRITONS ( Rohm & Haas Co . ) are general ly represent-ed as:
R-Ph-O ( CH2-CHZ-O ) yR' where R, R' is any alkane, alkene, aryl or alkynyl group or H, Ph is phenyl, y=1 to 50, and R is para to the ether linkage on the benzene ring.
The SURFYNOLS (Air Products & Chemicals, Inc.) are represented as H H
H,C-C-CH, H,-C-CH3 H3C-C-C = C-C-CH, O O
CHZ CHZ
n m OH OH
Case 189534 2~~~~9~
where n+m=0 to 50.
Examples of Bleed Alleviating Amphiphiles Zwitterionic surfactants, such as NDAO, NTAO, OOAO, 5 and NOAO, were tried first. These surfactants (except for NOAO) are totally miscible in aqueous solutions (about 0.1 to 20 wt%) of diethylene glycol, glycerol, and ethylene and propylene glycol. NOAO is also miscible if up to about 10 wt% of a straight chain primary alcohol, such as n-propa 10 nol, n-butanol, n-pentanol, is added.
Four examples are included in Table I. NDAO concen-trations at 0, 0.5%, 1.0%, and 5% surfactant in water was the vehicle. The colors were simultaneously printed side by side using a dot-on-dot (double pass) algorithm. The dyes used were 1.33% C.I. Acid Red 27 (#16185) 1.65% C.I.
Acid Blue 9 (#42090); 1.33% C.I. Direct Yellow 86 (#29325).
Table 1 shows that without NDAO, massive proliferation of the colors occurs (bleed). NDAO at 0.5% radically alters the extent of bleed, but it is not eliminated. Table I
also shows the effect of increased NDAO concentrations of 1% and 5%, respectively, concentrations which substantially eliminate bleed. Vehicles which contained 0 to 20% of di-ethylene glycol, propylene glycol, or glycerol or 0 to 15%
1,5-pentanediol gave similar results with NDAO at approxi-mately the same concentrations (see Table III below, Ink #1). NOAO and OOAO required 0 to about 10% of a co-sol-vent, such as 1-propanol, 1-butanol, or 1-pentanol, for solubility purposes (see Table III below, Inks #6-11, 13-16, 25-27, 29, 30, 31, 33).
The color bleed index values listed in Table I are de-rived from the scale provided in FIG. 1, which is a print of lines of red (magenta) ink on a background of yellow ink. For high text quality output, a value of <_2.5 is con-sidered to be acceptable. For somewhat lower quality de-wands, such as printing on boxes, plotting, and the like, Case 189534 a value of about 3 to 4 may be considered to be acceptable.
Inks commonly used commercially presently values, typ-have ically, of about 6 or more.
____________________-_ Table 1. Bleed Indices for VariousSystems.
S_ysteml Wt%2 Index3 NDAO 0 6.0+
0.5 4.0 1.0 2.5 5.0 1.0 n-pentanol: 1-5-pentanediol 2.0; 6.0 6.0 n-pentanol: 1,5-pentanediol; NDEC' 2.0; 6.0; 2.0 2.0 CTABr 2.0 3.5 DEG; CTABr 6.0; 2.0 2.5 SDS 2.0 3.5 n-butanol; 1,4-butanediol; SB3-16 2.0; 5.0; 8.0 4.0 DEG; PLURONIC L-63 5.0; 5.0 2.5 1,5-pentanediol; SURFYNOL S465 10.0; 2.0 5.0 1,5-pentanediol; SURFYNOL S465 10.0; 4.0 2.0 TRITON CF-21 0.7 6.0+
1.0 3.0 3.0 2.0 DEG 5.5 6.0 n-butanol 7.0 5.0 Case 189534 24~~~~8 Notes: 1 Dyes include AR27, 1.33%: DY86-Na, 1.33%; AB9-Na, 1.65%.
2 wt%, balance is water.
Color Bleed Index: a value of <_2.5 is considered acceptable for high quality text output.
N,N-dimethyl-N-dodecyl-N-(ethyl carboxylate).
Also shown in Table I is an example in which the vehi-cle consisted of 2% n-pentanol and 6% 1,5-pentanediol or of 7% n-butanol. The use of such paper wetting and penetrat-ing solvents in the inks alone does not alleviate bleed.
Table I shows the effect of employing a (betaine) zwitterionic surfactant (NDEC) in conjunction with a vehi cle of 2% n-pentanol and 6% 1,5-pentanediol in stopping bleed. The addition of NDEC surfactant markedly reduces the extent of bleed, as compared to the vehicle without surfactant.
Not all zwitterionic surfactants are efficient at eliminating bleed. For example, a system comprising 2% n butanol, 5% 1,4-butanediol, and 8% SB3-16 is not efficient as the other examples in alleviating bleed. On the other hand, while bleed is still present, it is reduced compared to that in which the vehicle is 5.5% DEG, where no surfac tant was present.
Small amounts of cationic surfactants in ink also eliminate bleed. A degree of bleed control (3.5) is achieved using 2% cetyl trimethylammonium bromide (CTABr) in water. The addition of co-solvent to the vehicle, spe-cifically 6% diethylene glycol with CTABr present at 2%, provides even better bleed control (2.5) than afforded with CTABr alone.
Anionic surfactants in inks can control bleed as well.
For example, 2% sodium dodecylsulfate (SDS) in water as ve-Case 189534 2~6~~~8 hicle controls bleed. Although the color bleed index is 3.5, such an ink would be acceptable for, e.g., plotters.
Only one non-ionic surfactant of the PLURONIC class, L-63, has been found to prevent bleed when present in the ink (see Table I).
Table I shows the effect of increasing SURFYNOL 465 concentration on eliminating bleed: 2% SURFYNOL 465 is not effective, but, 4% SURFYNOL 465 controls bleed well in ink vehicles containing 10% 1,5-pentanediol solvent.
Increasing concentrations of TRITON CF-21 detergent shows similar effects (cf. Table I).
These results show that different classes of surfac-tants exhibit concentration dependence on efficient bleed alleviation. Concentration effects were observed in the case of non-ionic surfactants, such as n-butyl carbitol, n-butyl propasol, and n-hexyl carbitol (not shown).
It is interesting to note common structural features among these bleed alleviating surfactants. All have fea-tures common among surfactants: long hydrocarbon (hydro-phobic) tails with polar (hydrophilic) headgroups. Other such detergents of similar structures can be formulated in inks to solve bleed, provided they have structural features common to these. This does not imply that the bleed alle-viating behavior is indigenous to all detergents.
The detection of the cmc or the onset of micellization in an ink can be determined by a number of methods. Typi-cally, sharp changes are seen in plots of surface tension vs. surfactant concentration (in the ink) or osmotic pres-sure vs. surfactant concentration (in the ink). These sharp changes are attributed to the cmc. Other methods, such as conductivity, turbidity, determination of equiva-lent conductance are precluded in water-soluble inks.
Case 189534 2~~~~9~
Americas, having the formula:
CH,- ( CH2 ) "- ( -O-CH2-CH2- ) m-OH
(where n=3 and m=2, this is n-butyl carbitol, a cellu-solve).
Also included in this category are the PLURONICS and the PLURAFACS (BASF) having the general formula:
HO- ( -CHZ-CH2-O- ) n- ( -CHZ-CH ( CH, ) -O- ) m CHZ-CH2-OH
The TRITONS ( Rohm & Haas Co . ) are general ly represent-ed as:
R-Ph-O ( CH2-CHZ-O ) yR' where R, R' is any alkane, alkene, aryl or alkynyl group or H, Ph is phenyl, y=1 to 50, and R is para to the ether linkage on the benzene ring.
The SURFYNOLS (Air Products & Chemicals, Inc.) are represented as H H
H,C-C-CH, H,-C-CH3 H3C-C-C = C-C-CH, O O
CHZ CHZ
n m OH OH
Case 189534 2~~~~9~
where n+m=0 to 50.
Examples of Bleed Alleviating Amphiphiles Zwitterionic surfactants, such as NDAO, NTAO, OOAO, 5 and NOAO, were tried first. These surfactants (except for NOAO) are totally miscible in aqueous solutions (about 0.1 to 20 wt%) of diethylene glycol, glycerol, and ethylene and propylene glycol. NOAO is also miscible if up to about 10 wt% of a straight chain primary alcohol, such as n-propa 10 nol, n-butanol, n-pentanol, is added.
Four examples are included in Table I. NDAO concen-trations at 0, 0.5%, 1.0%, and 5% surfactant in water was the vehicle. The colors were simultaneously printed side by side using a dot-on-dot (double pass) algorithm. The dyes used were 1.33% C.I. Acid Red 27 (#16185) 1.65% C.I.
Acid Blue 9 (#42090); 1.33% C.I. Direct Yellow 86 (#29325).
Table 1 shows that without NDAO, massive proliferation of the colors occurs (bleed). NDAO at 0.5% radically alters the extent of bleed, but it is not eliminated. Table I
also shows the effect of increased NDAO concentrations of 1% and 5%, respectively, concentrations which substantially eliminate bleed. Vehicles which contained 0 to 20% of di-ethylene glycol, propylene glycol, or glycerol or 0 to 15%
1,5-pentanediol gave similar results with NDAO at approxi-mately the same concentrations (see Table III below, Ink #1). NOAO and OOAO required 0 to about 10% of a co-sol-vent, such as 1-propanol, 1-butanol, or 1-pentanol, for solubility purposes (see Table III below, Inks #6-11, 13-16, 25-27, 29, 30, 31, 33).
The color bleed index values listed in Table I are de-rived from the scale provided in FIG. 1, which is a print of lines of red (magenta) ink on a background of yellow ink. For high text quality output, a value of <_2.5 is con-sidered to be acceptable. For somewhat lower quality de-wands, such as printing on boxes, plotting, and the like, Case 189534 a value of about 3 to 4 may be considered to be acceptable.
Inks commonly used commercially presently values, typ-have ically, of about 6 or more.
____________________-_ Table 1. Bleed Indices for VariousSystems.
S_ysteml Wt%2 Index3 NDAO 0 6.0+
0.5 4.0 1.0 2.5 5.0 1.0 n-pentanol: 1-5-pentanediol 2.0; 6.0 6.0 n-pentanol: 1,5-pentanediol; NDEC' 2.0; 6.0; 2.0 2.0 CTABr 2.0 3.5 DEG; CTABr 6.0; 2.0 2.5 SDS 2.0 3.5 n-butanol; 1,4-butanediol; SB3-16 2.0; 5.0; 8.0 4.0 DEG; PLURONIC L-63 5.0; 5.0 2.5 1,5-pentanediol; SURFYNOL S465 10.0; 2.0 5.0 1,5-pentanediol; SURFYNOL S465 10.0; 4.0 2.0 TRITON CF-21 0.7 6.0+
1.0 3.0 3.0 2.0 DEG 5.5 6.0 n-butanol 7.0 5.0 Case 189534 24~~~~8 Notes: 1 Dyes include AR27, 1.33%: DY86-Na, 1.33%; AB9-Na, 1.65%.
2 wt%, balance is water.
Color Bleed Index: a value of <_2.5 is considered acceptable for high quality text output.
N,N-dimethyl-N-dodecyl-N-(ethyl carboxylate).
Also shown in Table I is an example in which the vehi-cle consisted of 2% n-pentanol and 6% 1,5-pentanediol or of 7% n-butanol. The use of such paper wetting and penetrat-ing solvents in the inks alone does not alleviate bleed.
Table I shows the effect of employing a (betaine) zwitterionic surfactant (NDEC) in conjunction with a vehi cle of 2% n-pentanol and 6% 1,5-pentanediol in stopping bleed. The addition of NDEC surfactant markedly reduces the extent of bleed, as compared to the vehicle without surfactant.
Not all zwitterionic surfactants are efficient at eliminating bleed. For example, a system comprising 2% n butanol, 5% 1,4-butanediol, and 8% SB3-16 is not efficient as the other examples in alleviating bleed. On the other hand, while bleed is still present, it is reduced compared to that in which the vehicle is 5.5% DEG, where no surfac tant was present.
Small amounts of cationic surfactants in ink also eliminate bleed. A degree of bleed control (3.5) is achieved using 2% cetyl trimethylammonium bromide (CTABr) in water. The addition of co-solvent to the vehicle, spe-cifically 6% diethylene glycol with CTABr present at 2%, provides even better bleed control (2.5) than afforded with CTABr alone.
Anionic surfactants in inks can control bleed as well.
For example, 2% sodium dodecylsulfate (SDS) in water as ve-Case 189534 2~6~~~8 hicle controls bleed. Although the color bleed index is 3.5, such an ink would be acceptable for, e.g., plotters.
Only one non-ionic surfactant of the PLURONIC class, L-63, has been found to prevent bleed when present in the ink (see Table I).
Table I shows the effect of increasing SURFYNOL 465 concentration on eliminating bleed: 2% SURFYNOL 465 is not effective, but, 4% SURFYNOL 465 controls bleed well in ink vehicles containing 10% 1,5-pentanediol solvent.
Increasing concentrations of TRITON CF-21 detergent shows similar effects (cf. Table I).
These results show that different classes of surfac-tants exhibit concentration dependence on efficient bleed alleviation. Concentration effects were observed in the case of non-ionic surfactants, such as n-butyl carbitol, n-butyl propasol, and n-hexyl carbitol (not shown).
It is interesting to note common structural features among these bleed alleviating surfactants. All have fea-tures common among surfactants: long hydrocarbon (hydro-phobic) tails with polar (hydrophilic) headgroups. Other such detergents of similar structures can be formulated in inks to solve bleed, provided they have structural features common to these. This does not imply that the bleed alle-viating behavior is indigenous to all detergents.
The detection of the cmc or the onset of micellization in an ink can be determined by a number of methods. Typi-cally, sharp changes are seen in plots of surface tension vs. surfactant concentration (in the ink) or osmotic pres-sure vs. surfactant concentration (in the ink). These sharp changes are attributed to the cmc. Other methods, such as conductivity, turbidity, determination of equiva-lent conductance are precluded in water-soluble inks.
Case 189534 2~~~~9~
Bleed Alleviation - Possible Mechanisms Reference to FIG. 2 gives a hypothetical concentration of surface-active reagent versus bleed and text print qual-ity scale profiles. Basically, this Figure profiles the bleed and text quality responses observed for all surfac-tants under investigation. FIG. 2 assumes that other com-ponents of the ink vehicle and dyes) concentrations are fixed and that the surfactant concentration is the depen-dent variable. From FIG. 2, upon addition of a small amount of surfactant, there is little change in the bleed control and sharpness of the text print quality. With fur-ther additions of surfactant, degradation of text print quality results with little or no improvement (perhaps even a slight degradation in bleed alleviation occurs in some cases) in bleed. A surfactant concentration is finally achieved where the quality of text begins to improve and bleed is reduced. Further decreases in bleed and improve-ment of text quality may occur with increasing surfactant concentration in the ink.
The lowest surfactant concentration where bleed alle-viation and improvement of text print quality becomes ap-preciably effective is found to be near the critical mi-celle concentration (cmc) or critical monomer concentration of most surfactants . ( The cmc is the concentration of sur-factant where simple electrolyte or non-electrolyte chemis-try lessens in importance to colloid chemistry. For the simple surfactants previously described, this is the con-centration of surfactant where micelles, or aggregated sur-factant molecules, begin to appear.) Micellization is driven by entropic constraints - the hydrocarbon chains are driven into the interior of the mi-celle with the hydrophilic, water-soluble groups driven to the exterior. The resulting domainal fluid provides re-gions of olef in-rich and water-rich pockets , which can com-partmentalize organic solutes such as dyes, co-surfactants, Case 189534 and co-solvent molecules, depending on their hydrophobici-ty. In addition, micelles interact and find regions in so-lution where their positional (potential) energy is mini-mized. It is conceivable that micelles containing charged dye molecules behave in a similar fashion.
Inspection of Table II shows that the cmcs listed here nicely coincide with the onset of bleed alleviation in Ta-ble I. The cmcs indicated are for pure water. The tabu-lated cmc will differ from those in the ink because added salts and hydrophobes perturb micelle structure.
Table II. CMC Data for Surfactant Print Samples Class Mole wt . jcmc ] 1 M cmcl, wt%
Surfactant Zwitterionic:
NDAO 229 0.013 0.3 Cl,Fi2,N ( CH3 ) 2 ( CHZ ) zC00-285 0.015 0.5 SB3-12 335 0.012 0.4 Ionic:
CTABr 364 0.0008 0.03 SDS 288 0.008 0.23 Non-ionic:
SURFYNOL 465 634 0.03-0.05 2-3 TRITON CF-21 489 0.001 0.05 N-42 389 ca 0.001 0.04 Butyl carbitol 192 0.2-0.3 4-6 Note: 1 cmc in pure water at 25°C.
Case 189534 Incorporation of dyes into micelles is the probable method by which surfactant-containing inks control bleed.
Micelles with dye of one color shot out of an ink-jet pen will not exchange dye of another color in an adjacent mi-celle on paper medium, because the rate at which the mobile medium evaporates or adsorbs into the paper is much faster than the desorption rate of the dye molecules from the mi-celles or the rate at which dye molecules diffuse through the micellar medium. Bleed alleviation results.
The efficiency of this bleed alleviation depends upon the level of adsorption of the dyes into the micelles, the number concentration of micelles in the ink, and the diffu-sion of dye and micelles on the paper surface. FIGS. 3a and 3b show hypothetically the extent of adsorption of dye into micelles as a function of surfactant concentration for dye molecules that strongly adsorb to micelles (FIG. 3b) and for dye molecules that weakly adsorb (FIG. 3a). It will be noted that in the weakly adsorbing dye, a much higher surfactant concentration is necessary to bind the same amount of dye than in the case of the strongly adsorb-ing dye. Obviously, the propensity for dye to adsorb to micelles is a function of the structure (hydrophobicity) and interactions of the dye molecule, the surfactant, co-solvent, and co-surfactant (if any) present.
Thus, surfactant concentration affects bleed control.
Higher concentrations of micelles absorb more dye molecules and slow their diffusion rate.
Additionally, certain pH-sensitive zwitterionic sur factants will pick up H' from the paper and change it from a zwitterionic surfactant to a cationic one.
CH3 CH, Ci2H2s-N'-C + H' ø CWzS-N+-CH
\ (paper) \
CH3 CH, zwitterionic cationic Case 189534 2~~~~9~
The lowest surfactant concentration where bleed alle-viation and improvement of text print quality becomes ap-preciably effective is found to be near the critical mi-celle concentration (cmc) or critical monomer concentration of most surfactants . ( The cmc is the concentration of sur-factant where simple electrolyte or non-electrolyte chemis-try lessens in importance to colloid chemistry. For the simple surfactants previously described, this is the con-centration of surfactant where micelles, or aggregated sur-factant molecules, begin to appear.) Micellization is driven by entropic constraints - the hydrocarbon chains are driven into the interior of the mi-celle with the hydrophilic, water-soluble groups driven to the exterior. The resulting domainal fluid provides re-gions of olef in-rich and water-rich pockets , which can com-partmentalize organic solutes such as dyes, co-surfactants, Case 189534 and co-solvent molecules, depending on their hydrophobici-ty. In addition, micelles interact and find regions in so-lution where their positional (potential) energy is mini-mized. It is conceivable that micelles containing charged dye molecules behave in a similar fashion.
Inspection of Table II shows that the cmcs listed here nicely coincide with the onset of bleed alleviation in Ta-ble I. The cmcs indicated are for pure water. The tabu-lated cmc will differ from those in the ink because added salts and hydrophobes perturb micelle structure.
Table II. CMC Data for Surfactant Print Samples Class Mole wt . jcmc ] 1 M cmcl, wt%
Surfactant Zwitterionic:
NDAO 229 0.013 0.3 Cl,Fi2,N ( CH3 ) 2 ( CHZ ) zC00-285 0.015 0.5 SB3-12 335 0.012 0.4 Ionic:
CTABr 364 0.0008 0.03 SDS 288 0.008 0.23 Non-ionic:
SURFYNOL 465 634 0.03-0.05 2-3 TRITON CF-21 489 0.001 0.05 N-42 389 ca 0.001 0.04 Butyl carbitol 192 0.2-0.3 4-6 Note: 1 cmc in pure water at 25°C.
Case 189534 Incorporation of dyes into micelles is the probable method by which surfactant-containing inks control bleed.
Micelles with dye of one color shot out of an ink-jet pen will not exchange dye of another color in an adjacent mi-celle on paper medium, because the rate at which the mobile medium evaporates or adsorbs into the paper is much faster than the desorption rate of the dye molecules from the mi-celles or the rate at which dye molecules diffuse through the micellar medium. Bleed alleviation results.
The efficiency of this bleed alleviation depends upon the level of adsorption of the dyes into the micelles, the number concentration of micelles in the ink, and the diffu-sion of dye and micelles on the paper surface. FIGS. 3a and 3b show hypothetically the extent of adsorption of dye into micelles as a function of surfactant concentration for dye molecules that strongly adsorb to micelles (FIG. 3b) and for dye molecules that weakly adsorb (FIG. 3a). It will be noted that in the weakly adsorbing dye, a much higher surfactant concentration is necessary to bind the same amount of dye than in the case of the strongly adsorb-ing dye. Obviously, the propensity for dye to adsorb to micelles is a function of the structure (hydrophobicity) and interactions of the dye molecule, the surfactant, co-solvent, and co-surfactant (if any) present.
Thus, surfactant concentration affects bleed control.
Higher concentrations of micelles absorb more dye molecules and slow their diffusion rate.
Additionally, certain pH-sensitive zwitterionic sur factants will pick up H' from the paper and change it from a zwitterionic surfactant to a cationic one.
CH3 CH, Ci2H2s-N'-C + H' ø CWzS-N+-CH
\ (paper) \
CH3 CH, zwitterionic cationic Case 189534 2~~~~9~
This occurs on the paper surface. Anionic dyes such as those mentioned above complex with this cationic surfac-tant on the paper surface to produce a water-insoluble complex of dye and surfactant, such as / /
R-N'-OH + Dye-° -~ Dye-° ( R-N+-OH ) n 1 insoluble \ \ complex Because these insoluble complexes do not diffuse, bleed control is achieved.
INDUSTRIAL APPLICABILITY
The ink compositions of the invention are expected to find use in thermal ink-jet inks, especially color inks, where bleed of one color into another is a concern. The ink compositions of the invention reduce or even eliminate such color bleed.
EXAMPLES
The following inks were prepared, as listed in Table III, below (the dyes and dye concentrations were as listed above and the balance was water):
Table III. Ink Compositions.
Ink # Ampl Amp2 NaChl Solventl Solvent2 1% 6%
1.5% 6%
1.5% 10%
Case 189534 ~Q~~~~~
R-N'-OH + Dye-° -~ Dye-° ( R-N+-OH ) n 1 insoluble \ \ complex Because these insoluble complexes do not diffuse, bleed control is achieved.
INDUSTRIAL APPLICABILITY
The ink compositions of the invention are expected to find use in thermal ink-jet inks, especially color inks, where bleed of one color into another is a concern. The ink compositions of the invention reduce or even eliminate such color bleed.
EXAMPLES
The following inks were prepared, as listed in Table III, below (the dyes and dye concentrations were as listed above and the balance was water):
Table III. Ink Compositions.
Ink # Ampl Amp2 NaChl Solventl Solvent2 1% 6%
1.5% 6%
1.5% 10%
Case 189534 ~Q~~~~~
Ink Am~l Am~2 NaChl Solventl Solvent2 #
1.0% 0.5% 10%
5 2.5% 1.0% 10%
6 NOAO DEG n-BuOH3 4% 3% 7%
7 OOAO DEG n-BuOH
2% 6% 2%
8 NOAO S465 DEG n-BuOH
4% 0.5% 6% 7%
9 OOAO S465 DEG n-BuOH
2% 0.5% 6% 2%
10 NOAO DEG n-BuOH
4% 6% 7%
11 OOAO S465 DEG n-BuOH
2% 0.5% 3.7% 6% 2%
12 riBC
6%
13 NOAO S465 DEG n-BuOH
4% 1% 0.5% 6% 3%
14 NOAO nBC n-BuOH
6% 6% 2% 3%
15 OOAO S465 DEG n-BuOH
3% 0.5% 0.5% 6% 3%
16 OOAO S465 DPMs n-BuOH
3% 0.5% 0.5% 6% 3%
17 NOAO S465 1,4-BD6 6% 0.5% 2% 5%
18 NOAO S465 1,4-BD
6% 1% 2% 5%
1.0% 0.5% 10%
5 2.5% 1.0% 10%
6 NOAO DEG n-BuOH3 4% 3% 7%
7 OOAO DEG n-BuOH
2% 6% 2%
8 NOAO S465 DEG n-BuOH
4% 0.5% 6% 7%
9 OOAO S465 DEG n-BuOH
2% 0.5% 6% 2%
10 NOAO DEG n-BuOH
4% 6% 7%
11 OOAO S465 DEG n-BuOH
2% 0.5% 3.7% 6% 2%
12 riBC
6%
13 NOAO S465 DEG n-BuOH
4% 1% 0.5% 6% 3%
14 NOAO nBC n-BuOH
6% 6% 2% 3%
15 OOAO S465 DEG n-BuOH
3% 0.5% 0.5% 6% 3%
16 OOAO S465 DPMs n-BuOH
3% 0.5% 0.5% 6% 3%
17 NOAO S465 1,4-BD6 6% 0.5% 2% 5%
18 NOAO S465 1,4-BD
6% 1% 2% 5%
6% 0.5% 0.5% 5.7%
3% 0.5% 0.5% 5.7%
Case 189534 Ink # Amni Am~2 NaChl Solventl Solvent2 21 OOAO 5465 LiCh' DEG
3% 05% 0.5% 6%
Case 189534 Ink # Amni Am~2 NaChl Solventl Solvent2 21 OOAO 5465 LiCh' DEG
3% 05% 0.5% 6%
22 L63"
6%
2 3 n-BuP9 5%
24 nBC
8%
25 OOAO 1,4-BD n-BuOH
7% 5% 2%
26 NTAO 1,4-BD n-BuOH
7% 5% 2%
27* OOAO S465 1,5-PDl n-BuOH
3% 0.5% 6% 3%
28 nBC nHCll 4% 1%
29* NOAO NHAO 1,5-PD peOHl~
4% 6% 6% 2%
30 NHAO 1,4-BD BuOH
7% 5% 2%
31 OOAO 5465 1,4-BD BuOH
6% 0.25% 0.25% 5% 1.75%
32 OOAO nBC
3% 8% 2.5%
33* NOAO OOAO 1,5-PD peOH
6% 2% 7% 2%
Notes: ' sodium cholate ~ SURFYNOL 465 n-butanol n-butyl carbitol DOWANOL DPM~(cellusolve Chemical Co.) of Dow 1,4-butanediol ' lithium cholate * Trade-mark ° PLURONIC L-63 9 n-butylpropasol 1~5-pentanediol 11 n-hexyl carbitol 12 n-pentanol * These inks have a color bleed index of <_2.5; the remaining inks have a color bleed index ranging from about 3 to 4.
Case 189534
6%
2 3 n-BuP9 5%
24 nBC
8%
25 OOAO 1,4-BD n-BuOH
7% 5% 2%
26 NTAO 1,4-BD n-BuOH
7% 5% 2%
27* OOAO S465 1,5-PDl n-BuOH
3% 0.5% 6% 3%
28 nBC nHCll 4% 1%
29* NOAO NHAO 1,5-PD peOHl~
4% 6% 6% 2%
30 NHAO 1,4-BD BuOH
7% 5% 2%
31 OOAO 5465 1,4-BD BuOH
6% 0.25% 0.25% 5% 1.75%
32 OOAO nBC
3% 8% 2.5%
33* NOAO OOAO 1,5-PD peOH
6% 2% 7% 2%
Notes: ' sodium cholate ~ SURFYNOL 465 n-butanol n-butyl carbitol DOWANOL DPM~(cellusolve Chemical Co.) of Dow 1,4-butanediol ' lithium cholate * Trade-mark ° PLURONIC L-63 9 n-butylpropasol 1~5-pentanediol 11 n-hexyl carbitol 12 n-pentanol * These inks have a color bleed index of <_2.5; the remaining inks have a color bleed index ranging from about 3 to 4.
Case 189534
Claims (18)
1. A process for reducing color bleed in inks employed in thermal ink-jet printing, comprising printing on a medi-um with an ink having the following composition:
(a) a vehicle; and (b) about 0.1 to 10 wt% of at least one water-soluble dye dissolved therein, wherein said vehicle comprises (1) at least one member se-lected from the group consisting of zwitterionic surfac-tants and non-ionic amphiphiles, present in an amount that is at least equal to its critical micelle concentration:
(2) 0 to about 20 wt% of at least one organic solvent which supports the micelle formation of said at least one members and (3) the balance water.
(a) a vehicle; and (b) about 0.1 to 10 wt% of at least one water-soluble dye dissolved therein, wherein said vehicle comprises (1) at least one member se-lected from the group consisting of zwitterionic surfac-tants and non-ionic amphiphiles, present in an amount that is at least equal to its critical micelle concentration:
(2) 0 to about 20 wt% of at least one organic solvent which supports the micelle formation of said at least one members and (3) the balance water.
2. The process of Claim 1 wherein said zwitterionic surfactants are selected from the group consisting of non-ionic compounds and ionic compounds.
3. The process of Claim 2 wherein said non-ionic com-pounds are selected from the group consisting of (a) water-soluble amphiphile mimetics, (b) polyethers, polyethylene oxides, nonyl and octyl polyethylene oxides, and acetylenic backboned polyethylene oxides, and (c) amphoteric com-pounds.
4. The process of Claim 3 wherein said mimetics are branched polyethylene amines.
5. The process of Claim 3 wherein said polyethers are selected from the group consisting of ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol n-hexyl ether, triethylene glycol n-butyl ether, and propylene glycol isobutyl ether.
6. The process of Claim 3 wherein said amphoteric sur-factants are pH-sensitive surfactants selected from the group consisting of N,N-dimethyl-N-dodecyl amine oxide, N,N-dimethyl-N-tetradecyl amine oxide, N,N-dimethyl-N-hexadecyl amine oxide, N,N-dimethyl-N-octadecyl amine ox-ide, N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide, N-do-decyl-N,N-dimethyl glycine, phosphates, phosphites, phos-phonates, lecithins, phosphate esters, phospatidylethanol-amines, phosphatidylcholines, phosphatidyl serines, phos-phatidylinositols, and B'-O-lysylphosphatidylglycerols.
7. The process of Claim 3 wherein said amphoteric sur-factants are pH-insensitive surfactants comprising sulfobe-taines.
8. The process of Claim 2 wherein said ionic surfac-tants are selected from the group consisting of cetyl tri-methylammonium bromide, sodium dodecyl sulfate, sodium sul-fanates, and cellusolves.
9. The process of Claim 1 wherein said organic solvent is selected from the group consisting of glycols, diols, glycol esters, glycol ethers, mono and di glycol ethers, cellusolves, carbitols, long chain alcohols, esters, ke-tones, lactones, and glycerols, and derivatives thereof and mixtures thereof.
10. The process of Claim 9 wherein said solvent is se-lected from the group consisting of ethylene glycol, dieth-ylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene gly-col, and derivatives thereofs butanediol, pentanediol, hex-anediol, and homologous diols: propylene glycol laurate:
ethylene glycol monobutyl ether, diethylene glycol mono ethyl ether, diethylene glycol mono butyl ether, diethylene glycol mono hexyl ether, propylene glycol ether, dipropyl-ene glycol ether, and triethylene glycol ether; butyl al-cohol, pentyl alcohol, and homologous alcohols; sulfolane, .gamma.-butyrolactone, N-pyrrolidone and N-(2-hydroxyethyl)pyr-rolidone, and glycerols and their derivatives.
ethylene glycol monobutyl ether, diethylene glycol mono ethyl ether, diethylene glycol mono butyl ether, diethylene glycol mono hexyl ether, propylene glycol ether, dipropyl-ene glycol ether, and triethylene glycol ether; butyl al-cohol, pentyl alcohol, and homologous alcohols; sulfolane, .gamma.-butyrolactone, N-pyrrolidone and N-(2-hydroxyethyl)pyr-rolidone, and glycerols and their derivatives.
11. The process of Claim 1 wherein said dye is a wa-ter-soluble anionic dye selected from the group consisting of C.I. Acid Blue 9, C.I. Acid Red 18, C.I. Acid Red 27, C.I. Acid Red 52, C.I. Acid Yellow 23, C.I. Direct Blue 199, and C.I. Direct Yellow.
12. The process of Claim 11 wherein said anionic dye is associated with a cation selected from the group con-sisting of monovalent alkali earth ions, NH4+, and substi-tuted ammonium salts.
13. The process of Claim 1 wherein said ink consists essentially of:
about 3 wt% N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide;
about 0.5 wt% of an acetylenic polyethylene oxide surfactant;
about 6 wt% pentanediol;
about 3 wt% n-butanol;
a dye selected from the group consisting of 1.33 wt%
Acid Red 27, about 1.33 wt% Direct Yellow 86, and about 1.65 wt%
Acid Blue 9-Na: and the balance water.
about 3 wt% N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide;
about 0.5 wt% of an acetylenic polyethylene oxide surfactant;
about 6 wt% pentanediol;
about 3 wt% n-butanol;
a dye selected from the group consisting of 1.33 wt%
Acid Red 27, about 1.33 wt% Direct Yellow 86, and about 1.65 wt%
Acid Blue 9-Na: and the balance water.
14. The process of Claim 1 wherein said ink consists essentially of:
about 4 wt% N,N-dimethyl-N-octadecyl amine oxide;
about 6 wt% N,N-dimethyl-N-hexadecyl amine oxide;
about 6 wt% pentanediol;
about 2 wt% n-pentanol;
a dye selected from the group consisting of 1. 33 wt%
Acid Red 27, about 1.33 wt% Direct Yellow 86, and about 1.65 wt%
Acid Blue 9-Na; and the balance water.
about 4 wt% N,N-dimethyl-N-octadecyl amine oxide;
about 6 wt% N,N-dimethyl-N-hexadecyl amine oxide;
about 6 wt% pentanediol;
about 2 wt% n-pentanol;
a dye selected from the group consisting of 1. 33 wt%
Acid Red 27, about 1.33 wt% Direct Yellow 86, and about 1.65 wt%
Acid Blue 9-Na; and the balance water.
15. The process of Claim 1 wherein said ink consists essentially of:
about 6 wt% N,N-dimethyl-N-octadecyl amine oxide;
about 2 wt% N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide;
about 7 wt% pentanediol;
about 2 wt% n-pentanol;
a dye selected from the group consisting of 1.33wt%
Acid Red 27, about 1.33 wt% Direct Yellow 86, and about 1.65 wt%
Acid Blue 9-Na; and the balance water.
about 6 wt% N,N-dimethyl-N-octadecyl amine oxide;
about 2 wt% N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide;
about 7 wt% pentanediol;
about 2 wt% n-pentanol;
a dye selected from the group consisting of 1.33wt%
Acid Red 27, about 1.33 wt% Direct Yellow 86, and about 1.65 wt%
Acid Blue 9-Na; and the balance water.
16. A process for reducing color bleed in inks em-ployed in thermal ink-jet printing, comprising printing on a medium with an ink having the following composition:
(a) a vehicle: and (b) 0.1 to about 10 wt% of at least one water-soluble dye dissolved therein, wherein said vehicle comprises (1) at least one member selected from the group consisting of N,N-dimethyl-N-dodecyl amine oxide, N,N-dimethyl-N-hexadecyl amine oxide, N,N-dimethyl-N-octadecyl amine oxide, N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide, present in an amount that is at least equal to its critical micelle concentration: (2) 0 to about 20 wt% of at least one organic solvent selected from the group consisting of pentanediol, pentanol, and butanol:
and (3) the balance water.
(a) a vehicle: and (b) 0.1 to about 10 wt% of at least one water-soluble dye dissolved therein, wherein said vehicle comprises (1) at least one member selected from the group consisting of N,N-dimethyl-N-dodecyl amine oxide, N,N-dimethyl-N-hexadecyl amine oxide, N,N-dimethyl-N-octadecyl amine oxide, N,N-dimethyl-N-(Z-9-octadecenyl)-N-amine oxide, present in an amount that is at least equal to its critical micelle concentration: (2) 0 to about 20 wt% of at least one organic solvent selected from the group consisting of pentanediol, pentanol, and butanol:
and (3) the balance water.
17. The process of Claim 16 wherein said dye is a wa-ter-soluble anionic dye selected from the group consisting of C.I. Acid Blue 9, C.I. Acid Red 18, C.I. Acid Red 27, C.I. Acid Red 52, C.I. Acid Yellow 23, C.I. Direct Blue 199, and C.T. Direct Yellow.
18. The process of Claim 17 wherein said anionic dye is associated with a cation selected from the group con-sisting of monovalent alkali earth ions, NH4+, and substi-tuted ammonium salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/686,731 US5116409A (en) | 1991-04-17 | 1991-04-17 | Bleed alleviation in ink-jet inks |
| US686,731 | 1991-04-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2060598A1 CA2060598A1 (en) | 1992-10-18 |
| CA2060598C true CA2060598C (en) | 2001-10-16 |
Family
ID=24757508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002060598A Expired - Lifetime CA2060598C (en) | 1991-04-17 | 1992-02-04 | Bleed alleviation in ink-jet inks |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5116409A (en) |
| EP (1) | EP0509688B1 (en) |
| JP (1) | JP3197057B2 (en) |
| CA (1) | CA2060598C (en) |
| DE (1) | DE69211412T2 (en) |
| HK (1) | HK18497A (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CA2060598A1 (en) | 1992-10-18 |
| EP0509688B1 (en) | 1996-06-12 |
| JP3197057B2 (en) | 2001-08-13 |
| DE69211412T2 (en) | 1996-10-24 |
| US5116409A (en) | 1992-05-26 |
| HK18497A (en) | 1997-02-13 |
| JPH05132643A (en) | 1993-05-28 |
| EP0509688A1 (en) | 1992-10-21 |
| DE69211412D1 (en) | 1996-07-18 |
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