CA2100296A1 - Pigmented low volatile organic compound, ink jet composition and method - Google Patents
Pigmented low volatile organic compound, ink jet composition and methodInfo
- Publication number
- CA2100296A1 CA2100296A1 CA002100296A CA2100296A CA2100296A1 CA 2100296 A1 CA2100296 A1 CA 2100296A1 CA 002100296 A CA002100296 A CA 002100296A CA 2100296 A CA2100296 A CA 2100296A CA 2100296 A1 CA2100296 A1 CA 2100296A1
- Authority
- CA
- Canada
- Prior art keywords
- ink
- water
- composition
- ink jet
- volatile organic
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
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Classifications
-
- 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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
Abstract
ABSTRACT OF THE DISCLOSURE
An ink composition suitable for ink jet printing operations comprising an aqueous resin solution and an organic pigment where said ink composition is substantially free of volatile organic compounds.
Compositions are provided that form printed images that are solvent resistant to with isopropanol, ethanol, water, and mixtures thereof, and are retortable.
An ink composition suitable for ink jet printing operations comprising an aqueous resin solution and an organic pigment where said ink composition is substantially free of volatile organic compounds.
Compositions are provided that form printed images that are solvent resistant to with isopropanol, ethanol, water, and mixtures thereof, and are retortable.
Description
X~2~
PI~NENTED, LO~ VOLA~ ORGANIC CO~POUND, INR JE~ COMPO8I~ION ~D ~E~OD
FIELD OF ~HE INVENTION
The present invention relates to ink jet printing compositions and, more particularly, to ink jet printing compositisns that adhere to nonporous substrates and have reduced levels of volatile organic compounds.
}0 BACKGROUND OF THE INVENTION
Ink jet printing is a well-known technique by which printing is accomplished without contact between the printing device and the substrate on which the printed characters are deposited. Briefly described, ink jet printing involves the technique of projecting a stream of ink droplets to a surface and controlling the direction of the stream eleotronica}ly so that the droplets are cau~ed to form the desired printed image on that sur~ace. This technigue of noncontact printing is particularly well suited for application of characters onto irregularly shaped surfaces, including, for example, the botto~ of beverage containers.
In general, an ink jet composition must meet certain rigid requirements to be useful in ink jet printing ~5 operations~ These relate to viscosity, resistivity, solubility, compatibility of components and wetability o~
the substrate. Further, the ink must be quick-drying and smear resistant, must be capable of passlng through the ink jet nozzle wlthout clogging, and must permit rapid cleanup of the machine components with minimum ef~ort.
Many of the surfaces on which ink jet printing is utilized are nonporous, such as the above-mentioned beverage container. The ink used for these applications must adhere well to the nonporous substrate and normally must be water-resistant. Presently used ink for such applications conventionally contains a reRin, a dye, a carrier, and other components.
PI~NENTED, LO~ VOLA~ ORGANIC CO~POUND, INR JE~ COMPO8I~ION ~D ~E~OD
FIELD OF ~HE INVENTION
The present invention relates to ink jet printing compositions and, more particularly, to ink jet printing compositisns that adhere to nonporous substrates and have reduced levels of volatile organic compounds.
}0 BACKGROUND OF THE INVENTION
Ink jet printing is a well-known technique by which printing is accomplished without contact between the printing device and the substrate on which the printed characters are deposited. Briefly described, ink jet printing involves the technique of projecting a stream of ink droplets to a surface and controlling the direction of the stream eleotronica}ly so that the droplets are cau~ed to form the desired printed image on that sur~ace. This technigue of noncontact printing is particularly well suited for application of characters onto irregularly shaped surfaces, including, for example, the botto~ of beverage containers.
In general, an ink jet composition must meet certain rigid requirements to be useful in ink jet printing ~5 operations~ These relate to viscosity, resistivity, solubility, compatibility of components and wetability o~
the substrate. Further, the ink must be quick-drying and smear resistant, must be capable of passlng through the ink jet nozzle wlthout clogging, and must permit rapid cleanup of the machine components with minimum ef~ort.
Many of the surfaces on which ink jet printing is utilized are nonporous, such as the above-mentioned beverage container. The ink used for these applications must adhere well to the nonporous substrate and normally must be water-resistant. Presently used ink for such applications conventionally contains a reRin, a dye, a carrier, and other components.
2~ ~2~
Heretofore, to obtain satisfactory adhesion of a water-resistant ink jet composition to a nonporous substrata, it has been necessary to use an organic solvent as the carrier to dissolve the resin and/or the dye. For example, U.S. Patent No. 4,260,531 disicloses a~ ink jet printing composition comprising a styrene-acrylic copolymer resin, a dye, and a mixture of water and one or more water-miscible Cl-C3 alcohols as the dlluent. U.S.
Patent 4,246,154 discloses an ink jet printing composition comprising an aqueous vinyl polymer suspension which is added to a solution of a hydrophobic dye previously dissolved in an organic solvent.
Use of these organic solvents poses toxicity and flammability problems for the ink jet formulator.
However, the use of organic solvents i undesirable for an additional reason -- they pose an environmental hazard.
After the ink has been applied to the substrate, the solvent evaporates, releasing organic compounds into the atmosphere. These volatile organic compounds adversely affect the environment in the atmosphere and are the subject of both federal and state governmental regulations.
Volatile organic compounds, also known as VOC, are defined as any compound of carbon that evaporates from a paint or coating film under specific test conditionR. The amount of volatile organic compounds, present in a given composition in grams per liter of coating can be determined by using the following formula:
VOC (g/l) = Ws Ww ~ ~es V~n ~ Vw ~ V~s where W6 is the weight of volatile compounds in grams;
Ww is the weight o~ water in grams;
W~6 i~ the weight o~ exempt compounds in grams;
Vm is the volume o~ material in li~ers;
Vw is the volume of water in liters; and ~11 0~9~
Ves is the volume of exempt compounds in liter~.
In the above formula, exempt compounds are volatile organic compounds whose use is speci~ically sanctioned by regulatory agencies. Trichloroethane is an example of an exempt compound.
The ~aximum acceptable level of volatile organic compounds varies for different coating applications and from stats to state. For example, in California the maximum acceptable level of volatile organic compounds set for the aero~pace coatings industry is 340 grams~liter.
However, until the present invention, there was no pi~mented ink jet composition that met any of the government standards and still had the qualities necessary ~or sati~factory use in ink jet printing operations on nonporous substrates.
U.S. Patent No. 4,334,878 and Defensive Publication No. T 102,701 disclose ink jet compositions comprising a ; water-soluble dye, an ammonia soluble acrylic binder, and ammonium hydroxide. Japanese publication ~3-213583 relates to a general printing ink that employs an alkali-soluble resin, along with an alkaline reagent, in - combination with a pigment.
Copending application serial no. 07/692,300, by the same inventors as the pre~ent application, relates to an ink composition suitable for ink jet printing operations comprising an aqueous resin dispersion and an aqueous colorant where said ink composition is substantially free of volatile organic compounds. Such formulatîon~ have been found to give suitable results when the colorant is a dye, but uniformly ~ati~factory results have not been achieved when use is made of an organic piqment as the coloring agent. Further, when dyee are employed a~ the colorant, a natural limitation based upon tha ~olub~l~ty of the dye in the formulation is roached, that may not provide sufficient coloration ~or ~pecific applications.
.
s~ 9 ~
From the foregoing it is clear that a general need exists ~or a substantially volatile organic compound-~ree ink jet composition that contains organic pigments as the colorant, adheres to nonporous substrates, and is water-resistant, as well as ~or an ink jet composition which poses minimal toxicity and flammability problems, while being easily disposable by the formulator and end user. A specific need also exists ~or such an ink ~et composition suitable for use in ink jet printing operations on nonporous substrates which has a volatile organic compound level less than 500 grams/liter, preferably less than 340 grams/liter. Although such needs in the art have existed for years, no practical solution has yet been found.
Certain specialized application needs also exist which remain un~illed by present-day ink jet ~ormulations.
In many ins~ances printed images formed from the ink jet printing operation are printed onto substrates which must be sterilized, as through steam sterilization. For such applications, the ink jet formulation must be capable of forming printed images that remain substantially unaffected after retorting. Such retortability is especially critical with respect to containers ~or use in the food industry. Generally, such containers are made of glass or are can~ made of tin-free ~teel (I'TPS") or aluminum.
In other instances, the substrate with the printed image thereon must be exposed to aqueous and/or nonaqueous solvent-washing procedures. For such applications the jet ink must be capable of forming printed images that withstand solvents, such as isopropanol, ethanol, water, and mixtures thereof.
Hereto~ore, pigmented ink jet printing formulations meeting the aforementioned and other needs have not been availahle, or have been available only in formulations that contain large quantities of volatile solvents. Such :
~0~29~
needs are now satisfiad by the present invention, the description of which follows.
SUM~ARY OF THE INVENTION
The present invention provides an ink composition for use in ink jet applicationsl which i9 substantially ~ree of volatile organic compounds. The composition utilizes an aqueou~ resin solution and an organic pigment as the colorant, with substantially no organ~c solvent~. As a result, the toxicity, flammability and disposal problems inherent in the use o~ organic solvents are avoided. More importantly, the ink composition o~ the present invention complies w~th the present government standards for acceptable levels of volatile organic compounds.
Further, the present invention provides colored and black, ink jet compos1tions that directly, after application to a nonporous substrate, are retortable and resist solvents such as isopropanol, ethanol, water and mixtures thereof. Additionally, the present invention provides pigmented ink jet compositions that may be printed onto porous and nonporous substrates.
DETAILED DESCRIPTION OF THE PREFERRED EMBODTMENTS
As described hereinabove, the ink compositions of the present invention comprise an aqueous resin solution, an organic pigment, water, and other optional components which may be present in carefully balanced proportions to achieve preferred operation of the ink in an ink jet printing apparatus.
In one embodiment, the present invention provldes an ink composition suitable for ink jet printing onto a nonporous surface to ~orm printed images, as on glass, tin-ree steel and aluminum, capable of being retorted, without prior heat curin~ and being capable of being washed with water, isopropanol, ethanol, or mixtures ~ thereof, without substantial degradation of the printed - image~l said composition comprieing an aqueous re~in that ~ .
.
2~ 01~9~
is soluble in water at a basic pH and insoluble at acidic pH, said composition being substantially free of volatile organic compounds.
The present invention also provides a method of forming sterilized, printed images, on a nonporous substrate, such as glass, tin-free steel and aluminum, comprising printing onto said substrate, by ink jet printing, a jet ink comprising an aqueous resin that is soluble in water at a basic pH and insoluble at an acidic pHt said composition being substantially ~ree o~ volatile organic compounds and, without prior heat curing, retorting of said substrate.
In addition, there is provided a method of forming solvent-washed, printed images, on a nonporous substrate, such as glass, tin-free steel and aluminum, comprising printing onto said subætrate, by ink jet printing, a ~et ink comprising an aqueous resin that is soluble in water at a basic pH and insoluble at an acidic pH, and an organic pigment, said composition being substantially ~ree of volatile organic compounds and, without prior heat curing, washing the printed substrate with a solvent selected from the group consisting of ethanol, isopropanol, water and mixtures thereo~.
In general, the ink compositions o~ the present invention e~hibit the following characteristics ~or u~e in ink jet printing systems: (l) a viscosity from about 1.6 to about 7.0 centipoises at 25 C; (2) an electrical resistivity from about 50 to about 2000 ohm-cm; and (3) a sonic velocity from about 1200 to about 1300 meters/second.
The inks dry within about 4-10 seconds, with good adhesion when printed on nonporous substrates, such as bare tinplate, aluminum, polymeric-coated tin or aluminum, or polymeric-coated tin cans, TFS, glass, or aluminum.
The ink compositions of the present invention .may also be used for graphic applications on porous substrates such as paper, glossy paper, Tyvek~ envelopes, corrugated ' ,: , '~ ' 2 ~ ~
cardboard and other graphic paper products. Additionally, where carbon black is used as the colorant, the ink composition of the present invention can be used to print bar codes that can be scanned visually or by infrared (IR) spectroscopy.
The ink compositions of the present invention are, as indlcated, also substantlally free of vola~ile organic compounds. To be substantially free of volatile organic compounds (VOC), the ink composition should be formulated so that it has a volatile organic compound lev~l of less than 500 grams/li~er. Preferably, the ink compositions of the present invention have a volatile organic compound level of less than 340 grams/liter, with a volatile organic compound level of 300 gramstliter or le~s being most preferred.
The Resin Suitable aqueous resins ~or use in the ink compositions oP the present invention must meet certain requirements. The improved ink jet printing of the invention employs inks containing as binders polymers which have unesterified free carboxyl groups along their chains; or example, polymers or copolymers of acrylic or alkyl acrylic acids. In accordance with one aspect of the invention, these polymers are soluble in basic solutions of water. In accordance with a related aspect o~ the invention, where the solubilizing base is volatile, for example, ammonia obtained from a source such as ammonium hydroxida, ammonium carbonate, morpholine or th~ like, after drying, and removal of base by evaporation, the polymer is insoluble in water and alcohol, and is resistant to removal by abrasion.
The acrylic poly~er may be of any of a number of known polymers of acrylic or lower alkyl acrylic which have a plurality of carboxyl groups and which are soluble in basic ammonia watsr solutions. Such materials are commercially available as PHOPLEX B-336 of the Rohm and .
~o~
Haas Company; BRIGHT PLATE 23 and JONCRYL of S.C. Johnson and Sons, Inc.; and as CARBOSET resins from the B.F.
Goodrich Chemical Co. While higher molecular weigh~
materials can be employed, low to moderate molecular 5weights are preferred to obtain higher polymer content in the low viscosity inks.
The carboxylic acid group is an active group capable of being solubilized in the ink as by a fugitive amine such as ammonia. The other binder constituent is a 10compound of a group such as styrene which helps insolubilize the copolymer of acrylic ac~d once the ink is printed and some of the pH adjusting agent is driven off.
A copolymer of styrene and acrylic acid of a molecular weight of about 10,000, and having a styrene to 15acrylic acid proportion by weight of about 2 to 1 is most preferred. Once such binder is Joncryl 67, a styrenated acrylic from S.C. Johnson Co.
While Joncryl 67 represents the pre~erred binder component, other water saponifiable, styrene-acrylic acid 20or alkyl acrylate acid polymer can be used. The amount of such resinous binder can be varied within the range of about 5 to 20% by weight of the ink composition, but it is preferred to make use of an amount within the range of about 10 to about 15%, by weight of the ink compQsition.
25Other specific resins believed to be suitable in the inks of the present invention include Joncryl 682, 50, 57, 60, 134, and 142, styrene/acrylic resins, manufactured by Johnson Wax S.C., Johnson & Johnson, Inc.; Lucidene styrene/acrylic resin manufactured by Morton Chemical Co.
30a division of Morton Norwich Products Inc.; Roplex AC-417, AC-829, and AC-64 styrene/acrylic resin manufactured by Rohm and Haas Co.; PVP K 15, polyvinyl pyrrolidone manufactured by GAF Chemicals; Pentalyn 261, Dresinol 210 B. Natrosol, and Klucel rosin derivatives manufacture~ by 35Hercules Inc.; Scripset 550, modified polystyrene manufactured by Monsanto Co.; and Meoprene Latex 115, synthetic rubber manufactured by Du Pont.
9 ~
The pH Adiustinq Aqents It is important to include a basic reagent in the ink composition to insure that the resinous binders remain soluble throughout the range of wa~er content and throughout the period of storage and use. For this purpose, it is desirable to maintain the p~ of the ink at about 7.0-10.5, e.g., about 7.5 and 10. Tha pH is dependent upon the particular resin and other components which are employed. Although use can be made of inorganic bases such as sodium hydroxide and potassium hydroxide, their presence in the printed character lead~ to poor water resistance after drying. It is preferred to make use of an organic ba~e which can be eliminated by evaporation. Best use is made of a pH adjusting agent that evaporates rapidly to accelerate development of water resistance upon aging. Thus, while use can be made of organic amines, it is preferred to make use of ammonium hydroxide for controlling pH within the desired range.
Morpholine can also be used for long term stability during storage of the ink composition.
~ ecause ammonium hydroxide is also an ionizable material, it i5 also capable of imparting conductivity to the ink, bringing the resistivity down below 2000 ohm-cm and into the operating range for proper ink drop charging for jet printing.
The Piqm~nts The pigment partiales in the dispersion should be uniform in size, with a particle size from about 0.01 to about 1.0 microns and should be stable in dispersion.
Di~persion properties should remain constant at temperatures up to about 120F, and the dispersion should not show any sedimentation for at least 18 months. There should additionally be no agglomeration of pigmelnt particles in the disparsion.
As indicated, one of the organic pigments useful in the present invention is carbon black, which is 2 1 ~ fj -commercially available in a pigment dispersion as Black Acroverse Dispersion # 32B32D fro~ Penn Color.
Examples of other organic pigments useful in the present invention arP those pigments listed in Table 1 helow.
~ABLE 1 COLOR INDEX NUMBER PRODUCT NAME
__ _ _ Pigment Yellow 14 FLEXO PLUS Yellow Paste WY-7714 Pigment Yellow 14 FLEXO PLUS Yellow Paste WY-7724 Pigment Yellow 14 FLEXO PLUS Yellow Paste WY-7784 Pigment Orange 46 FLEXO P~US Orange Paste W0-7783 Pigment Red 49 FLEXO PLUS Red Paste WR-7789 Pigment Blue 15.3 FLEXO PLUS Blue Paste WB-7785 Pigment Blue 15:3 FLEXO PLUS Blue Paste WB-7715 RBH Dispersion, Inc. Calcium Lithol CI #15630.2 RBH Dispersion/ Inc. Lithol Rubine CI #15850.1 RBH Dispersion, Inc. Alkali Blue CI #42765.1 RBH Dispersion, Inc~ Phthalo Blue CI #74260 RBH Dispersion, Inc. Diarylide Yellow CI #21108 In general, an aqueous pigment dispersion should be present in the ink composition in an amount from about 5%
to about 20% by weight of the composition.
The Carrier Water is used as the carrier for the aqueous solution resin and the aqueous colorant in the ink compositions of the present invention. Typically, water is present in an amount from about 40% to about 80~ by weight o~ the ink composition, preferably from about 75% to about 85%.
The resins in the inks of the present invention are ~elievad to be present as true solutions. Howev~r, colloidal solutions may be used if filterable without substantial separation through a filter having a pore slze substantially smaller than the printer capillary tube, ior example through a filter having a pore size of about one micron.
2l0a2~6 Optional Curin~
curing may optionally be u~ed to increase solvent resistance. Curing may be accomplished under noncritical curing conditions. ~ypically, curing temperatures will be from about 100C to about 160C, pre~erably from about 125C to about 150C, and curing times will be from about 15 seconds to about 60 seconds, preferably from about 30 seconds to about 60 seconds. A general cure condition is about one minute at about 150 C. The ~emperature at which the heat curing occurs i~ not critical, nor ls ~he time of curing. Obviously, the length o~ the cure time will vary with the cure temperature. ~he only requirement is that the curing conditions be such that sub~tantial degradation of the components of the ink jet composition occurs.
Optional Com~onents Other components may also be included in the ink compositions of the present invention to impart characteristics desirable for ink jet printing applications. These components include defoamers, which improve processing and printer performance. Suitable de~oamers include acetylenic diols (commercially available as Surfynol 104 from Air Products and Chemicals, Inc.) and butanol. Small amount~ of organic ~olvents may also be added to improve drying time and reduce surface tension.
Suitable solvent include n-methyl-2-pyrrolidone and butanol.
It also may be desirable to add humectants, such as ethylene glycol or propylene glycol methyl ether, to prevent the ink jet tip from drying. Electrolytes can be added to adjust the specific resistivity of the ink.
Usable electrolytes includa dimethylamine hydrochloride and hydroxylamine hydrochloride. Finally, crosslink~ng resins, such a~ m~lamine resin~, may be added to cros~
link with other polymers to glve improved adhesion and increased solvent resistance.
21 ~02~
The following examples are illustrative of ink compositions of the present invention.
EXAMPLE I
The following composition was formulated:
Lithol Rubine Red Paste ~RBH, Inc.) 12.0% by weight Joncryl 67 resin (20.0 % in water) 50.0% hy weight DI Water 35.8% by weight Surfynol 104 (defoamer) 0.5% by weight N-methyl 2-pyrrolidone (solvent) 1.5% by weight Giv Gard DXN 0,2~ by weight 100.0% by weight The resulting ink composition had a viscosity of 4.5 cps, a resistivity o~ 67 ohm-cm, a pH of 9.13. The jet printed message adhered well to nonporous substrates such as tin plate, glass and plastics. The level o~ volatile organic compounds present in the ink composition was 132 grams/liter.
EXAMPLE II
The following composition was formulated:
5urfyno} 104 (1:1 in N-Methyl-2-Pyrrolidone) 0.5% by weight N-~ethyl-2-Pyrrolidone 1.5% by weight Giv-Gard DXN 0.2% by weiyht Water 45.8% by weiyht Joncryl 60 40.0% by weiyht Carbon Black Dispersion (Penn Color) 12.0~ by weiqht 100.0% by weight The resulting ink composition had a viscosity of 4.8 cps, a resistivity of 61 ohm-cm, a pH of 8.~. The jet printed message adhered well to nonporous substrates s~ch as tin plate, glass and plastics. The level of volati.le organ~c compounds present in the ink composition was 120 grams/liter.
210029~
EXAMPLE III
The following composition was formulated:
Surfynol 104 (1:1 in N-Methyl-2-Pyrrolidone) 0.5% by weight N-Methyl-2-Pyrrolidone1.5% by weight Giv-Gard DXM 0.2% by weight Water 39.8% by weight Joncryl 50 50.0% by weight Lithol Rubine 9~750 (RBH, Inc.~ 8.0~ by wei~
100.0~ by weight : The resulting ink composition had a viscosity of 6.15 cps, a resistivity of 67 ohm-cm, a pH of 8.8. The jet printed message adhered well to nonporous substrates such as tin plate, glass and plastics. The level of volatile organic compounds preSQnt in the ink composition was 60 grams/liter.
EXAMPLE IV
The ~ollowing composition was formulated:
Surfynol 104 (1:1 in N-Methyl-2-Pyrrolidone) 0.5% by weight N-Methyl-2-Pyrrolidone1.5% by weight : Giv-Gard DXM 0.2~ by weight Water 39.8% by weight ~: Joncryl 57 40.0% by weight Alkali Blue 97013 (RBH, Inc.) 8.0~ by weiqht 100.0% by weight The resulting ink composition had a viscosity of 5.20 cps, a resistivity of 59 ohm-cm, a pH of 8.9. The jet printed message adhered well to nonporous substrates such as tin plate, glass and plastics. The level of volat.ile organic compounds present in the ink composition was 62 grams/liter.
Heretofore, to obtain satisfactory adhesion of a water-resistant ink jet composition to a nonporous substrata, it has been necessary to use an organic solvent as the carrier to dissolve the resin and/or the dye. For example, U.S. Patent No. 4,260,531 disicloses a~ ink jet printing composition comprising a styrene-acrylic copolymer resin, a dye, and a mixture of water and one or more water-miscible Cl-C3 alcohols as the dlluent. U.S.
Patent 4,246,154 discloses an ink jet printing composition comprising an aqueous vinyl polymer suspension which is added to a solution of a hydrophobic dye previously dissolved in an organic solvent.
Use of these organic solvents poses toxicity and flammability problems for the ink jet formulator.
However, the use of organic solvents i undesirable for an additional reason -- they pose an environmental hazard.
After the ink has been applied to the substrate, the solvent evaporates, releasing organic compounds into the atmosphere. These volatile organic compounds adversely affect the environment in the atmosphere and are the subject of both federal and state governmental regulations.
Volatile organic compounds, also known as VOC, are defined as any compound of carbon that evaporates from a paint or coating film under specific test conditionR. The amount of volatile organic compounds, present in a given composition in grams per liter of coating can be determined by using the following formula:
VOC (g/l) = Ws Ww ~ ~es V~n ~ Vw ~ V~s where W6 is the weight of volatile compounds in grams;
Ww is the weight o~ water in grams;
W~6 i~ the weight o~ exempt compounds in grams;
Vm is the volume o~ material in li~ers;
Vw is the volume of water in liters; and ~11 0~9~
Ves is the volume of exempt compounds in liter~.
In the above formula, exempt compounds are volatile organic compounds whose use is speci~ically sanctioned by regulatory agencies. Trichloroethane is an example of an exempt compound.
The ~aximum acceptable level of volatile organic compounds varies for different coating applications and from stats to state. For example, in California the maximum acceptable level of volatile organic compounds set for the aero~pace coatings industry is 340 grams~liter.
However, until the present invention, there was no pi~mented ink jet composition that met any of the government standards and still had the qualities necessary ~or sati~factory use in ink jet printing operations on nonporous substrates.
U.S. Patent No. 4,334,878 and Defensive Publication No. T 102,701 disclose ink jet compositions comprising a ; water-soluble dye, an ammonia soluble acrylic binder, and ammonium hydroxide. Japanese publication ~3-213583 relates to a general printing ink that employs an alkali-soluble resin, along with an alkaline reagent, in - combination with a pigment.
Copending application serial no. 07/692,300, by the same inventors as the pre~ent application, relates to an ink composition suitable for ink jet printing operations comprising an aqueous resin dispersion and an aqueous colorant where said ink composition is substantially free of volatile organic compounds. Such formulatîon~ have been found to give suitable results when the colorant is a dye, but uniformly ~ati~factory results have not been achieved when use is made of an organic piqment as the coloring agent. Further, when dyee are employed a~ the colorant, a natural limitation based upon tha ~olub~l~ty of the dye in the formulation is roached, that may not provide sufficient coloration ~or ~pecific applications.
.
s~ 9 ~
From the foregoing it is clear that a general need exists ~or a substantially volatile organic compound-~ree ink jet composition that contains organic pigments as the colorant, adheres to nonporous substrates, and is water-resistant, as well as ~or an ink jet composition which poses minimal toxicity and flammability problems, while being easily disposable by the formulator and end user. A specific need also exists ~or such an ink ~et composition suitable for use in ink jet printing operations on nonporous substrates which has a volatile organic compound level less than 500 grams/liter, preferably less than 340 grams/liter. Although such needs in the art have existed for years, no practical solution has yet been found.
Certain specialized application needs also exist which remain un~illed by present-day ink jet ~ormulations.
In many ins~ances printed images formed from the ink jet printing operation are printed onto substrates which must be sterilized, as through steam sterilization. For such applications, the ink jet formulation must be capable of forming printed images that remain substantially unaffected after retorting. Such retortability is especially critical with respect to containers ~or use in the food industry. Generally, such containers are made of glass or are can~ made of tin-free ~teel (I'TPS") or aluminum.
In other instances, the substrate with the printed image thereon must be exposed to aqueous and/or nonaqueous solvent-washing procedures. For such applications the jet ink must be capable of forming printed images that withstand solvents, such as isopropanol, ethanol, water, and mixtures thereof.
Hereto~ore, pigmented ink jet printing formulations meeting the aforementioned and other needs have not been availahle, or have been available only in formulations that contain large quantities of volatile solvents. Such :
~0~29~
needs are now satisfiad by the present invention, the description of which follows.
SUM~ARY OF THE INVENTION
The present invention provides an ink composition for use in ink jet applicationsl which i9 substantially ~ree of volatile organic compounds. The composition utilizes an aqueou~ resin solution and an organic pigment as the colorant, with substantially no organ~c solvent~. As a result, the toxicity, flammability and disposal problems inherent in the use o~ organic solvents are avoided. More importantly, the ink composition o~ the present invention complies w~th the present government standards for acceptable levels of volatile organic compounds.
Further, the present invention provides colored and black, ink jet compos1tions that directly, after application to a nonporous substrate, are retortable and resist solvents such as isopropanol, ethanol, water and mixtures thereof. Additionally, the present invention provides pigmented ink jet compositions that may be printed onto porous and nonporous substrates.
DETAILED DESCRIPTION OF THE PREFERRED EMBODTMENTS
As described hereinabove, the ink compositions of the present invention comprise an aqueous resin solution, an organic pigment, water, and other optional components which may be present in carefully balanced proportions to achieve preferred operation of the ink in an ink jet printing apparatus.
In one embodiment, the present invention provldes an ink composition suitable for ink jet printing onto a nonporous surface to ~orm printed images, as on glass, tin-ree steel and aluminum, capable of being retorted, without prior heat curin~ and being capable of being washed with water, isopropanol, ethanol, or mixtures ~ thereof, without substantial degradation of the printed - image~l said composition comprieing an aqueous re~in that ~ .
.
2~ 01~9~
is soluble in water at a basic pH and insoluble at acidic pH, said composition being substantially free of volatile organic compounds.
The present invention also provides a method of forming sterilized, printed images, on a nonporous substrate, such as glass, tin-free steel and aluminum, comprising printing onto said substrate, by ink jet printing, a jet ink comprising an aqueous resin that is soluble in water at a basic pH and insoluble at an acidic pHt said composition being substantially ~ree o~ volatile organic compounds and, without prior heat curing, retorting of said substrate.
In addition, there is provided a method of forming solvent-washed, printed images, on a nonporous substrate, such as glass, tin-free steel and aluminum, comprising printing onto said subætrate, by ink jet printing, a ~et ink comprising an aqueous resin that is soluble in water at a basic pH and insoluble at an acidic pH, and an organic pigment, said composition being substantially ~ree of volatile organic compounds and, without prior heat curing, washing the printed substrate with a solvent selected from the group consisting of ethanol, isopropanol, water and mixtures thereo~.
In general, the ink compositions o~ the present invention e~hibit the following characteristics ~or u~e in ink jet printing systems: (l) a viscosity from about 1.6 to about 7.0 centipoises at 25 C; (2) an electrical resistivity from about 50 to about 2000 ohm-cm; and (3) a sonic velocity from about 1200 to about 1300 meters/second.
The inks dry within about 4-10 seconds, with good adhesion when printed on nonporous substrates, such as bare tinplate, aluminum, polymeric-coated tin or aluminum, or polymeric-coated tin cans, TFS, glass, or aluminum.
The ink compositions of the present invention .may also be used for graphic applications on porous substrates such as paper, glossy paper, Tyvek~ envelopes, corrugated ' ,: , '~ ' 2 ~ ~
cardboard and other graphic paper products. Additionally, where carbon black is used as the colorant, the ink composition of the present invention can be used to print bar codes that can be scanned visually or by infrared (IR) spectroscopy.
The ink compositions of the present invention are, as indlcated, also substantlally free of vola~ile organic compounds. To be substantially free of volatile organic compounds (VOC), the ink composition should be formulated so that it has a volatile organic compound lev~l of less than 500 grams/li~er. Preferably, the ink compositions of the present invention have a volatile organic compound level of less than 340 grams/liter, with a volatile organic compound level of 300 gramstliter or le~s being most preferred.
The Resin Suitable aqueous resins ~or use in the ink compositions oP the present invention must meet certain requirements. The improved ink jet printing of the invention employs inks containing as binders polymers which have unesterified free carboxyl groups along their chains; or example, polymers or copolymers of acrylic or alkyl acrylic acids. In accordance with one aspect of the invention, these polymers are soluble in basic solutions of water. In accordance with a related aspect o~ the invention, where the solubilizing base is volatile, for example, ammonia obtained from a source such as ammonium hydroxida, ammonium carbonate, morpholine or th~ like, after drying, and removal of base by evaporation, the polymer is insoluble in water and alcohol, and is resistant to removal by abrasion.
The acrylic poly~er may be of any of a number of known polymers of acrylic or lower alkyl acrylic which have a plurality of carboxyl groups and which are soluble in basic ammonia watsr solutions. Such materials are commercially available as PHOPLEX B-336 of the Rohm and .
~o~
Haas Company; BRIGHT PLATE 23 and JONCRYL of S.C. Johnson and Sons, Inc.; and as CARBOSET resins from the B.F.
Goodrich Chemical Co. While higher molecular weigh~
materials can be employed, low to moderate molecular 5weights are preferred to obtain higher polymer content in the low viscosity inks.
The carboxylic acid group is an active group capable of being solubilized in the ink as by a fugitive amine such as ammonia. The other binder constituent is a 10compound of a group such as styrene which helps insolubilize the copolymer of acrylic ac~d once the ink is printed and some of the pH adjusting agent is driven off.
A copolymer of styrene and acrylic acid of a molecular weight of about 10,000, and having a styrene to 15acrylic acid proportion by weight of about 2 to 1 is most preferred. Once such binder is Joncryl 67, a styrenated acrylic from S.C. Johnson Co.
While Joncryl 67 represents the pre~erred binder component, other water saponifiable, styrene-acrylic acid 20or alkyl acrylate acid polymer can be used. The amount of such resinous binder can be varied within the range of about 5 to 20% by weight of the ink composition, but it is preferred to make use of an amount within the range of about 10 to about 15%, by weight of the ink compQsition.
25Other specific resins believed to be suitable in the inks of the present invention include Joncryl 682, 50, 57, 60, 134, and 142, styrene/acrylic resins, manufactured by Johnson Wax S.C., Johnson & Johnson, Inc.; Lucidene styrene/acrylic resin manufactured by Morton Chemical Co.
30a division of Morton Norwich Products Inc.; Roplex AC-417, AC-829, and AC-64 styrene/acrylic resin manufactured by Rohm and Haas Co.; PVP K 15, polyvinyl pyrrolidone manufactured by GAF Chemicals; Pentalyn 261, Dresinol 210 B. Natrosol, and Klucel rosin derivatives manufacture~ by 35Hercules Inc.; Scripset 550, modified polystyrene manufactured by Monsanto Co.; and Meoprene Latex 115, synthetic rubber manufactured by Du Pont.
9 ~
The pH Adiustinq Aqents It is important to include a basic reagent in the ink composition to insure that the resinous binders remain soluble throughout the range of wa~er content and throughout the period of storage and use. For this purpose, it is desirable to maintain the p~ of the ink at about 7.0-10.5, e.g., about 7.5 and 10. Tha pH is dependent upon the particular resin and other components which are employed. Although use can be made of inorganic bases such as sodium hydroxide and potassium hydroxide, their presence in the printed character lead~ to poor water resistance after drying. It is preferred to make use of an organic ba~e which can be eliminated by evaporation. Best use is made of a pH adjusting agent that evaporates rapidly to accelerate development of water resistance upon aging. Thus, while use can be made of organic amines, it is preferred to make use of ammonium hydroxide for controlling pH within the desired range.
Morpholine can also be used for long term stability during storage of the ink composition.
~ ecause ammonium hydroxide is also an ionizable material, it i5 also capable of imparting conductivity to the ink, bringing the resistivity down below 2000 ohm-cm and into the operating range for proper ink drop charging for jet printing.
The Piqm~nts The pigment partiales in the dispersion should be uniform in size, with a particle size from about 0.01 to about 1.0 microns and should be stable in dispersion.
Di~persion properties should remain constant at temperatures up to about 120F, and the dispersion should not show any sedimentation for at least 18 months. There should additionally be no agglomeration of pigmelnt particles in the disparsion.
As indicated, one of the organic pigments useful in the present invention is carbon black, which is 2 1 ~ fj -commercially available in a pigment dispersion as Black Acroverse Dispersion # 32B32D fro~ Penn Color.
Examples of other organic pigments useful in the present invention arP those pigments listed in Table 1 helow.
~ABLE 1 COLOR INDEX NUMBER PRODUCT NAME
__ _ _ Pigment Yellow 14 FLEXO PLUS Yellow Paste WY-7714 Pigment Yellow 14 FLEXO PLUS Yellow Paste WY-7724 Pigment Yellow 14 FLEXO PLUS Yellow Paste WY-7784 Pigment Orange 46 FLEXO P~US Orange Paste W0-7783 Pigment Red 49 FLEXO PLUS Red Paste WR-7789 Pigment Blue 15.3 FLEXO PLUS Blue Paste WB-7785 Pigment Blue 15:3 FLEXO PLUS Blue Paste WB-7715 RBH Dispersion, Inc. Calcium Lithol CI #15630.2 RBH Dispersion/ Inc. Lithol Rubine CI #15850.1 RBH Dispersion, Inc. Alkali Blue CI #42765.1 RBH Dispersion, Inc~ Phthalo Blue CI #74260 RBH Dispersion, Inc. Diarylide Yellow CI #21108 In general, an aqueous pigment dispersion should be present in the ink composition in an amount from about 5%
to about 20% by weight of the composition.
The Carrier Water is used as the carrier for the aqueous solution resin and the aqueous colorant in the ink compositions of the present invention. Typically, water is present in an amount from about 40% to about 80~ by weight o~ the ink composition, preferably from about 75% to about 85%.
The resins in the inks of the present invention are ~elievad to be present as true solutions. Howev~r, colloidal solutions may be used if filterable without substantial separation through a filter having a pore slze substantially smaller than the printer capillary tube, ior example through a filter having a pore size of about one micron.
2l0a2~6 Optional Curin~
curing may optionally be u~ed to increase solvent resistance. Curing may be accomplished under noncritical curing conditions. ~ypically, curing temperatures will be from about 100C to about 160C, pre~erably from about 125C to about 150C, and curing times will be from about 15 seconds to about 60 seconds, preferably from about 30 seconds to about 60 seconds. A general cure condition is about one minute at about 150 C. The ~emperature at which the heat curing occurs i~ not critical, nor ls ~he time of curing. Obviously, the length o~ the cure time will vary with the cure temperature. ~he only requirement is that the curing conditions be such that sub~tantial degradation of the components of the ink jet composition occurs.
Optional Com~onents Other components may also be included in the ink compositions of the present invention to impart characteristics desirable for ink jet printing applications. These components include defoamers, which improve processing and printer performance. Suitable de~oamers include acetylenic diols (commercially available as Surfynol 104 from Air Products and Chemicals, Inc.) and butanol. Small amount~ of organic ~olvents may also be added to improve drying time and reduce surface tension.
Suitable solvent include n-methyl-2-pyrrolidone and butanol.
It also may be desirable to add humectants, such as ethylene glycol or propylene glycol methyl ether, to prevent the ink jet tip from drying. Electrolytes can be added to adjust the specific resistivity of the ink.
Usable electrolytes includa dimethylamine hydrochloride and hydroxylamine hydrochloride. Finally, crosslink~ng resins, such a~ m~lamine resin~, may be added to cros~
link with other polymers to glve improved adhesion and increased solvent resistance.
21 ~02~
The following examples are illustrative of ink compositions of the present invention.
EXAMPLE I
The following composition was formulated:
Lithol Rubine Red Paste ~RBH, Inc.) 12.0% by weight Joncryl 67 resin (20.0 % in water) 50.0% hy weight DI Water 35.8% by weight Surfynol 104 (defoamer) 0.5% by weight N-methyl 2-pyrrolidone (solvent) 1.5% by weight Giv Gard DXN 0,2~ by weight 100.0% by weight The resulting ink composition had a viscosity of 4.5 cps, a resistivity o~ 67 ohm-cm, a pH of 9.13. The jet printed message adhered well to nonporous substrates such as tin plate, glass and plastics. The level o~ volatile organic compounds present in the ink composition was 132 grams/liter.
EXAMPLE II
The following composition was formulated:
5urfyno} 104 (1:1 in N-Methyl-2-Pyrrolidone) 0.5% by weight N-~ethyl-2-Pyrrolidone 1.5% by weight Giv-Gard DXN 0.2% by weiyht Water 45.8% by weiyht Joncryl 60 40.0% by weiyht Carbon Black Dispersion (Penn Color) 12.0~ by weiqht 100.0% by weight The resulting ink composition had a viscosity of 4.8 cps, a resistivity of 61 ohm-cm, a pH of 8.~. The jet printed message adhered well to nonporous substrates s~ch as tin plate, glass and plastics. The level of volati.le organ~c compounds present in the ink composition was 120 grams/liter.
210029~
EXAMPLE III
The following composition was formulated:
Surfynol 104 (1:1 in N-Methyl-2-Pyrrolidone) 0.5% by weight N-Methyl-2-Pyrrolidone1.5% by weight Giv-Gard DXM 0.2% by weight Water 39.8% by weight Joncryl 50 50.0% by weight Lithol Rubine 9~750 (RBH, Inc.~ 8.0~ by wei~
100.0~ by weight : The resulting ink composition had a viscosity of 6.15 cps, a resistivity of 67 ohm-cm, a pH of 8.8. The jet printed message adhered well to nonporous substrates such as tin plate, glass and plastics. The level of volatile organic compounds preSQnt in the ink composition was 60 grams/liter.
EXAMPLE IV
The ~ollowing composition was formulated:
Surfynol 104 (1:1 in N-Methyl-2-Pyrrolidone) 0.5% by weight N-Methyl-2-Pyrrolidone1.5% by weight : Giv-Gard DXM 0.2~ by weight Water 39.8% by weight ~: Joncryl 57 40.0% by weight Alkali Blue 97013 (RBH, Inc.) 8.0~ by weiqht 100.0% by weight The resulting ink composition had a viscosity of 5.20 cps, a resistivity of 59 ohm-cm, a pH of 8.9. The jet printed message adhered well to nonporous substrates such as tin plate, glass and plastics. The level of volat.ile organic compounds present in the ink composition was 62 grams/liter.
Claims (9)
1. An ink composition suitable for ink jet printing operations comprising an aqueous resin solution and an organic pigment, said composition being substantially free of volatile organic compounds, said aqueous resin solution comprising water and a resin that is soluble in water at a basic pH and insoluble in water at an acidic pH, and a sufficient amount of a basic pH adjusting agent to render the resin soluble in the water.
2. The ink composition of claim 1 wherein the resin is present in an amount from about 20 weight percent to about 60 weight percent, based on the total weight of the composition.
3. The ink composition of claim 1 which has a viscosity from about 1.6 to about 7.0 centipoises at 25°C.
and an electrical resistivity from about 50 to about 2000 ohm-cm.
and an electrical resistivity from about 50 to about 2000 ohm-cm.
4. The ink composition of claim 1 wherein the volatile organic compounds are present in an amount less than about 340 grams/liter.
5. The ink composition of claim 1 wherein the volatile organic compounds are present in an amount less than about 300 grams/liter.
6. The ink composition of claim 1 that is bar code readable.
7. An ink composition suitable for ink jet printing onto a nonporous surface selected from the group consisting of glass, tin-free steel and aluminum, to form printed images on glass, tin-free steel and aluminum capable of being retorted, capable of being washed with water, isopropanol, ethanol, or mixtures thereof, without substantial degradation of the printed images, said aqueous resin solution comprising water and a resin that is soluble in water at a basic pH and insoluble in water at an acidic pH, and sufficient amount of a basic pH
adjusting-agent to rende ? e ?esin soluble in the water, said composition being ?s?tially free of volatile organic compounds.
adjusting-agent to rende ? e ?esin soluble in the water, said composition being ?s?tially free of volatile organic compounds.
8. A method of forming sterilized, printed images, on a nonporous substrate selected from the group consisting of glass, tin-free steel and aluminum, comprising printing onto said substrate, by ink jet printing, the jet ink of claim 7.
9. A method of forming solvent-washed, printed images, on a nonporous substrate selected from the group consisting of glass, tin-free steel and aluminum, comprising printing onto said substrate, by ink jet printing, the jet ink of claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/958,267 US5316575A (en) | 1992-10-08 | 1992-10-08 | Pigmented, low volatile organic compound, ink jet composition and method |
| US958,267 | 1992-10-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2100296A1 true CA2100296A1 (en) | 1994-04-09 |
Family
ID=25500799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002100296A Abandoned CA2100296A1 (en) | 1992-10-08 | 1993-07-09 | Pigmented low volatile organic compound, ink jet composition and method |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5316575A (en) |
| CA (1) | CA2100296A1 (en) |
Families Citing this family (62)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2043246C (en) * | 1990-06-25 | 1997-05-13 | Bruce A. Lent | Ink jet composition and method |
| DE69420065T2 (en) * | 1993-03-15 | 2000-04-20 | Canon Kk | Ink, ink jet recording method using the same, and apparatus |
| JP2672458B2 (en) * | 1993-11-05 | 1997-11-05 | ツヤック株式会社 | Low temperature dyeing agent for protein fiber products and dyeing method using the same |
| US5973025A (en) * | 1994-04-12 | 1999-10-26 | Sri International | Aqueous ink compositions containing a binder of a neutralized acidic resin |
| MX9705875A (en) * | 1995-02-03 | 1997-12-31 | Videojet Systems Internat | An ink composition. |
| US5594044A (en) * | 1995-03-03 | 1997-01-14 | Videojet Systems International, Inc. | Ink jet ink which is rub resistant to alcohol |
| EP0732382B1 (en) * | 1995-03-17 | 1999-06-02 | Toyo Ink Manufacturing Co., Ltd. | Inkjet ink and process for the production thereof |
| US5596027A (en) * | 1995-07-13 | 1997-01-21 | Videojet Systems International, Inc. | Condensation and water resistant jet ink |
| US6060537A (en) * | 1995-12-12 | 2000-05-09 | Matthews International Corporation | Water based ink jet printing ink |
| US5889083A (en) * | 1996-09-06 | 1999-03-30 | Videojet Systems International, Inc. | Aqueous jet ink compositions |
| US5925692A (en) * | 1997-03-12 | 1999-07-20 | Lexmark International, Inc. | High performance ink compositions |
| US5994427A (en) * | 1997-03-12 | 1999-11-30 | Lexmark International, Inc. | High performance ink compositions with non-benzidine based colorants |
| US6063631A (en) * | 1997-05-21 | 2000-05-16 | 3M Innovative Properties Company | Sterilization indicator |
| US6238623B1 (en) | 1997-05-21 | 2001-05-29 | 3M Innovative Properties Company | Labels and tracking systems for sterilization procedures |
| US6287518B1 (en) | 1997-06-25 | 2001-09-11 | 3M Innovative Properties Company | Sterilization monitors |
| US6302536B1 (en) | 1997-07-31 | 2001-10-16 | Trident International, Inc. | Fast drying ink jet ink compositions for capping ink jet printer nozzles |
| DE69936410T2 (en) | 1998-02-27 | 2008-02-28 | Videojet Technologies Inc., Wood Dale | Fast drying ink jet ink composition |
| US6251175B1 (en) * | 1998-08-06 | 2001-06-26 | Marconi Data Systems Inc. | Jet ink composition |
| US6439709B1 (en) | 1998-09-04 | 2002-08-27 | Trident International, Inc. | Method for reducing cavitation in impulse ink jet printing device |
| US7030173B2 (en) * | 1998-09-04 | 2006-04-18 | Illinois Tool Works, Inc. | High resolution pigment ink for impulse ink jet printing |
| US6391943B2 (en) | 1998-09-04 | 2002-05-21 | Trident International, Inc. | High resolution pigment ink for impulse ink jet printing |
| US6688738B2 (en) | 1998-09-04 | 2004-02-10 | Illinois Tool Works Inc | Method for reducing cavitation in impulse ink jet printing devices |
| US6281267B2 (en) | 1998-10-29 | 2001-08-28 | Hewlett-Packard Company | Ink to ink bleed and halo control using specific polymers in ink-jet printing inks |
| US6300391B2 (en) | 1998-10-29 | 2001-10-09 | Hewlett-Packard Company | Inks containing glycol ethers and specific polymers for dry time and bleed improvements in ink-jet printing inks |
| US6455132B1 (en) | 1999-02-04 | 2002-09-24 | Kodak Polychrome Graphics Llc | Lithographic printing printable media and process for the production thereof |
| US6231654B1 (en) * | 1999-04-30 | 2001-05-15 | Macdermid Acumen, Inc. | Ink composition and a method of making the ink composition |
| US6485979B1 (en) | 1999-08-05 | 2002-11-26 | 3M Innovative Properties Company | Electronic system for tracking and monitoring articles to be sterilized and associated method |
| US6478862B1 (en) | 2000-03-14 | 2002-11-12 | Macdermid Acumen, Inc. | Pigmented inks and a method of making pigmented inks |
| US6500880B1 (en) | 2000-10-26 | 2002-12-31 | Hewlett-Packard Comapny | Black to color bleed control using specific polymers in ink-jet printing inks containing pigmented inks requiring dispersants |
| JP2004526019A (en) | 2001-02-16 | 2004-08-26 | マクダーミド・カラースパン・インコーポレーテツド | Direct dye ink and method for producing direct dye ink |
| GB0123505D0 (en) * | 2001-09-28 | 2001-11-21 | Coates Electrographics Ltd | Ink jet inks for use on textile materials, and their use |
| US6779530B2 (en) * | 2002-01-23 | 2004-08-24 | Schweitzer-Mauduit International, Inc. | Smoking articles with reduced ignition proclivity characteristics |
| US20040071953A1 (en) * | 2002-09-30 | 2004-04-15 | Sobieski Robert T. | Ink formulations and methods |
| US7431956B2 (en) * | 2003-06-20 | 2008-10-07 | Sensient Imaging Technologies, Inc. | Food grade colored fluids for printing on edible substrates |
| US7001936B2 (en) * | 2003-07-16 | 2006-02-21 | Lexmark International, Inc. | Pigmented inkjet ink |
| DE10347034B4 (en) * | 2003-10-09 | 2006-11-09 | J. S. Staedtler Gmbh & Co. Kg | Using an ink |
| US7081158B2 (en) * | 2003-11-21 | 2006-07-25 | Imaje S.A. | Ink composition for continuous deflected jet printing, especially on letters and postal articles |
| US7247199B2 (en) * | 2004-05-12 | 2007-07-24 | Baydo Robert A | Food grade ink jet inks for printing on edible substrates |
| US7431957B2 (en) * | 2004-06-10 | 2008-10-07 | Sensient Imaging Technologies, Inc. | Food grade ink jet inks for printing on edible substrates |
| US8151806B2 (en) * | 2005-02-07 | 2012-04-10 | Schweitzer-Mauduit International, Inc. | Smoking articles having reduced analyte levels and process for making same |
| FR2883294B1 (en) * | 2005-03-18 | 2009-03-06 | Imaje Sa Sa | INK COMPOSITION FOR CONTINUOUS JET PRINTING DEVICE |
| US20080032011A1 (en) * | 2005-07-01 | 2008-02-07 | Sensient Colors Inc. | Flavored and Edible Colored Fluids for Printing on Edible Substrates and Precision Deposition Thereof |
| EP2277957A1 (en) * | 2005-07-01 | 2011-01-26 | Sensient Imaging Technologies Inc. | Ink-jettable flavored fluids for printing on edible substrates |
| US20070129463A1 (en) * | 2005-12-05 | 2007-06-07 | Zeying Ma | Pigment-based ink formulations including dispersants and binders and methods of making same |
| US20070231435A1 (en) | 2006-03-29 | 2007-10-04 | Wm Wrigley Jr. Company | Non-contact printed edible product and method for producing same |
| US20090186121A1 (en) * | 2006-05-01 | 2009-07-23 | Sensient Colors Inc. | Modified edible substrates suitable for printing |
| US8869805B2 (en) * | 2006-06-01 | 2014-10-28 | Schweitzer-Mauduit International, Inc. | Free air burning smoking articles with reduced ignition proclivity characteristics |
| US10531681B2 (en) * | 2008-04-25 | 2020-01-14 | Sensient Colors Llc | Heat-triggered colorants and methods of making and using the same |
| US20090298952A1 (en) * | 2008-05-07 | 2009-12-03 | Brimmer Karen S | Platable soluble dyes |
| US9113647B2 (en) * | 2008-08-29 | 2015-08-25 | Sensient Colors Llc | Flavored and edible colored waxes and methods for precision deposition on edible substrates |
| FR2943068B1 (en) | 2009-03-13 | 2011-04-15 | Markem Imaje | INK COMPOSITION FOR CONTINUOUS JET PRINTING IN PARTICULAR ON WET GLASS |
| CN102449557B (en) | 2009-06-30 | 2013-08-07 | 惠普深蓝有限责任公司 | Marking agent concentration methods, marking agents, and hard imaging methods |
| FR2957605B1 (en) | 2010-03-19 | 2012-05-18 | Markem Imaje | INK COMPOSITION FOR FLUID PRINTING. |
| EP2582762B1 (en) * | 2010-06-16 | 2014-04-30 | Hewlett-Packard Development Company, L.P. | Blue ink for postage printing |
| FR2972457B1 (en) | 2011-03-09 | 2014-09-12 | Markem Imaje | INK COMPOSITION FOR CONTINUOUS JET PRINTING. |
| US9247769B2 (en) | 2012-10-11 | 2016-02-02 | Schweitzer-Mauduit International, Inc. | Wrapper having reduced ignition proclivity characteristics |
| FR2997956B1 (en) | 2012-11-15 | 2015-04-10 | Markem Imaje | INK COMPOSITION FOR CONTINUOUS JET PRINTING IN PARTICULAR ON ORGANIC POLYMER SUBSTRATES. |
| FR3001733B1 (en) | 2013-02-01 | 2015-03-20 | Markem Imaje | INK COMPOSITION FOR FLUID PRINTING. |
| US20170114238A1 (en) * | 2014-05-29 | 2017-04-27 | E I Du Pont De Nemours And Company | Aqueous ink-jet ink comprising an antifoaming agent |
| FR3022913B1 (en) | 2014-06-26 | 2017-12-22 | Markem-Imaje Holding | INK COMPOSITION FOR CONTINUOUS JET PRINTING, IN PARTICULAR FOR SECURITY MARKINGS. |
| FR3033572B1 (en) | 2015-03-13 | 2019-05-10 | Dover Europe Sarl | INK COMPOSITION FOR CONTINUOUS JET PRINTING IN PARTICULAR ON ORGANIC POLYMER SUBSTRATES. |
| FR3046418B1 (en) | 2016-01-06 | 2020-04-24 | Dover Europe Sarl | LIQUID COMPOSITION, ESPECIALLY INKED, FOR CONTINUOUS JET BINARY JET PRINTING WITH UNLOADED DROPS, USE OF SAID COMPOSITION, MARKING METHOD, AND SUBSTRATE MARKED. |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072644A (en) * | 1976-05-17 | 1978-02-07 | Monsanto Company | Water based printing ink |
| US4963188A (en) * | 1988-09-30 | 1990-10-16 | Union Camp Corporation | Novel water-based ink composition |
-
1992
- 1992-10-08 US US07/958,267 patent/US5316575A/en not_active Expired - Fee Related
-
1993
- 1993-07-09 CA CA002100296A patent/CA2100296A1/en not_active Abandoned
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| US5316575A (en) | 1994-05-31 |
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