WO2003011983A2 - Ink compositions containing ultraviolet absorbers - Google Patents

Ink compositions containing ultraviolet absorbers Download PDF

Info

Publication number
WO2003011983A2
WO2003011983A2 PCT/US2001/024069 US0124069W WO03011983A2 WO 2003011983 A2 WO2003011983 A2 WO 2003011983A2 US 0124069 W US0124069 W US 0124069W WO 03011983 A2 WO03011983 A2 WO 03011983A2
Authority
WO
WIPO (PCT)
Prior art keywords
group
ink
ink composition
lower alkyl
ink jet
Prior art date
Application number
PCT/US2001/024069
Other languages
French (fr)
Other versions
WO2003011983A3 (en
Inventor
Ann P. Holloway
James F. Feeman
Original Assignee
Lexmark International, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lexmark International, Inc. filed Critical Lexmark International, Inc.
Priority to PCT/US2001/024069 priority Critical patent/WO2003011983A2/en
Priority to AU2001279116A priority patent/AU2001279116A1/en
Publication of WO2003011983A2 publication Critical patent/WO2003011983A2/en
Publication of WO2003011983A3 publication Critical patent/WO2003011983A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/38Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present invention relates to ink compositions, and more particularly, to ink compositions comprising ultraviolet absorbers.
  • the ink compositions are particularly suitable for ink jet printing.
  • Inkjet printing is accomplished by ejecting ink from a nozzle toward paper or another print medium.
  • the ink may be driven toward the medium in a variety of ways.
  • electrostatic printing the ink is driven from a nozzle toward a medium by an electrostatic field.
  • squeeze tube Another ink jet printing procedure, known as squeeze tube, employs a piezo-electric element in the ink nozzle. Electrically-caused distortions of the piezo-electric element pump the ink through the nozzle and toward the print medium.
  • thermal or bubble ink jet printing the ink is driven from the nozzle toward the print medium by the formation of an expanding vapor phase bubble in the nozzle.
  • Ink compositions used in ink jet printers generally comprise deionized water, a water-soluble or water-miscible organic solvent, and a colorant.
  • a water-soluble or water-miscible organic solvent generally comprise deionized water, a water-soluble or water-miscible organic solvent, and a colorant.
  • colorant is a soluble dye or pigment.
  • inks comprising soluble dyes or pigments can exhibit many problems, such as poor water-fastness, poor light-fastness,
  • UVAs ultraviolet absorbers
  • an object of the present-invention to provide an ultraviolet absorber that is water-soluble and can be easily and directly added into ink compositions, particularly ink compositions suitable for ink jet printing.
  • the present invention relates to an aqueous ink composition suitable for use in ink jet printers and comprising ink and a water-soluble ultraviolet absorbing compound of the formula
  • R is selected from the group consisting of
  • R 2 is selected from the group consisting of -H and halogen
  • R 3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • R 7 is selected from the group consisting of -H, -SO 3 M and -NHCO-lower alkyl
  • R g is selected from the group consisting of -H, -CO 2 M and -SO 3 M
  • R ⁇ is selected from the group consisting of -H, -CO 2 M, -SO 3 M and -NHCO-lower alkyl
  • M is selected from the group consisting of -H, -Na, -K, -Li and -N-(R 10 ) 4 wherein each R, 0 is independently selected from the group consisting of -H, lower alkyl and -(CH 2 -CH-O) n -H;
  • R n is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 ; and n is from 1 to 4; and wherein the compound contains one or two -SO 3 M groups, one -SO 3 M and one -CO 2 M group, or two -CO 2 M groups.
  • the present invention is directed to an ink jet print cartridge
  • composition comprising ink and a water-soluble ultraviolet absorbing compound of
  • R is selected from the group consisting of
  • R 2 is selected from the group consisting of -H and halogen
  • R 3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • R 7 is selected from the group consisting of -H, -SO 3 M and -NHCO-lower alkyl
  • R g is selected from the group consisting of -H, -CO 2 M and -SO 3 M
  • R is selected from the
  • each R 10 is independently selected from the group consisting of -H, lower alkyl and
  • R is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 ; and n is from 1
  • Another aspect of the present invention comprises an aqueous ink composition comprising ink and a water soluble ultraviolet absorbing compound of the formula
  • R 2 is selected from the group consisting of -H and halogen; R 3 is selected
  • R 4 is selected from the group consisting of halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • R 4 is selected from the group consisting of halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • R 5 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, and -OH
  • R ⁇ is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • M is selected from the group consisting of -H, -Na, -Li and -N-(R !0 ) 4 wherein each R J0 is individually selected from the group consisting of -H, lower alkyl and -(CH 2 -CH-O) ⁇ -H;
  • R,, R, is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 ; and n is from 1 to 4; and wherein the compound contains one or two -SO 3 M groups, one -SO 3 M and one -CO 2 M group or two -CO 2 M groups, with the provision that either (1) R 2 and R 3 are not both hydrogen, or (2) R s is not hydrogen.
  • the ink compositions of the present invention are advantageous in exhibiting good color lightfastness when printed.
  • the compositions are particularly advantageous for use in ink jet printers owing to the easy and direct combination of the aqueous ink and the water soluble ultraviolet absorber.
  • the present invention relates to ink jet ink compositions comprising ink and a
  • R( is selected from the group consisting of
  • R 2 is selected from the group consisting of -H and halogen;
  • R 3 is selected from the
  • R 7 is selected from the group consisting of -H, -SO 3 M and -NHCO-lower alkyl
  • R 8 is selected from the group consisting of -H, -CO 2 M and -SO 3 M
  • Rg is selected from the group consisting of -H, -CO 2 M, -SO 3 M and -NHCO-lower alkyl
  • M is selected from the group consisting of -H, -Na, -K, -Li and -N-(R I0 ) 4 wherein each R 10 is independently selected from the group consisting of -H, lower alkyl and
  • Rn R n is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 ; and n is from 1 to 4; and wherein the compound contains one or two -SO 3 M groups, one -SO 3 M and one -CO 2 group, or two -CO 2 M groups.
  • references to lower alkyl throughout this specification refers to C r C g alkyl, preferably C,-C 4 alkyl.
  • reference to lower alkoxy throughout this specification refers to Cj-Cg alkoxy, preferably C,-C 4 alkoxy.
  • R 2 is selected from the group consisting of -H and halogen
  • R 3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO 2 M and - SO 3 M
  • R 4 is selected from the group consisting of halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • R 5 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, and -OH
  • R is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • M is selected from the group consisting of -H, -Na, -Li and -N-(R 10 ) 4 wherein each R ]0 is individually selected from the group consisting of -H, lower alkyl and -(CH 2 -CH-O) n -H;
  • R M is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 ; and n is from 1 to 4; and wherein the compound contains one or two -SO 3 M groups, one -SO 3 M and one -CO 2 M group or two -CO 2 M groups, with the provision that either (1) R 2 and R 3 are not both hydrogen, or (2) R 5 is not hydrogen.
  • Preferred ultraviolet absorbing compounds of the present invention have the following structural formulas
  • the ultraviolet absorbers of the present invention are highly water-soluble, readily dissolve in the usual aqueous vehicles employed in common ink jet compositions, and remain in solution upon extended
  • the ultraviolet absorbing compound is included in the ink compositions in an amount sufficient to improve the light-fastness of printed images.
  • the ink compositions of the present invention comprise from about 0.1 to about 5% by weight of the ultraviolet absorbing compounds. More preferably, the ink compositions
  • the ultraviolet absorbing compounds contain from about 1 to about 3% of the ultraviolet absorbing compounds.
  • .ultraviolet absorbing compounds are preferably used in a salt form, which exhibits satisfactory water solubility.
  • the salt form include sodium, potassium,
  • the ultraviolet absorbent compounds are isolable in the free acid form and convertable to any of the salt forms, or alternatively, may be
  • the ultraviolet absorbing compounds of the present invention may be prepared
  • Suitable ortho-nitro anilines include, for example, 2-nitroaniline, 2- nitroaniline-4-sulfonic acid, 4-amino-3-nitro-benzoic acid, 4-methyl-2-nitroaniline, 4- methoxy-2-nitroaniline, 4-chloro-2-nitroaniline, 5-chloro-2-nitroaniline, 4,5-dichloro- 2-nitroaniline, and 4-ethyl-2-nitroaniline, among others.
  • Suitable phenolic couplers include, for example, 4-hydroxybenzene sulfonic
  • naphthols include, for example, 2-naphthol, 2-na ⁇ hthol-
  • naphthol-6-carboxylic acid l-naphthol-3,6-disulfonic acid, l-naphthol-3 -sulfonic acid, l-naphthol-4-sulfonic acid; l-naphthol-5-sulfonic acid, 2-acetamido-5-hydroxy-
  • naphthalene-7-sulfonic acid 2-acetamido-8-hydroxy-naphthalene-6-suIfonic acid
  • the ink compositions of the present invention are aqueous compositions.
  • water may contain one or more water-miscible solvents, for example in an
  • a suitable carrier mixture depends on the requirements of the specific application involved, such as desired surface tension and viscosity, the selected pigment or dye, the desired drying time of the ink, and the type of paper onto which the ink will be printed.
  • water soluble organic solvents that may be selected include (1) alcohols, such as methyl
  • ketones or ketoalcohols such as acetone, methylethyl ketone and diacetone alcohol
  • ethers such as tetrahydrofuran and dioxane
  • ethers such as
  • polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol,
  • propylene glycol tetraetheylene glycol
  • polyethylene glycol glycerol, 2-methyl-2,4-
  • Preferred water soluble organic solvents include polyhydric alcohols, such as
  • glycol ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6- hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol; diols, such as butanediol, pentanediol, hexanediol and homologous diols; glycol ethers, such as
  • propylene glycol laureate glycerol
  • polyalkyl glycols such as polyethylene glycol
  • lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl or monoethyl ether, diethylene glycol methyl or ethyl ether, and triethylene glycol monomethyl or monoethyl ether.
  • Particularly preferred organic solvents include ethylene glycol, diethylene glycol, and tetraethylene glycol.
  • ultraviolet absorbing compound as disclosed above, and an aqueous carrier.
  • the key selection criteria for the pigment is that they must be dispersable in the aqueous
  • pigment means an insoluble colorant.
  • pigment particles are sufficiently small to permit free flow of the ink through the ink
  • the jet printing device especially at the ejecting nozzles that usually have a diameter ranging from about 10 microns to about 50 microns.
  • the particle size also has an
  • ink It is also desirable to use small particles for maximum color strength and gloss.
  • the range of useful particle size is from approximately 0.05 micron to approximately
  • the pigment particle size should range from about 0.05 micron to about 5 microns and most preferably, from about 0.05 micron to about 1 micron.
  • Pigments suitable for use in the present invention include, for example, azo
  • pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments, polycyclic pigments, perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments,
  • isoindolinone pigments quinophthalone pigments and dry lakes.
  • Additional organic pigments include nitro pigments, nitroso pigments, aniline black and daylight fluorescent pigments.
  • Preferred pigments include titanium oxide, iron oxide, and
  • the present invention include the following: Heliogen® Blue L 690 IF (BASF),
  • Heucophthal® Blue G XBT-583D Heubach
  • Irgalite® Rubine 4 BL Ciba-Geigy
  • the ink compositions may also contain conventional amounts of various modifiers such as binders, surfactants, polymer dispersants, biocides, corrosion
  • inhibitors such as sequestrants, pH buffers, and/or conductivity addivitives. They may also contain further water-soluble ultraviolet light absorbers, if desired.
  • Another embodiment of the present invention comprises an ink jet print cartridge comprising an ink jet ink storage receptacle, an ink jet printhead and an ink jet ink composition comprising ink and a water-soluble ultraviolet absorbing
  • R 2 is selected from the group consisting of -H and halogen
  • R 3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO 2 M and - SO 3 M
  • R 4 is selected from the group consisting of halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • R s is selected from the group consisting o -H, halogen, lower alkyl, lower alkoxy, and -OH
  • Rg is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO 2 M and -SO 3 M
  • M is selected from the group consisting of -H, -Na, -Li and -N-(R 1D ) 4 wherein each R 10 is individually selected from the group consisting of -H, lower alkyl and -(CH 2 -CH-O) n -H;
  • R n is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 ; and n is from 1 to 4; and wherein the compound contains one or two -SO 3 M groups, one -SO 3 M and one -CO 2 M group or two -CO 2 M groups, with the provision that either (1) R 2 and R 3 are not hydrogen, or (2) R 5 is not hydrogen.
  • This example is directed to ink compositions of the present invention which
  • the ink jet ink compositions were formulated using conventional ink jet inks comprising either sodium dye salts or tetramethylammonium (TMA) dye salt.
  • TMA tetramethylammonium
  • yellow ink was formulated employing a tetramethylammonium (TMA) dye salt and 3% of the ultraviolet absorbing compound (V).
  • Magenta and cyan inks were formulated using sodium dye salts and 3% of the ultraviolet absorbing compound (V).
  • Comparative ink jet compositions were formulated using conventional cyan, magneta and yellow inks without incorporating the 3% ultraviolet absorbing compound.
  • the ink jet ink compositions comprising the ultraviolet absorbing compound showed dramatic improvement in light-fastness for most of the ink compositions in various paper types. Furthermore, the most dramatic improvement in light-fastness was demonstrated by the yellow ink containing the 3% ultraviolet absorbing compound.
  • the yellow ink employs a tetramethylammonium (TMA) dye salt as compared to the sodium dye salts used in the magenta and cyan inks.
  • TMA tetramethylammonium
  • ink jet ink compositions were prepared using conventional ink jet inks and 3% of the ultraviolet absorbing compound VIII as shown above. Comparative ink jet ink compositions were formulated comprising the same ink jet inks without the 3% ultraviolet absorbing
  • the yellow ink was prepared using a TMA dye salt while the magenta and cyan inks were prepared using sodium dye salts.
  • Example 1 Similar to Example 1, the ink jet ink compositions of the present invention and the comparative ink jet inks were then used in ink jet printing on the three types of paper as described in Example 1. Light-fastness of the ink jet ink compositions was
  • the ink jet ink compositions of the present invention employing a 3% ultraviolet absorbing compound showed dramatically lower delta E values than the comparative ink jet ink compositions. Therefore, the ink jet ink compositions of the present invention have superior light-fastness as compared to conventional ink jet ink compositions. It can be noted from Table 2 that the most dramatic improvement with the 3% ultraviolet absorbing compound was seen with the yellow ink.
  • Inkjet ink compositions of the present invention which utilize the ultraviolet absorbing compound of Example 2 were formulated. Tetramethylammonium dye salts were employed in making the yellow, magenta and cyan inks. The tetramethylammonium dye salts were mixed with 3% of the ultraviolet absorbing compound to form yellow, magenta and cyan ink jet ink compositions. Comparative ink jet ink compositions were also prepared as detailed in Example 1. The ink jet ink compositions of the present invention and the comparative ink jet ink compositions were then used for ink jet printing to measure light-fastness as described in Example 1. Table 3 details the results of this example.
  • ink jet ink compositions comprising the ultraviolet absorbing compounds of the present invention demonstrate improvements in light- fastness. Moreover, the most dramatic improvement in light-fastness was seen with the ink jet ink compositions comprising tetramethylammonium dye salts and the
  • present invention exhibit surprising results in the improvement of light-fastness over

Abstract

Ink compositions containing ultraviolet absorbing compounds of formula I, wherein R1, R2, and R3 are defined herein, and wherein the compound contains one or two -SO3M groups, one -SO3M and one -CO3M group, or two -CO2M groups. Ink jet ink compositions containing ultraviolet absorbing compounds of formula IV, wherein R2, R3, R4, R5 and R6 are defined herein, and wherein the compound contains one or two -SO3M groups, one -SO3M and one -CO2M group or two -CO2M groups, with the provision that either (1) R2 and R3 are not both hydrogen, or (2) R5 is not hydrogen. The ink compositions are adapted for ink jet printing.

Description

INK COMPOSITIONS CONTAINING ULTRAVIOLET ABSORBERS
FIELD OF THE INVENTION
The present invention relates to ink compositions, and more particularly, to ink compositions comprising ultraviolet absorbers. The ink compositions are particularly suitable for ink jet printing.
BACKGROUND OF THE INVENTION
Inkjet printing is accomplished by ejecting ink from a nozzle toward paper or another print medium. The ink may be driven toward the medium in a variety of ways. For example, in electrostatic printing, the ink is driven from a nozzle toward a medium by an electrostatic field. Another ink jet printing procedure, known as squeeze tube, employs a piezo-electric element in the ink nozzle. Electrically-caused distortions of the piezo-electric element pump the ink through the nozzle and toward the print medium. In still another ink jet printing procedure, known as thermal or bubble ink jet printing, the ink is driven from the nozzle toward the print medium by the formation of an expanding vapor phase bubble in the nozzle. These various printing methods are described in "Output Hard Copy Devices," edited by Durbeck and Sherr, Academic Press, 1988 (see particularly Chapter 13, entitled, "Ink Jet Printing").
Ink compositions used in ink jet printers generally comprise deionized water, a water-soluble or water-miscible organic solvent, and a colorant. Generally, the
colorant is a soluble dye or pigment. Unfortunately, inks comprising soluble dyes or pigments can exhibit many problems, such as poor water-fastness, poor light-fastness,
clogging of the jetting channels as a result of solvent evaporation and changes in the solubility of the dye, dye crystallization, poor ink quality including ink bleeding and feathering, poor thermal stability, chemical instability, and ease of oxidation.
The need for more light-fast inks for ink jet printing is increasing as photo images become more popular. Resistance to fading due to light has been aided in industrial products by incorporation of ultraviolet absorbers (UVAs). Commercially available UVAs are used in textile dying and for additives and coatings. To be effective, UVAs processed during textile dying typically require high temperature exposure for a duration of time; these high temperature requirements making the UVAs impractical for personal ink jet printing applications. UVAs used in the coating industry have limited solubility in water and therefore cannot be easily incorporated in conventional aqueous ink jet ink compositions.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present-invention to provide an ultraviolet absorber that is water-soluble and can be easily and directly added into ink compositions, particularly ink compositions suitable for ink jet printing.
Other objects and advantages of the present invention will become apparent from the following disclosure.
In a first aspect, the present invention relates to an aqueous ink composition suitable for use in ink jet printers and comprising ink and a water-soluble ultraviolet absorbing compound of the formula
Figure imgf000004_0001
wherein R, is selected from the group consisting of
Figure imgf000004_0002
R2 is selected from the group consisting of -H and halogen; R3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; R7 is selected from the group consisting of -H, -SO3M and -NHCO-lower alkyl; Rg is selected from the group consisting of -H, -CO2M and -SO3M; R^ is selected from the group consisting of -H, -CO2M, -SO3M and -NHCO-lower alkyl; and M is selected from the group consisting of -H, -Na, -K, -Li and -N-(R10)4 wherein each R,0 is independently selected from the group consisting of -H, lower alkyl and -(CH2-CH-O)n-H;
Rn is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1 to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and one -CO2M group, or two -CO2M groups. In a second aspect, the present invention is directed to an ink jet print cartridge
comprising an ink jet storage receptacle, an ink jet printhead and an ink jet ink
composition comprising ink and a water-soluble ultraviolet absorbing compound of
the formula
Figure imgf000005_0001
wherein R, is selected from the group consisting of
Figure imgf000005_0002
R2 is selected from the group consisting of -H and halogen; R3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; R7 is selected from the group consisting of -H, -SO3M and -NHCO-lower alkyl; Rg is selected from the group consisting of -H, -CO2M and -SO3M; R, is selected from the
group consisting of -H, -CO2M, -SO3M and -NHCO-lower alkyl; and M is selected
from the group consisting of -H, -Na, -K, -Li and -N-(R10)4 wherein each R10 is independently selected from the group consisting of -H, lower alkyl and
-(CH2-CH-O)n-H;
)
R,, is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1
to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and
one -CO2M group, or two -CO2M groups. Another aspect of the present invention comprises an aqueous ink composition comprising ink and a water soluble ultraviolet absorbing compound of the formula
Figure imgf000006_0001
wherein R2 is selected from the group consisting of -H and halogen; R3 is selected
from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and - SO3M; R4 is selected from the group consisting of halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; R5 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, and -OH; R^ is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; M is selected from the group consisting of -H, -Na, -Li and -N-(R!0)4 wherein each RJ0 is individually selected from the group consisting of -H, lower alkyl and -(CH2-CH-O)π-H;
I
R,, R,, is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1 to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and one -CO2M group or two -CO2M groups, with the provision that either (1) R2 and R3 are not both hydrogen, or (2) Rs is not hydrogen.
The ink compositions of the present invention are advantageous in exhibiting good color lightfastness when printed. The compositions are particularly advantageous for use in ink jet printers owing to the easy and direct combination of the aqueous ink and the water soluble ultraviolet absorber.
Still other objects, advantages and novel features of the present invention will become apparent to those skilled in the art from the following detailed description, which is simply by way of illustration various modes contemplated for carrying out the invention. As will be realized, the invention is capable of other different obvious aspects all without departing from the invention. Accordingly, the description is
illustrative in nature and not restrictive.
DETAILED DESCRIPTION
The present invention relates to ink jet ink compositions comprising ink and a
water-soluble ultraviolet absorbent compound of the formula
Figure imgf000007_0001
wherein R( is selected from the group consisting of
Figure imgf000007_0002
R2 is selected from the group consisting of -H and halogen; R3 is selected from the
group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; R7 is selected from the group consisting of -H, -SO3M and -NHCO-lower alkyl; R8 is selected from the group consisting of -H, -CO2M and -SO3M; Rg is selected from the group consisting of -H, -CO2M, -SO3M and -NHCO-lower alkyl; and M is selected from the group consisting of -H, -Na, -K, -Li and -N-(RI0)4 wherein each R10 is independently selected from the group consisting of -H, lower alkyl and
-(CH2-CH-O)n-H;
I
Rn Rn is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1 to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and one -CO2 group, or two -CO2M groups.
Reference to lower alkyl throughout this specification refers to CrCg alkyl, preferably C,-C4 alkyl. In addition, reference to lower alkoxy throughout this specification refers to Cj-Cg alkoxy, preferably C,-C4 alkoxy.
Preferred ultraviolet absorbing compounds according to this embodiment of the present invention have the following structural formulas:
Figure imgf000008_0001
Another embodiment of the present invention comprises an ink composition
comprising ink and a water-soluble ultraviolet absorbing compound of the formula
Figure imgf000009_0001
wherein R2 is selected from the group consisting of -H and halogen; R3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and - SO3M; R4 is selected from the group consisting of halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; R5 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, and -OH; R is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; M is selected from the group consisting of -H, -Na, -Li and -N-(R10)4 wherein each R]0 is individually selected from the group consisting of -H, lower alkyl and -(CH2-CH-O)n-H;
Figure imgf000009_0002
RM is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1 to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and one -CO2M group or two -CO2M groups, with the provision that either (1) R2 and R3 are not both hydrogen, or (2) R5 is not hydrogen.
Preferred ultraviolet absorbing compounds of the present invention have the following structural formulas
Figure imgf000010_0001
The ultraviolet absorbing compounds of this invention have been found to be
particularly efficacious in improving light-fastness of prints made with ink jet printers
containing conventional dyes employed for such purposes including monoazo, poly- azo and copper phthalocyanine dyes. The ultraviolet absorbers of the present invention are highly water-soluble, readily dissolve in the usual aqueous vehicles employed in common ink jet compositions, and remain in solution upon extended
storage.
The ultraviolet absorbing compound is included in the ink compositions in an amount sufficient to improve the light-fastness of printed images. Preferably, the ink compositions of the present invention comprise from about 0.1 to about 5% by weight of the ultraviolet absorbing compounds. More preferably, the ink compositions
contain from about 1 to about 3% of the ultraviolet absorbing compounds. The
.ultraviolet absorbing compounds are preferably used in a salt form, which exhibits satisfactory water solubility. Examples of the salt form include sodium, potassium,
lithium, ammonium, triethanolammonium, and tetramethylammonium salts, and
mixtures of various salt forms. The ultraviolet absorbent compounds are isolable in the free acid form and convertable to any of the salt forms, or alternatively, may be
synthesized directly in the desired salt form.
The ultraviolet absorbing compounds of the present invention may be prepared
by diazotizing and coupling an optionally substituted ortho-nitroaniline with a
substituted phenol or naphthol which couples in the ortho position to the hydroxyl group, and subsequently reducing the resultant ortho-nitro-ortho'-hydroxy-azo
compound to the corresponding benzotriazole in alkaline aqueous medium using, for
example, zinc, or more advantageously, hydrogen in the presence of a group VIII noble metal catalyst. These reactions are well known to one of ordinary skill in the art and are more fully described in the chemical literature.
Suitable ortho-nitro anilines include, for example, 2-nitroaniline, 2- nitroaniline-4-sulfonic acid, 4-amino-3-nitro-benzoic acid, 4-methyl-2-nitroaniline, 4- methoxy-2-nitroaniline, 4-chloro-2-nitroaniline, 5-chloro-2-nitroaniline, 4,5-dichloro- 2-nitroaniline, and 4-ethyl-2-nitroaniline, among others.
Suitable phenolic couplers include, for example, 4-hydroxybenzene sulfonic
acid, guaiacol sulfonic acid, o-cresol-4-sulfonic acid, p-cresol, 2,4-dimethyl-phenol,
2-hydroxy-5-methyl-benzoic acid, 4-hydroxy-benzoic acid, 2-hydroxy-5-methoxy-
benzoic acid, 4-methoxy-phenol, 4-chloro-phenol, 2,4-dichloro-phenol, and 3,4- dichloro-phenol, among others. Examples of suitable naphthols include, for example, 2-naphthol, 2-naρhthol-
4-sulfonic acid, 2-naphthol-6-sulfonic acid, 2-naphthol-8-sulfonic acid, 2-naphthol-
3,6-disulfonic acid, 2-naphthol-6,8-disuIfonic acid, 2-naρhthol-3-carboxylic acid, 2-
naphthol-6-carboxylic acid, l-naphthol-3,6-disulfonic acid, l-naphthol-3 -sulfonic acid, l-naphthol-4-sulfonic acid; l-naphthol-5-sulfonic acid, 2-acetamido-5-hydroxy-
naphthalene-7-sulfonic acid, 2-acetamido-8-hydroxy-naphthalene-6-suIfonic acid, and
l-acetamido-8-hydroxy-naphthalene-3,6-disulfonic acid, among others.
The ink compositions of the present invention are aqueous compositions.
They contain at least 30% by weight of water, preferably deionized water. In addition
to water, they may contain one or more water-miscible solvents, for example in an
amount of up to 70% by weight. Selection of a suitable carrier mixture depends on the requirements of the specific application involved, such as desired surface tension and viscosity, the selected pigment or dye, the desired drying time of the ink, and the type of paper onto which the ink will be printed. Representative examples of water soluble organic solvents that may be selected include (1) alcohols, such as methyl
alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, iso-butyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl
alcohol; (2) ketones or ketoalcohols, such as acetone, methylethyl ketone and diacetone alcohol; (3) ethers, such as tetrahydrofuran and dioxane; (4) ethers, such as
ethyl acetate, ethyl lactate, ethylene carbonate and propylene carbonate; (5) polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol,
propylene glycol, tetraetheylene glycol, polyethylene glycol, glycerol, 2-methyl-2,4-
pentanediol, 1,2,6-hexanetriol and thiodiglycol; (6) lower alkyl mono- or di-ethers derived from alkylene glycols, such as ethylene glycol monomethyl (or monoethyl)
ether, diethylene glycol monomethyl (or monoethyl) ether, propylene glycol
monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl)
ether and diethylene glycol dimethy (or diethyl) ether; (7) nitrogen-containing cyclic
compounds, such as pyrrolidone, N-methyl-2-pyrrolidone and 1 ,3-dimethyl-2- imidazolidinone; and (8) sulfur-containing compounds, such as dimethyl sulfoxide
and tetramethylene sulfone. Other useful organic solvents include lactones and
lactams.
Preferred water soluble organic solvents include polyhydric alcohols, such as
ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6- hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol; diols, such as butanediol, pentanediol, hexanediol and homologous diols; glycol ethers, such as
propylene glycol laureate; glycerol; polyalkyl glycols, such as polyethylene glycol; and lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl or monoethyl ether, diethylene glycol methyl or ethyl ether, and triethylene glycol monomethyl or monoethyl ether. Particularly preferred organic solvents include ethylene glycol, diethylene glycol, and tetraethylene glycol.
In another embodiment of the present invention, the aqueous ink compositions
preferably comprise from about 0.5% to about 10% by weight of an insoluble pigment, from about 0,1% to about 5%, preferably from about 1% to about 3%, of an
ultraviolet absorbing compound as disclosed above, and an aqueous carrier.
A wide variety of organic and inorganic pigments, alone or in combination,
may be selected for use in the aqueous inks of the present invention. The key selection criteria for the pigment is that they must be dispersable in the aqueous
medium. The term "pigment," as used herein, means an insoluble colorant. The
pigment particles are sufficiently small to permit free flow of the ink through the ink
jet printing device, especially at the ejecting nozzles that usually have a diameter ranging from about 10 microns to about 50 microns. The particle size also has an
influence on pigment dispersion stability, which is critical throughout the life of the
ink. It is also desirable to use small particles for maximum color strength and gloss.
The range of useful particle size is from approximately 0.05 micron to approximately
15 microns. Preferably, the pigment particle size should range from about 0.05 micron to about 5 microns and most preferably, from about 0.05 micron to about 1 micron.
Pigments suitable for use in the present invention include, for example, azo
pigments, such as azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments, polycyclic pigments, perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments,
isoindolinone pigments, quinophthalone pigments and dry lakes. Additional organic pigments include nitro pigments, nitroso pigments, aniline black and daylight fluorescent pigments. Preferred pigments include titanium oxide, iron oxide, and
carbon black. Examples of commercially available pigments which may be used in
the present invention include the following: Heliogen® Blue L 690 IF (BASF),
Heliogen® Blue NBD 7010 (BASF), Heliogen® Blue K 7090 (BASF),
Heucophthal® Blue G XBT-583D (Heubach), Irgalite® Rubine 4 BL (Ciba-Geigy),
Quindo® Magenta (Mobay), Indofast® Brilliant Scarlet (Mobay), Hostaperm® Scarlet GO (Hoechst), Permanent Rubine F6B (Hoechst), Monostral® Scarlet (Ciba-
Geigy), Raven® 1170 (Col. Chem.), Special Black 4A (Degussa), Black FW 18
(Degussa), Sterling® NS Black (Cabot), Sterling® NSX 76 (Cabot), Monarch® 880
(Cabot), Tipure® R-101 (DuPont), Mogul L (Cabot), B 8200 (Paul Uhlich),
Heliogen® Green K 8683 (BASF), Heliogen® Green L 9140 (BASF), Monostral®
Red B (Ciba-Geigy), Monastral® Violet R (Ciba-Geigy), Hostaperm® Orange GR (Hoechst), Paliogen® Orange (BASF), L75-2377 Yellow (Sun Chem.), L74-1357
Yellow (Sun Chem.), Hostaperm® Yellow H4G (Hoechst), Irgazin® Yellow 5GT (Ciba-Geigy), Permanent Yellow G3R-01 (Hoechst), Novoperm® Yellow FGL
(Hoechst), Chromophthal® Yellow 3G (Ciba-Geigy), Hansa Yellow X (Hoechst), Dalamar® Yellow YT-858-D (Heubach) and Hansa Brilliant Yellow 5GX-02 (Hoechst).
The ink compositions may also contain conventional amounts of various modifiers such as binders, surfactants, polymer dispersants, biocides, corrosion
inhibitors, sequestrants, pH buffers, and/or conductivity addivitives. They may also contain further water-soluble ultraviolet light absorbers, if desired.
Another embodiment of the present invention comprises an ink jet print cartridge comprising an ink jet ink storage receptacle, an ink jet printhead and an ink jet ink composition comprising ink and a water-soluble ultraviolet absorbing
compound of the formula
Figure imgf000015_0001
wherein R2 is selected from the group consisting of -H and halogen; R3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and - SO3M; R4 is selected from the group consisting of halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; Rs is selected from the group consisting o -H, halogen, lower alkyl, lower alkoxy, and -OH; Rg is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; M is selected from the group consisting of -H, -Na, -Li and -N-(R1D)4 wherein each R10 is individually selected from the group consisting of -H, lower alkyl and -(CH2-CH-O)n-H;
I R..
Rn is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1 to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and one -CO2M group or two -CO2M groups, with the provision that either (1) R2 and R3 are not hydrogen, or (2) R5 is not hydrogen.
Suitable ink jet ink storage receptacles and ink jet printheads are disclosed, for example, in U.S. Patents Nos. 5,661,510, 5,751,324, 5,818,478 and 5,719,605, all of
which are incorporated herein by reference.
The following examples demonstrate various embodiments and advantages of the ink compositions and ink jet print cartridges containing the ultraviolet absorbing compounds of the present invention. In the examples and throughout the present
specification, parts and percentages are by weight unless otherwise indicated. Example 1:
This example is directed to ink compositions of the present invention which
utilize the ultraviolet absorbing compound having the structural formula
Figure imgf000017_0001
The ink jet ink compositions were formulated using conventional ink jet inks comprising either sodium dye salts or tetramethylammonium (TMA) dye salt. A
yellow ink was formulated employing a tetramethylammonium (TMA) dye salt and 3% of the ultraviolet absorbing compound (V). Magenta and cyan inks were formulated using sodium dye salts and 3% of the ultraviolet absorbing compound (V). Comparative ink jet compositions were formulated using conventional cyan, magneta and yellow inks without incorporating the 3% ultraviolet absorbing compound.
Light-fastness was measured by determining the delta E value between a control ink that has had no exposure to light and a sample that has been exposed to a Xenon Arc lamp for 48 hours. Therefore, the lower the delta E value, the better the light-fastness of the ink composition. Each of the ink compositions of the present invention and the comparative ink compositions of this example were used in ink jet recording on three different types of paper: plain (Xerox 4200), coated (Hi Res), and photo (Lexmark). Table 1 summarizes the delta E values for the ink jet ink compositions of the present invention and the comparative ink jet ink compositions. Table 1
Figure imgf000018_0002
As can be seen by the results in Table 1, the ink jet ink compositions comprising the ultraviolet absorbing compound showed dramatic improvement in light-fastness for most of the ink compositions in various paper types. Furthermore, the most dramatic improvement in light-fastness was demonstrated by the yellow ink containing the 3% ultraviolet absorbing compound. The yellow ink employs a tetramethylammonium (TMA) dye salt as compared to the sodium dye salts used in the magenta and cyan inks. Example 2:
This example is directed to ink jet ink compositions of the present invention comprising the ultraviolet absorbing compound having the following structural formula
Figure imgf000018_0001
Similar to the methods shown in Example 1, ink jet ink compositions were prepared using conventional ink jet inks and 3% of the ultraviolet absorbing compound VIII as shown above. Comparative ink jet ink compositions were formulated comprising the same ink jet inks without the 3% ultraviolet absorbing
compound. The yellow ink was prepared using a TMA dye salt while the magenta and cyan inks were prepared using sodium dye salts.
Similar to Example 1, the ink jet ink compositions of the present invention and the comparative ink jet inks were then used in ink jet printing on the three types of paper as described in Example 1. Light-fastness of the ink jet ink compositions was
then measured as described in Example 1. Table 2 details the delta E values for the present example.
Table 2
Figure imgf000019_0001
As shown in Table 2, the ink jet ink compositions of the present invention employing a 3% ultraviolet absorbing compound showed dramatically lower delta E values than the comparative ink jet ink compositions. Therefore, the ink jet ink compositions of the present invention have superior light-fastness as compared to conventional ink jet ink compositions. It can be noted from Table 2 that the most dramatic improvement with the 3% ultraviolet absorbing compound was seen with the yellow ink. Example 3;
Inkjet ink compositions of the present invention which utilize the ultraviolet absorbing compound of Example 2 were formulated. Tetramethylammonium dye salts were employed in making the yellow, magenta and cyan inks. The tetramethylammonium dye salts were mixed with 3% of the ultraviolet absorbing compound to form yellow, magenta and cyan ink jet ink compositions. Comparative ink jet ink compositions were also prepared as detailed in Example 1. The ink jet ink compositions of the present invention and the comparative ink jet ink compositions were then used for ink jet printing to measure light-fastness as described in Example 1. Table 3 details the results of this example.
Table 3
Figure imgf000020_0001
As shown in Table 3, ink jet ink compositions comprising the ultraviolet absorbing compounds of the present invention demonstrate improvements in light- fastness. Moreover, the most dramatic improvement in light-fastness was seen with the ink jet ink compositions comprising tetramethylammonium dye salts and the
ultraviolet absorbing compounds of the present invention. The examples demonstrate that the ink jet ink compositions according to the
present invention exhibit surprising results in the improvement of light-fastness over
conventional ink jet ink compositions.
The various preferred embodiments and examples set forth herein are presented in order to further illustrate the claimed invention and are not intended to be limiting thereof. Additional embodiments and alternatives within the scope of the claimed invention will be apparent to those of ordinary skill in the art.

Claims

What is claimed is: 1. An ink composition comprising ink and a water soluble ultraviolet absorbing
compound of the formula
Figure imgf000022_0001
wherein R, is selected from the group consisting of
Figure imgf000022_0002
R2 is selected from the group consisting of -H and halogen; R3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; R7 is selected from the group consisting of -H, -SO3M and -NHCO-lower alkyl; R8 is selected from the group consisting of -H, -CO2M and -SO3M; R^, is selected from the group consisting of -H, -CO2M, -SO3M and -NHCO-lower alkyl; and M is selected from the group consisting of -H, -Na, -K, -Li and -N-(R10)4 wherein each R10 is independently selected from the group consisting of -H, lower alkyl and -(CH2-CH-O)n-H;
I
R„ Rn is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1 to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and
one -CO2M group, or two -CO2M groups. The ink composition of claim 1, wherein R, is
Figure imgf000023_0001
The ink composition of claim 2, wherein R8 is -H.
4. The ink composition of claim 2, wherein R, is -SO3M.
The ink composition of claim 3, wherein Rg is -SO3M.
The ink composition of claim 2, wherein p is -H.
7. The ink composition of claim 2, wherein Rg is -CO2M.
8. The ink composition of claim 5, wherein R2 is -H.
9. The ink composition of claim 8, wherein R3 is -SO3M.
10. The ink composition of claim 7, wherein R2 is -H.
11. The ink composition of claim 10, wherein R3 is -SO3M.
12. The ink composition of claim 1, wherein R, is
Figure imgf000024_0001
13. The ink composition of claim 12, wherein R2 is -H and R3 is -H.
14. The ink composition of claim 12, wherein R7 is -SO3M.
15. The ink composition of claim 13, wherein R7 is -SO3M.
16. The ink composition of claim 13, wherein R7 is -CO2M.
17. The ink composition of claim 1 , wherein the ink comprises ammonium d e salt.
18. The ink composition of claim 17, wherein the ink comprises tetramethylammonium dye salt.
19. The ink composition of claim 2, wherein the ink comprises ammonium dye salt,
20. The ink composition of claim 19, wherein the ink comprises tetramethylammonium dye salt.
21. The ink composition of claim 12, wherein the ink comprises ammonium dye salt.
22. The ink composition of claim 21 , wherein the ink comprises tetramethylammonium dye salt.
23. An ink jet print cartridge comprising an ink jet ink storage receptacle, an ink
jet printhead and an ink jet ink composition comprising ink and a water soluble ultraviolet absorbing compound of the formula
Figure imgf000025_0001
wherein R, is selected from the group consisting of
Figure imgf000025_0002
R2 is selected from the group consisting of -H and halogen; R3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; R7 is selected from the group consisting of -H, -SO3M and -NHCO-lower alkyl; R8 is selected from the group consisting of -H, -CO2M and -SO3M; g is selected from the group consisting of -H, -CO2M, -SO3M and -NHCO-lower alkyl; and M is selected from the group consisting of -H, -Na, -K, -Li and -N-(R10)4 wherein each RI0 is
independently selected from the group consisting of -H, lower alkyl and -(CH2-CH-O)n-H;
I
Rn is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1 to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and one -CO2M group, or two -CO2M groups.
24. An ink composition comprising ink and a water soluble ultraviolet absorbing compound of the formula
Figure imgf000026_0001
wherein R2 is selected from the group consisting of -H and halogen; R3 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and - SO3M; R4 is selected from the group consisting of halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; R5 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, and -OH; R6 is selected from the group consisting of -H, halogen, lower alkyl, lower alkoxy, -CO2M and -SO3M; M is selected from the group consisting of -H, -Na, -Li and -N-(R10)4 wherein each R10 is individually selected from the group consisting of -H, lower alkyl and -(CH2-CH-O)n-H;
I Rπ is selected from the group consisting of -H, -CH3 and -CH2-CH3; and n is from 1 to 4; and wherein the compound contains one or two -SO3M groups, one -SO3M and
one -CO2M group or two -CO2M groups, with the provision that either (1) R2 and R3 are not both hydrogen, or (2) Rs is not hydrogen.
25. The ink composition of claim 24, wherein the ink comprises ammonium dye salt.
26. The ink composition of claim 25, wherein the ink comprises tetramethylammonium dye salt.
PCT/US2001/024069 2001-08-01 2001-08-01 Ink compositions containing ultraviolet absorbers WO2003011983A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2001/024069 WO2003011983A2 (en) 2001-08-01 2001-08-01 Ink compositions containing ultraviolet absorbers
AU2001279116A AU2001279116A1 (en) 2001-08-01 2001-08-01 Ink compositions containing ultraviolet absorbers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2001/024069 WO2003011983A2 (en) 2001-08-01 2001-08-01 Ink compositions containing ultraviolet absorbers

Publications (2)

Publication Number Publication Date
WO2003011983A2 true WO2003011983A2 (en) 2003-02-13
WO2003011983A3 WO2003011983A3 (en) 2009-06-11

Family

ID=21742742

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/024069 WO2003011983A2 (en) 2001-08-01 2001-08-01 Ink compositions containing ultraviolet absorbers

Country Status (2)

Country Link
AU (1) AU2001279116A1 (en)
WO (1) WO2003011983A2 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4041044A (en) * 1974-11-25 1977-08-09 Ciba-Geigy Corporation Process for the production of 2-aryl-2H-benzotriazoles
US5124723A (en) * 1989-08-25 1992-06-23 Ciba-Geigy Corporation Light-stabilized ink composition
US5498345A (en) * 1990-12-13 1996-03-12 Ciba-Geigy Corporation Aqueous dispersion of sparingly soluble UV absorbers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4041044A (en) * 1974-11-25 1977-08-09 Ciba-Geigy Corporation Process for the production of 2-aryl-2H-benzotriazoles
US5124723A (en) * 1989-08-25 1992-06-23 Ciba-Geigy Corporation Light-stabilized ink composition
US5498345A (en) * 1990-12-13 1996-03-12 Ciba-Geigy Corporation Aqueous dispersion of sparingly soluble UV absorbers

Also Published As

Publication number Publication date
AU2001279116A1 (en) 2003-02-17
WO2003011983A3 (en) 2009-06-11
AU2001279116A8 (en) 2009-07-30

Similar Documents

Publication Publication Date Title
US6706102B2 (en) Dye mixture for ink jet ink
US7066991B2 (en) Ink jet ink set
JP2009507991A (en) Inkjet ink and ink set
US6685768B2 (en) Ink jet ink set
US20050087099A1 (en) Ink jet ink set
RU2373239C2 (en) Dye sets for creation of images using paints for inkjet printers
US5795375A (en) Water color ink for recording and ink-jet recording process
CN114364755B (en) Dye ink composition, cyan dye ink, dye ink for inkjet recording, inkjet recording method, and dye aqueous solution
WO2008048872A1 (en) Ink compositions and methods for making the same
WO2012070645A1 (en) Ink set for inkjet recording, recording method, and colored material produced using the ink set
US6511170B1 (en) Ink jet printing method
US6511169B1 (en) Ink jet printing method
JP2002285048A (en) Ink-jet recording ink
JP2000178490A (en) Water-color ink and ink-jet recorder
JP3957423B2 (en) Aqueous magenta ink composition and ink jet recording method
US6251173B1 (en) Ink compositions containing ultraviolet absorbers
JPH11293164A (en) Water-based ink
JP2003238870A (en) Ink set and ink jet recording method
JP2003268281A (en) Ink-jet ink set
JP2002275402A (en) Ink set for ink jet recording
EP1281736A1 (en) Ink jet ink set and printing method
EP1281738B1 (en) Dye mixture for ink jet ink and printing method
WO2003104341A1 (en) Ink compositions containing ultraviolet absorbers
WO2003011983A2 (en) Ink compositions containing ultraviolet absorbers
JP5885665B2 (en) Ink set for ink jet recording, recording method, and colored body using the same

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IN IS JP KE KG KP KR KZ LC LK LR LS LU LV MA MD MG MK MN MW MX NZ PL PT RO RU SD SE SG SI SK SL TM TR TT TZ UA UG UZ VN YU ZA

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZW AM AZ BY KG KZ MD TJ TM AT BE CH CY DE DK ES FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase in:

Ref country code: DE

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase in:

Ref country code: JP