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Patent US5973036 - Reversibly-crosslinked-polymers for shear-thinning phase change ink jet inks - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsPhase-change (hot melt) ink compositions for use in a phase change (hot melt) ink jet recording device are disclosed to comprise: (a) from about 0.1% to about 30% of one or more colorants; and (b) from about 0.1 to about 99.9% of one or more reversibly-crosslinked-polymers. Recording is conducted by...http://www.google.com/patents/US5973036?utm_source=gb-gplus-sharePatent US5973036 - Reversibly-crosslinked-polymers for shear-thinning phase change ink jet inksAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS5973036 APublication typeGrantApplication numberUS 09/074,756Publication dateOct 26, 1999Filing dateMay 8, 1998Priority dateMay 8, 1998Fee statusLapsedAlso published asCA2279614A1Publication number074756, 09074756, US 5973036 A, US 5973036A, US-A-5973036, US5973036 A, US5973036AInventorsMichael D. Matzinger, Robert P. RodebaughOriginal AssigneeWestvaco CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (3), Referenced by (21), Classifications (29), Legal Events (7) External Links: USPTO, USPTO Assignment, EspacenetReversibly-crosslinked-polymers for shear-thinning phase change ink jet inks
1. A reversibly-crosslinked-polymer composition useful in phase change ink jet inks comprising a polymer selected from the group consisting of alginic acid, carboxymethyl cellulose, pectinic acid, rosin esters, lignosulfonates, nitrocellulose, alcohol-soluble polysaccharides, polyacrylamide, polyacrylic acid, polyethylene oxide, polyethylene glycol, polymethacrylic acid, polyitaconic acid, polymaleic acid, polyvinyl alcohol, polyvinyl methyl ether, styrene/acrylic acid, ethylene/vinyl acetate, acrylic acid/N-vinyl pyrrolidinone, and vinylnaphthalene/itaconate, wherein said polymer is characterized by having chemically attached thereto a crosslinking agent selected from the group consisting of aluminum octoate, aluminum palmitate, aluminum stearate, aluminum distearate, aluminum tristearate, barium stearate, calcium stearate, lead stearate, magnesium stearate, zinc palmitate, zinc stearate, oxyaluminum octoate oxyaluminum stearate, titanium (IV) ethoxide, titanium (IV) butoxide, titanium (IV) isoproxide, isopropyl triisostearoyl titanate, isopropyl tri(dodecyl)benzenesulfonyl titanate, di(cumyl)phenyl oxoethylene titanate, di(butyl, methyl)pyrophosphato ethylene titanate, tetraisopropyldi(dioctyl)phosphito titanate, zirconium (IV) butoxide, dineopentyl(diallyl)oxy neopentyl(diallyl)oxy trineodecanoyl zirconate, neopentyl(diallyl)oxy tri(dodecyl)benzene-sulfonyl zirconate, cyclo(dioctyl)pyrophosphato dioctyl zirconate, cyclo[(dineopentyl(diallyl)]pyrophosphato dineopentyl(diallyl)zirconate, and silicon-based coupling agents selected from the group consisting of silanes and siloxanes, and wherein the polymer is further characterized by one or more functional groups capable of reacting reversibly with the crosslinking agent, said reactive functional groups being selected from the group consisting of alcohols, alkenes, alkanes, aldehydes, amines, azides, aziridines, carboxylic acids, epoxides, nitriles, phenols, phosphates, phosphites, and phosphines.
2. The reversibly-crosslinked-polymer composition of claim 1 wherein the polymer is characterized by an acid number from about 10 to about 300, a weight average molecular weight from about 500 to about 250,000, a softening point from about 0 to about 150� C., and a glass transition temperature from about -25 to about 180� C.
3. The reversibly-crosslinked-polymer composition of claim 2 wherein the polymer is characterized by an acid number from about 20 to about 80, a weight average molecular weight from about 2,000 to about 35,000 a softening point from about 40 to about 90� C., and a glass transition temperature from about 25 to about 80� C.
4. The reversibly-crosslinked-polymer composition of claim 1 wherein the reversibly-crosslinked-polymer is prepared by a polymerization method selected from the group consisting of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
In CIJ printing systems, a continuous stream of liquid ink droplets is ejected from a nozzle and is directed, with the assistance of an electrostatic changing device in close proximity to the print head, either to a substrate to form a printed image or to a recirculating system. Inks for CIJ printing systems are typically based on solvents such as methyl ethyl ketone and ethanol.
The following properties are required of an ink composition for ink printing:
(f) long-term reliability (no corrosion to nozzle clogging).
The use of polymers in phase change (hot melt) inks and printing of such inks has been disclosed in the following publications:
U.S. Pat. No. 5,531,819 teaches the use of an "acrylic resin," "rosin resin," "hydrogenated rosin resin," "protroleum resin," "hydrogenated petroleum resin," or "terpene resin" with a wax, a colorant, and a plasticizer.
U.S. Pat. No. 5,397,388 teaches the use of "acrylic resin," "rosin resin," "petroleum resin," "modified petroleum resin," "hydrogenated petroleum resin," or "terpene resin," with a wax, an organic substrate miscible with the wax, and a colorant.
The present invention overcomes many of the problems associated with the use of prior art phase change (hot melt) ink compositions while achieving distinct advantages thereof. Accordingly, an object of the present invention is directed to a reversibly-crosslinked-polymer that provides an ink composition for ink jet printing with excellent jetting properties. Other objects and advantages of the present invention will become apparent from the following disclosure.
In accordance with the present invention, phase change (hot melt) inks useful in ink jet, hot melt gravure, and similar printing devices is provided. The phase change (hot melt) inks preferably are fur use in a phase change (hot melt) ink jet recording device in which recording is conducted by thermally melting the ink at a temperature above ambient temperature (20� C.) to provide prints that possess high quality images, scratch resistance, abrasion resistance, low-temperature storage stability and flexibility, offset and pick resistance, adhesion, and other desired properties (including corrosion resistance). Furthermore, the present invention also includes methods for the preparation of reversibly-crosslinked-polymers and for their use in the above-described inks.
No particular limitation is imposed on the type or the amount of pigment used. The term "pigment" refers to a solvent insoluble colorant. A large range of pigments, organic and inorganic, may be used either alone or in combination. Pigments used in ink jet inks typically are in the dispersed state and are kept from agglomerating and settling out of the carrier medium by placing acidic or basic functional groups on the surface of the pigments, attaching a polymer onto the surface of the pigments, or adding a surfactant to the sink.
The pigment particles need to be small enough in size so that they move freely through the printing device. Because the ejecting nozzles of ink jet printers range in diameter from about 10 to 100 microns, pigments suitable for use in the present invention may have a range of particle sizes from about 0.01 microns to 100 microns, preferably from about 0.01 microns to 10 microns, and more preferably from about 0.01 microns to 5 microns.
No particular limitation is imposed on the type of crosslinking agent used. The crosslinking agents suitable in the present invention may include organic or inorganic reagents based on metals, non-metals, and metalloids. A crosslinking agent may consist of any reagent which could be used to covalently or noncovalently ink reactive functional groups in a polymer or other reagents such as a wax, plasticizer, solvent or pigment. No limitation is placed on the type of reactive functional groups interacting with the crosslinking agent. Those reactive functionalities may include alcohols, alkenes, alkyenes, aldehydes, amines, azides, aziridines, carboxylic acids, epoxides, nitriles, phenols, phosphates, phosphites, pohophines, and the like. The amount of crosslinking agent present in the ink compositions is from about 0.01 to 30% based on the weight of the gelled polymer, preferably from about 0.2 to 10%.
Suitable organometallic reagents for use as crosslinkers in the present invention include metallic soaps such as aluminum octoate, aluminum palmitate, aluminum stearate, aluminum distearate, aluminum tristearate, barium stearate, calcium stearate, lead stearate, magnesium stearate, zinc palmitate, and zinc stearate; oxyaluminum acylates such as oxyaluminum octoate and oxyaluminum stearate; alkoxy aluminum chelates such as diisobutyl(oleyl)acetoacetyl aluminate and diisopropyl(oleyl)acetoacetyl aluminate; other aluminum reagents such as Ketalin� and CycoGel� (Chattem Chemicals); alkoxy titanates such as titanium (IV) ethoxide, titanium (IV) butoxide, and titanium (IV) isoproxide; monoalkoxy titanates such as isopropyl triisostearoyl titanate and isopropyl tri(dodecyl)benzenesulfonyl titanate; chelated titanium agents such as di(cumyl)phenyl oxoethylene titanate and di(butyl, methyl)pyrophosphato ethylene titanate; amine adducts of titanates such as KR� 138D and KR�238J (Kenrich Petrochemicals, Inc.); coordinate titanates such as tetraisopropyldi(dioctyl)phosphito titanate; alkoxy zirconates such as zirconium (IV) butoxide; neoalkoxy zirconates such as neopentyl(diallyl)oxy trineodecanoyl zirconate and neopentyl(diallyl)oxy tri(dodecyl)benzenesulfonyl zirconate; and cycloheteroatom zirconates such as cyclo(dioctyl)pyrophosphato dioctyl zirconate and cyclo[dineopentyl(diallyl)]pyrophsophato dineopentyl(diallyl) zirconate.
Phase change (hot melt) ink compositions prepared in accordance with the present invention are in a molten state during printing. To prevent thermally induced oxidation from occurring in this state, antioxidants may be added to the ink composition. Suitable antioxidants, present preferably in the amount of about 0.1% to 1.0% by weight of the ink compositions, include, for example, Irganox� 1010 (Ciba-Geigy Corp.).
Inks suitable for use with phase change (hot melt) ink jet printers should be solid at room temperature, by which is meant about 18� C. to about 27� C., and are transformed into a molten state at temperatures ranging from 45� to 150� C. Most preferably those inks should melt from about 65� C. to 130� C. The phase change inks also should exhibit a relatively low melt viscosity of 1 to 50 cP between 100� C. and 150� C., most preferably 5 to 20 cP. The inks also should exhibit excellent dispersion and stability of this dispersion, especially when exposed to the elevated temperatures at which the ink is commonly stored and jetted in the printing device. The ink compositions of the present invention meet the aforementioned requirements.
Inks suitable for use with phase change (hot melt) ink jet printers should possess desirable corrosion inhibition properties. The components of a phase change ink should not cause corrosion to the materials which compose the printing device. Thus, the inks should not cause corrosion to parts such as the printhead, which are made form metals such as electrodeposited nickel. The present ink composiions are not corrosive to these materials, since corrosion-causing functionalities such as carboxylic acids are effectively protected through incorporation of crosslinking agents via the reversibly-crosslinked-polymer of the invention.
The ink compositions of the present invention possess desirable non-Newtonian properties. That is, these inks exhibit a relatively high viscosity at relatively low shear rates, e.g., 12 cP or more, but a much reduced viscosity at relatively high shear rages, e.g., 104 sec-1 or more. The high viscosity at low shear helps to keep the colorant in suspension when the ink is being stored whereas the low viscosity at high shear reduced the energy required to eject the ink droplet from the printhead.
The composition of the present invention may be used in phase change (hot melt) ink jet, hot melt gravure, and similar printing methods. A preferred method of printing involves phase change (hot melt) ink jet printing using piezo ink jet printers. The specific ink jet printer employed is not critical.
Specific embodiments of the phase change (hot melt) inks of the present invention are provided in further detail herein below. These examples are intended to be illustrative, and the invention is not limited to the materials set forth in these embodiment. All parts are by weight unless otherwise noted.
To a three-liter, five-neck, round-bottom flash, equipped with an agitator shaft and blade, thermocouple, condenser, and two stoppers, 1000 parts of Rosin SS (Westvaco Corp.) was charged. The Rosin SS was heated to 185� C. to melt the rosin. Then, 57.6 parts of maleic anhydride (Aldrich Chemical Co.) was added, and the temperature was increased to 205� C. After 1 hour at this temperature, 175 parts of stearic acid (Aldrich Chemical Co.), 92 parts of glycerol (Aldrich Chemical Co.), and 92 parts of pentaerythritol (Aldrich Chemical Co.) were added. A Dean-Stark trap was inserted between the round-bottom flask and the condenser. The contents of the flask were heated to 265� C. over one hour. The temperature was held at 265� C. for three hours, then 150 parts of a styrene acrylic polymer. JONREZ� H-2704 (Westvaco Corp.), was added, and the temperature was maintained for an additional 1.5 hours. The reaction was sparged with nitrogen for one hour to remove water and reaction oils. The resulting polymer had an acid number of 22, a ring and ball softening point of 75� C., and a Brookfield viscosity of 1580 cP at 135� C.
The following components were mixed in a three-gallon plastic container: 3190 parts dicyclopentadiene (Lyondell Chemical Corp.), 1021 parts LRO-90 (Lyondell Chemical Corp.), and 294 parts of Neodene� 16 (Shell Chemical Co.). Then, the contents of a plastic container and 507.4 parts stearic acid (Aldrich Chemical Co.) were charged to a two-gallon Parr reactor. The mixture was heated to 110� C. and then was sparged with nitrogen for thirty minutes. The nitrogen was then turned off, the reactor was sealed, and the mixture was heated to 260� C. The temperature was held at 260� C. for five hours. The temperature was then cooled to 140� C., and the reactor was vented to atmospheric pressure. The contents of the Parr reactor were transferred to a five-liter, five-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, nitrogen sparge tube, condenser and Dean-Stark trap, and stopper. The contents of the flask was heated to 200� C. and sparged with nitrogen for approximately five hours. The resulting polymer had an acid number of 1.9, a ring and ball softening point of 50� C., and a Brookfield viscosity of 455 cP at 130� C.
To a two-liter, five-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, condenser, nitrogen sparge tube and stopper, 250 parts Rosin WW (Westvaco Corp.) and 700 parts of the polymer described in Example 2 were charged. The contents were heated to 180� C. under a nitrogen blanket and agitation was begun once the contents were molten. Then, 14.4 parts maleic anhydride (Aldrich Chemical Co.) and 44 parts stearic acid (Aldrich Chemical Co.) were added, and the temperature was increased to 205� C. After 1.5 hours, 16.8 parts pentaerythritol (Aldrich Chemical Co.) and 31.6 parts glycerol (Aldrich Chemical Co.) were added. A Dean-Stark trap was inserted between the round-bottom flask and the condenser. The contents of the flask were then heated to 265� C. over one hour. The temperature was held at 265� C. for three hours and then the contents were sparged with nitrogen for one hour. The resulting polymer had an acid number of 9.3, a ring and ball softening point of 76� C., a Brookfield viscosity of 192 cP at 135� C.
To a three-liter, five-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, condenser, nitrogen sparge tube and a stopper, 1200 parts Rosin SS (Westvaco Corp.) was charged. The contents were heated to 180� C. under a nitrogen blanket and agitation was begun once the contents were molten. Then, 69.1 parts maleic anhydride (Aldrich Chemical Co.) and 200 parts stearic acid (Aldrich Chemical Co.) were added and the temperature was increased to 205� C. After one hour at this temperature, 110 parts pentaerythritol (Aldrich Chemical Co.), 110 parts glycerol (Aldrich Chemical Co.), and 1.9 parts magnesium oxide (Aldrich Chemical Co.) were added. A Dean-Stark trap was inserted between the round-bottom flask and the condenser. The contents of the flask then were heated to 265� C. over one hour. The temperature was held at 265� C. for three hours and then the contents were sparged with nitrogen for one hour. The resulting polymer had an acid number of 17, a ring and ball softening point of 70� C., a weight average molecular weight of 1910 daltons, a polydispersity of 2.2, a DSC glass transition temperature of 18� C., and a Brookfield viscosity of 1380 cP at 130� C.
To a three-liter, five-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, condenser, nitrogen sparge tube and a stopper, 900 parts Rosin SS (Westvaco Corp.) was charged. The rosin was then heated to 180� C. under a nitrogen blanket and agitation was begun once the rosin was molten. Then, 51.8 parts maleic anhydride (Aldrich Chemical Co.) and 300 parts stearic acid (Aldrich Chemical Co.) were added and the temperature was increased to 205� C. After one hour at this temperature, 92 parts pentaerythritol (Aldrich Chemical Co.) and 92 parts glycerol (Aldrich Chemical Co.) were added. A Dean-Stark trap was inserted between the round-bottom flask and the condenser. The contents of the flask then were heated to 265� C. over one hour. The temperature was held at 265� C. for three hours and then the contents were sparged with nitrogen for one hour. The resulting polymer has an acid number of 21, a ring and ball softening point of 43� C., a Brookfield viscosity of 208 cP at 130� C.
To a two-liter, five-neck, round bottom flask equipped with an agitator shaft and blade, condenser and Dean-Stark trap, thermocouple, nitrogen sparge tube and a stopper, 175 parts dimethylphthalate (Aldrich Chemical Co.), 100 parts glycerol (Aldrich Chemical Co.), and 340 parts stearic acid (Aldrich Chemical Co.) were added. The contents were then heated to 180� C. under a nitrogen black and agitation was begun once the contents were molten. Then, the temperature was increased to 220� C. and water and methanol produced during the reaction were collected. After forty-five minutes, the temperature was increased to 250� C. and held for five hours. The contents were then sparged with nitrogen for one hour. The resulting polymer had a Brookfield viscosity at of 6 cP at 130� C., a weight average molecular weight of 960 daltons, and a polydispersity of 1.2
To a three-liter, five-neck, round bottom flask equipped with an agitator shaft and blade, condenser and Dean-Stark trap, thermocouple, nitrogen sparge tube and a stopper, 600 parts Rosin SS (Westvaco Corp.) was added. The contents were then heated to 180� C. and agitation was begun once the contents were molten. Then, 568 parts stearic acid (Aldrich Chemical Co.) and 166.14 parts ethylene glycol (Aldrich Chemical Co.) were added and the temperature was increased to 190� C. and held for 90 minutes. The temperature was increased to 265� C. over one hour and held for three hours. The contents were then sparged with nitrogen for one hour. The resulting polymer had an acid number of 14, and a Brookfield viscosity of 8.8 cP at 130� C.
To a 250-ml, three-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, nitrogen sparge tube, and a condenser, 30 parts of the polymer described in Example 1 and 30 parts montan wax (Frank B. Ross, Inc.) was charged. The contents were heated to 180� C. (at 100� C., slow agitation was begun). The contents were held at 180� C. until the mixture was homogenous. The temperature was decreased to 160� C. and the agitation was increased until a vortex was present. Based on the total weight of the mixture, 1.5% of a 1:1 mixture of oxyaluminum octoate (Chattam Chemical Co.)/alkaline refined linseed oil (Elf Atochem) was added, and the contents were stirred for forty-five minutes. Another 1% of the 1:1 mixture was added, and the contents were stirred for an additional forty-five minute period. The resulting composition had a Brookfield viscosity of 265 cP at 130� C.
To a 250-ml, three-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, nitrogen sparge tube, and a condenser, 60 parts of the polymer described in Example 5 and 60 parts alkaline refined linseed oil (Elf Atochem) were charged. The contents were then heated to 180� C. (at 100� C., a slow agitation was begun). The contents were held at 180� C. until the mixture was homogenous. The temperature was decreased to 115� C. and the agitation was increased until a vortex was present. Based on the total weight of the mixture, 0.5% of zirconium(IV)butoxide (Aldrich Chemical Co.) was added, and the contents were stirred for thirty minutes. Another 3.5% of the zirconium reagent was added, and the contents were stirred for an additional thirty minute period. The temperature was increased to 170� C. and the contents were stirred for one hour. The resulting polymer had a Laray viscosity of 1.95 see at 30� C.
To a 250-ml, three-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, nitrogen sparge tube, and a condenser, 30 parts of the polymer described in Example 4 and 30 parts castor wax (Amber Inc.) were charged. The contents were heated to 180� C. (at 100� C., a slow agitation was begun). The contents were held at 180� C. until the mixture was homogenous. The temperature was decreased to 130� C. and the agitation was increased until a vortex was present. Based on the total weight of the mixture, 1.5% of KR-TTS� (isopropyl triisostearoyl titanate supplied by Kenrich Petrochemicals, Inc.) was added, and the contents were stirred for six hours. The resulting polymer had a Brookfield viscosity of 45 cP at 130� C.
To a 250-ml, three-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, nitrogen sparge tube, and a condenser, 40 parts of the polymer described in Example 3 and 30 parts montan wax (Frank B. Ross, Inc.) were charged. The contents were heated to 180� C. (at 100� C., a slow agitation was begun). The contents were held at 180� C. until all the resin was in solution. The temperature was decreased to 160� C. and the agitation was increased until a vortex was present. Based on the total weight of the mixture, 1.5% of a 1:1 oxyaluminum octoate (Chattem Chemical Co.)/alkaline refined linseed oil (Elf Atochem) mixture was added, and stirred for forty-five minutes. Another 0.75% of the 1:1 mixture was added, and the contents were then stirred for six hours. The resulting polymer had a Brookfield viscosity of 76 cP at 130� C.
To a 250-ml, three-neck, round bottom flask equipped with an agitator shaft and blade, thermocouple, nitrogen sparge tube, and a condenser, 40 parts castor wax (Amber, Inc.) was charged. The contents were heated to 160� C. The agitation was increased until a vortex was present. Then, 2% of oxyaluminum octoate (Chattem Chemical Co.) was added, and stirred for six hours. The resulting polymer had a Brookfield viscosity of 19.5 cP at 130� C.
The following components were heated while stirring until a homogenous mixture was obtained: 50 parts of the composition described in Example 9, 28 parts 18-pentatriactontanone (TCI), and 20 parts Unilin 350 (saturated, long-chain, linear alcohol supplied by a Baker Petrolite). To this mixture, 2 parts Monolite� Blue 3R (Zeneca, Inc.) was added, and stirring was continued until a homogenous mixture was obtained. The pigment was further dispersed by passing the ink composition through a three roll mill (Charles Ross and Son) five times.
The following components were heated while stirring until a homogenous mixture was obtained: 20 parts of the composition described in Example 12, 40 parts montan wax (Frank B. Ross, Inc.), 15 parts of the polymer described in Example 7, 7.1 parts 18-pentatriacontanone (TCI), 14.1 parts Uniplex 260 (glycerol tribenzoate supplied by Unitex Chemical Co.), and 1.8 parts tributyl phosphate (Aldrich Chemical Co.). Then, 2.1 parts Sunfast� Magenta 122 (Sun Chemical Co.) was added, and stirring was continued until a homogeneous mixture was obtained. The pigment was further dispersed by passing the ink composition through a three roll mill (Charles Ross and Son) five times.
The following components were heated while stirring until a homogeneous mixture was obtained: 30 parts of the composition described in Example 11, 32 parts montan wax (Frank B. Ross, Inc.), 9.4 parts 18-pentatriacontanone (TCI), 18.8 parts Uniplex 260 (glyceryl tribenzoate supplied by Unitex Chemical Co.) 5 parts dimethyl phthalate (Aldrich Chemical Co.) and 2.3 parts tributyl phosphate (Aldrich Chemical Co.). Then, 2.8 parts Sunfast� Magenta 122 (Sun Chemical Co.) was added, and stirring was continued until a homogeneous mixture was obtained. The pigment was further dispersed by passing the ink composition through a three roll mill (Charles Ross and Son) five times.
The following components were heated while stirring until a homogeneous mixture was obtained: 20 parts of the composition described in Example 13, 40 parts of montan wax (Frank B. Ross, Inc.), 15 parts of the polymer described in Example 7, 7.1 parts 18-pentatriacatanone (TCI), 14.1 parts Uniplex 260 (glycerol tribenzoate supplied by Unitex Chemical Co.), and 1.8 parts tributyl phosphate (Aldrich Chemical Co.). Then, 2.1 parts Sunfast� Magenta 122 (Sun Chemical Co.) was added, and stirring was continued until a homogeneous mixture was obtained. The pigment was further dispersed by passing the ink composition through a three roll mill (Charles Ross and Son) five times.
The following components were heated while stirring until a homogeneous mixture was obtained: 25 parts of the composition described in Example 8, 45 parts montan wax (Frank B. Ross, Inc.), 7.1 parts 18-pentatriacontanone (TCI), 14.1 parts Uniplex 260 (glycerol tribenzoate supplied by Unitex Chemical Co.), and 6.8 parts tributyl phosphate (Aldrich Chemical Co.). Then, 2.1 parts Sunfast� Magenta 122 (Sun Chemical Co.) was added, and stirring was continued until a homogenous mixture was obtained. The pigment was further dispersed by passing the ink composition through a three roll mill (Charles Ross and Son) five times.
The following components were heated while stirring until a homogeneous mixture was obtained: 20.2 parts of the composition described in Example 8, 30.4 parts of the polymer described in Example 6, 32.5 parts 18-pentatriacontanone (TCI), and 15.5 parts of the polymer described in Example 7. Then, 1.4 Sunfast� Yellow 83 (Sun Chemical Co.) was added, and stirring was continued until a homogenous mixture was obtained. The pigment was further dispersed by passing the ink composition through a three roll mill (Charles Ross and Son) five times.
The following components were heated while stirring until a homogeneous mixture was obtained: 23 parts of the polymer described in Example 1, 55 parts 18-pentatriacontanone (TCI), and 20 parts Unilin 350 (saturated, long-chain, linear alcohol supplied by Baker Petrolite). Then, 2 parts Monolite� Blue 3R (Zeneca, Inc.) was added, and stirring was continued until a homogenous mixture was obtained. The pigment was further dispersed by passing the ink composition through a three roll mill (Charles Ross and Son) five times.
The following components were heated while stirring until a homogeneous mixture was obtained: 60 parts Montan wax, 15 parts of the polymer described in Example 7, 7.1 parts 18-pentatriacontanone (TCI), 14.1 parts Uniplex 260 (glyceryl tribenzoate supplied by Unitex Chemical Co.), and 1.8 parts tributyl phosphate (Aldrich Chemical Co.). Then, 2.1 parts Sunfast� Magenta 122 (Sun Chemical Co.) was added, and stirring was continued until a homogenous mixture was obtained. The pigment was further dispersed by passing the ink composition through a three roll mill (Charles Ross and Son) five times.
The following properties of the ink composition described in Examples 14-21 were evaluated: Brookfield viscosity, pigment dispersion stability, pigment dispersion, and print quality.
TABLE I______________________________________ Brookfield          PigmentExam- Viscosity          Dipersion                   Pigment Print Quality*ple # (cP)     Stability                   Dispersion*                           Color                                Adhesion                                       Tack______________________________________14    14.0     &gt;72 hrs  10      8     10    1015    22.0     &gt;72 hrs  10      10    10    916    35.8     &gt;72 hrs  10      10    10    917    20.3     &gt;72 hrs  9       9     10    1018    27.0     &gt;72 hrs  10      9     10    1019    39.0     &gt;72 hrs  9       10    10    720    8.7       8 hrs   8       7     10    1021    17.5     &lt;1 hr    3       5     8     10______________________________________ *Pigment dispersion and Print Quality rating system: 10 = excellent &#8594; 1 = poor
The complex viscosity of the ink compositions described in Examples 14-21 was evaluated using a Rheometrics Dynamic Rheometer with 40 mm parallel plates (gap width--0.4 mm). The complex viscosity was determined at increasing oscillatory frequencies, the stress was maintained at 500 dynes/cm2, and the temperature was kept constant. The results are shown in Table II.
TABLE II______________________________________Complex Viscosity (P) at Various Frequencies  0.1     0.4     1.0   10    100   251.2                                         %Example  rad/s   rad/s   rad/s rad/s rad/s rad/s                                         Chg.4______________________________________141  198     148     121   51    18    16   92152  1128    770     737   534   167   101  91162  768     493     325   107   33    23   97172  252     27      23    17    10    9    96182  3256    2003    1878  1295  382   186  94193  79252   7669    3298  877   297   216  99201  70      34      32    23    10    10   86212  2068    1028    904   831   750   653  68______________________________________ 1 Viscosities determined at 80� C. 2 Viscosities determined at 75� C. 3 Viscosities determined at 65� C. 4 % Change represents the percent change in the complex viscosity between readings at 0.1 rad/s and 1.2 rad/s.
These data shown that in ink formulations employing a reversibly-crosslinked-polymer, such as Examples 14-19, much enhanced % changes in complex viscosities were achieved, as compared with ink formulations without a polymer which is reversibly-crosslinked.
From this disclosure it will be seen that the subject matter of the claimed invention is:
(1) A reversibly-crosslinked-polymer composition useful in phase change ink jet inks comprising a polymer having chemically attached thereto a crosslinking agent wherein the polymer possesses at least one functional group capable of reacting reversibly with the crosslinking agent;
(2) the reversibly-crosslinked-polymer composition of (1) wherein the polymer is characterized by an acid number from about 10 to about 300, a weight average molecular weight from about 500 to about 250,000, a softening point from about 0 to about 15� C., and a glass transition temperature from about -25 to about 180� C.;
(3) the reversibly-crosslinked-polymer composition of (2) wherein the polymer is characterized by an acid number from about 20 to about 80, a weight average molecular weight from about 2,000 to about 35,000, a softening point from about 40 to about 90� C., and a glass transition temperature from about 25 to about 80� C.;
(4) the reversibly-crosslinked-polymer composition of (2) wherein the polymer is selected from the group consisting of naturally occurring polymers, synthetic analogues of naturally occurring polymers, synthetic polymers, and synthetic copolymers.
(5) the reversibly-crosslinked-polymers composition of (4) wherein the naturally occurring polymer is selected from the group consisting of alginic acid, carboxymethyl cellulose, and pectinic acid;
(6) the reversibly-crosslinked-polymer composition of (4) wherein the synthetic analogue of a naturally occurring polymer is selected from the group consisting of rosin esters, lignosulfonates, nitrocellulose, and alcohol-soluble polysaccharides;
(7) the reversibly-crosslinked-polymer composition of (4) wherein the synthetic polymer is selected from the group consisting of polyacrylamide, polyacrylic acid, polyethylene oxide, polyethylene glycol, polymethacrylic acid, polyitaconic acid, polymaleic acid, polyvinyl alcohol, and polyvinyl ether;
(8) the reversibly-crosslinked-polymer composition of (4) wherein the synthetic copolymer is selected from the group consisting of styrene/acrylic acid, ethylene/vinyl acetate, acrylic acid/N-vinyl pyrrolidinone, and vinylnaphthalene/itaconic copolymers;
(9) the reversibly-crosslinked-polymer composition of (4) wherein the reversibly-crosslinked-polymer is prepared by a polymerization method selected from the group consisting of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization;
(10) the reversibly-crosslinked-polymer composition of (2) wherein the crosslinking agent is selected from the group of reagents consisting of organic reagents and inorganic reagents and wherein the reagents are based on a member of the group consisting of metals, non-metals, and metalloids;
(11) the reversibly-crosslinked-polymer composition of (10) wherein the organic reagents are selected from the group of organometallic reagents consisting of metallic soaps, oxyaluminum acylates, alkoxy aluminum chelates, alkoxy titanates, monoalkoxy titanates, chelated titanium agents, amine adducts of titanates, coordinate titanates, alkoxy zirconates, neoalkoxy zirconates, and cycloheteroatom zirconates.
(12) the reversibly-crosslinked-polymer composition of (1) wherein the metallic soaps are selected from the group of organometallic reagents consisting of aluminum octoate, aluminum palminate, aluminum stearate, aluminum distearate, aluminum tristearate, barium stearate, calcium stearate, lead stearate, magnesium stearate, zinc palminate, and zinc stearate;
(13) the reversibly-crosslinked-polymer composition of (10) wherein the oxyaluminum acylates are selected from the group of organometallic reagents consisting of oxyaluminum octoate and oxyaluminum stearate;
(14) the reversibly-crosslinked-polymer composition of (10) wherein the alkoxy titanates are selected from the group of organometallic reagents consisting of titanium (IV) ethoxide, titanium (IV) butoxide, and titanium (IV) isoproxide;
(15) the reversibly-crosslinked-polymer composition of (10) wherein the monoalkoxy titanates are selected from the group of organometallic reagents consisting of isopropyl triisostearoyl titanate and isopropyl tri(dodecyl)benzenesulfonyl titanate;
(16) the reversibly-crosslinked-polymer composition of (10) wherein the chelated titanium agents are selected from the group of organometallic reagents consisting of di(cumyl)phenyl oxoethylene titanate and di(butyl, methyl)pyrophosphato ethylene titanate;
(17) the reversibly-crosslinked-polymer compostion of (10) wherein the coordinate titanate is tetraisopropyldi(dioctyl)phosphito titanate;
(18) the reversibly-crosslinked-polymer composition of (10) wherein the alkoxy zirconate is zirconium (IV) butoxide;
(19) the reversibly-crosslinked-polymer composition of (10) wherein the neoalkoxy zirconate is selected from the group of organometallic reagents consisting of neopentyl(diallyl)oxy trineodecanoyl zirconate and neopentyl(diallyl)oxy tri(dodecyl)benzenesulfonyl zirconate;
(20) the reversibly-crosslinked-polymer composition of (10) wherein the cycloheteroatom zirconates are selected from the group of organometallic reagents consisting of cyclo(dioctyl)pyrophosphato dioctyl zirconate and cyclo[dineopentyl(diallyl)]pyrophosphato dineopentyl(diallyl);
(21) the reversibly-crosslinked-polymer composition of (9) wherein the crosslinking agent is a member of the group of reagents selected from alkoxy reagents, chelated reagents, and metallocene reagents based on a member of the group of elements selected from antimony, copper, gallium, germanium, indium, iron, lanthanum, manganese, nickel, niobium, selenium, tin, thallium, and zinc; and
(22) the reversibly-crosslinked-polymer composition of (10) wherein the crosslinking agent is a silicon based coupling agent selected from a member of the group consisting of silanes and siloxanes.
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