Patent Grant
8147608
The present invention relates to a method of making self-dispersing pigments. More particularly, the present invention relates to the surface modification of pigments, as well as inks, such as inkjet inks, comprising surface-modified pigments.
Pigments offer several advantages over water-soluble dyes when it comes to inkjet inks. Pigments may exhibit at least one of greater light resistance, water resistance, optical density and edge acuity than water-soluble dyes. Unfortunately, pigments also have a greater propensity to settle during storage, thus initially limiting their use in inkjet inks. The advent of media mills to grind pigment particles to sub-micron level combined with chemical additives for colloidal stability has propelled the use of pigment dispersions in inkjet ink formulations. However, chemical additives can increase the viscosity of a dispersion such that it becomes difficult to jet the ink from the small orifices in an inkjet printhead. Moreover, chemical additives can add significant cost to the preparation of inkjet inks and are therefore economically unfavorable as well. A need remains for improved ink compositions, especially for use in inkjet printers, which overcome the problems typically associated with current dye-based systems and pigment systems employing chemical additives.
In one embodiment, the invention provides a method of modifying a pigment comprising sulfonating a pigment, and subsequently oxidizing the pigment to produce a modified pigment.
In another embodiment the invention provides a modified pigment comprising a pigment having a surface, sulfonic acid surface modifying groups and carboxyl surface modifying groups attached to the surface of the pigment, and charge-balancing counterions associated with the surface modifying groups, wherein the modified pigment comprises about 0.02 to about 1.0 mMoles of S and about 0.2 to about 2.0 mMoles of active hydrogen per gram of pigment.
In yet another embodiment, the invention provides a dispersion comprising a self-dispersing pigment comprising about 0.02 to about 1.0 mMoles of S and about 0.2 to about 2.0 mMoles of active hydrogen per gram of pigment, and water.
Other aspects of the invention will become apparent by consideration of the detailed description and accompanying drawings.
Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items.
It also is understood that any numerical range recited herein includes all values from the lower value to the upper value. For example, if a concentration range is stated as 1% to 50%, it is intended that values such as 2% to 40%, 10% to 30%, or 1% to 3%, etc., are expressly enumerated in this specification. These are only examples of what is specifically intended, and all possible combinations of numerical values between and including the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
Surface Modified Pigments
One aspect of the present invention relates to a method for making stable, self-dispersing pigments.
As used herein, the term “pigment” means a colored material insoluble in a solvent medium used to impart color to a substrate such as plain or coated paper, film and other types of receiving media.
As used herein, the term “self-dispersing pigment” means a pigment having stabilizing groups covalently attached to its surface such that the pigment forms a stable aqueous dispersion in the absence of any additional dispersing agents.
As used herein, the term “stable” means that on aging the dispersion will undergo minimal changes as demonstrated by less than 10% change in measured critical properties such as mean particle size, large particle count, viscosity, surface tension or pH, when the dispersion is stored at ambient temperature for at least about 3 months, at least about 6 months, or at least about 2 years, or when the dispersion is stored at 70° C. for at least about 1 week, at least about 2 weeks, at least about 3 weeks or at least about 4 weeks.
The method for making the self-dispersed pigments generally comprises (1) attaching hydrophilic groups to the surface of the pigment by sulfonation and (2) subsequently oxidizing the surface of the pigment to impart greater charge density around the particle. The oxidation step adds surface modifying groups that may include carboxyl groups, lactone groups, phenolic groups, quinone groups and combinations thereof. More particularly, the oxidation step adds surface modifying groups comprising carboxyl groups.
Pigments
Pigments that may be surface modified according to the present invention may include, but are not limited to, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, thioindigo pigment, triphenylmethane lake pigment, and oxazine lake pigment. Specifically, those having yellow colors include, for example, C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 65, 74, 83, 97, 138 and 155. Those having red colors include, for example, C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 49, 50, 51, 52, 53, 55, 60, 64, 83, 87, 88, 89, 90, 112, 114, 122, 123 and 163. Those having blue colors include, for example, Solvent Blue 67 and C. I. Pigment Blue 2, 3, 15, 16, 22 and 25. Those having black colors include, for example, C. I. Pigment Black 1 and 7. Commercially available colored pigments include, for example, Pigment Red 122 (available from Lansco Colors, Montvale, N.J.), Pigment Red 122 (available from BASF Color, Charlotte, N.C.), Pigment Red 122 (available from Clariant Colors, Charlotte, N.C.), Pigment Red 122 (available from Sun Chemical, Cincinnati, Ohio), Pigment Blue 15:1 (available from Fanwood Chemical, Fanwood, N.J.), Pigment Blue 15:3 (available from BASF Corporation, Charlotte, N.C.) and Solvent Yellow 33 (available from Rainbow Chemicals, Northbrook, Ill.).
Suitable pigments also include carbon black. Carbon black is the generic name for carbon particles derived from the thermal decomposition or the incomplete combustion of natural gas and hydrocarbons, such as aromatic oils on coal tar basis, mineral oils, coal tar distillate, and acetylene. More than 100 individual grades of carbon black are available on the market today, each with its own distinctive set of characteristics and properties. Any acidic carbon black, neutral carbon black and alkaline carbon black may be beneficially subjected to the treatment disclosed in the present invention. This includes channel blacks, gas blacks, lamp blacks, thermal blacks, acetylene blacks and furnace blacks. More particularly, suitable carbon blacks include channel blacks. The quality of carbon black utilized will have an impact on the critical properties of the dispersion such as mean particle size, opacity, color shade, stability, etc. Examples of commercially available carbon blacks include, but are not limited to, those available from Cabot (Elftex 8, Black Pearls® 490, Black Pearls® 120, Monarch® 120, Monarch® 700, Monarch® 880, Monarch® 1000, Monarch® 1100, Monarch® 1300, Monarch® 1400, Mogul® L, Regal® 99R, Regal® 250R, Regal® 300R, Regal® 330R, Regal® 400R, Regal® 500R, Regal® 660R), Degussa (NIPex® 150 IQ, NIPex® 150, Printex® 55, Printex® 80, Printex® 90, Printex® A, Printex® G, Printex® U, Printex® V, Printex® 140U, Printex® 140V, Purex® LS 35, Corax® HP 160, Thermal Black N 990, NIPex® 160 IQ, NIPex® 90, Special black 4, Special black 4A, Special black 5, Special black 6, Special black 100, Special black 250, Color black FW1, Color black FW2, Color black FW2V, Color black FW 18, Color black FW200, Color black S 150, Color black S 160 and Color black S 170), Columbian (Raven° 780, Raven° 5000 UII, Raven® 1255, Raven® 2500 U, Raven® 3600 U, Raven® 3500, Raven® 7000, Raven® 1220 and Raven® 1225) and Mitsubishi Kagaku K.K. (MA8, MA11, MA77, MA100, MA220, MA230, MA600, MCF88, #10B, #20B, #30, #33, #40, #44, #45, #45L, #50, #55, #95, #260, #900, 970#, #1000, #2200B, #2300, #2350, #2400B, #2650, #2700, #4000B and CF9).
Carbon black is available in a variety of particle sizes. Generally, smaller particle sizes are associated with larger surface areas, and larger surface areas can accommodate a higher concentration of hydrophilic surface groups, which ultimately enhance the dispersibility of the carbon black in aqueous-based media. Therefore, particle size can influence the dispersibility of a surface-modified pigment. The average primary particle size of carbon blacks in the present invention may be less than about 30 nm, particularly less than about 20 nm, and more particularly less than about 10 nm. Aggregates of carbon black particles may be less than about 200 nm, particularly less than about 150 nm, and more particularly less than about 100 nm. The surface area of carbon black particles may be greater than about 100 m2/g, particularly greater than about 150 m2/g, and more particularly greater than about 200 m2/g. Carbon black particles with larger dimensions may be comminuted to a desired size either before or during surface modification using any number of techniques known to those skilled in the art. Such techniques may include, but are not limited to, a ball mill, an attritor, a flow jet mixer, an impeller mill, a colloidal mill and a sand mill (e.g., one commercially sold under the tradename ‘Super Mill’, ‘Agitator Mill’, ‘Dyno-mill’ or ‘Beads Mill’). Mill media may include, but are not limited to, glass beads, zirconia beads and stainless steal beads. Mill media may comprise particles ranging in size from about 0.01 mm to about 5 mm, and more particularly from about 0.1 mm to about 0.3 mm. If the carbon black is easily crumbled, a rotary homogenizer or an ultrasonic homogenizer may be used to reduce particle size. In one embodiment, a surface-modified black pigment is made from a commercial grade carbon black pigment consisting of primary particle sizes less than about 30 nm and aggregates not more than about 200 nm with a surface area greater than about 100 m2/g.
By way of example, surface modification of carbon black will be generally described below. However, the surface modification may be similarly applied to other colored pigments, such as those mentioned above and described in the Example section below.
Sulfonation
Hydrophilic groups comprising sulfonic acid are attached to carbon black by sulfonation with sulfuric acid, oleum (fuming sulfuric acid) or a combination thereof. Attachment of sulfonic acid groups directly on the surface of the carbon black pigment may also be achieved by sulfonating with other known chemical agents such as chlorosulfonic acid or by displacement of a leaving group attached to the pigment, such as halogen with a suitable reagent such as sodium bisulfite.
In the case of sulfonating carbon black with sulfuric acid, oleum or a combination thereof, a suitable acid strength for sulfonation lies in the range of about 85% to about 104% (weight of sulfuric acid/total weight), particularly in the range of about 90% to about 102% (weight of sulfuric acid/total weight), and more particularly in the range of about 99% to about 101% (weight of sulfuric acid/total weight). The combination of acid strength, reaction temperature and duration determine how many sulfonic acid groups are attached to the surface of the pigment, therefore strength of sulfuric acid used in the present invention is best determined in conjunction with other critical parameters. In one embodiment, as represented by Example 2, sulfonation is carried out with a mixture of carbon black and equal amounts of concentrated sulfuric acid and oleum (20% excess SO3). In other embodiments, as represented by Example 1, sulfonation is carried out with a mixture of carbon black and 20% oleum. In yet other embodiments, as represented by Example 3, sulfonation is carried out with a mixture of carbon black and 99.4% sulfuric acid. Similar acid strengths may be employed in the sulfonation of pigments other than carbon black. In one embodiment, as represented by Example 12, sulfonation is carried out with a mixture of C.I. Pigment Red 122 and 90% sulfuric acid.
The ratio (by weight) of carbon black to acid is largely determined as a function of operational efficiency which includes mixing, ease of transfer and cost. A minimum of acid to carbon ratio of about 4:1 (wt/wt) is needed to get good mixing throughout the reaction. A large excess such as a ratio of about 20:1 (wt/wt) does not result in significant benefit but increases the cost of both materials and waste handling.
Sulfonation of the carbon black is carried out at elevated temperatures for a period of up to about 2 days. The reaction temperature during sulfonation may be at least about 25° C., particularly at least about 80° C., and more particularly at least about 120° C. Furthermore, the reaction temperature during sulfonation may be less than or equal to about 160° C., particularly less than or equal to about 140° C., and more particularly less than or equal to about 120° C. This includes embodiments where the reaction temperature during sulfonation is about 80° C. to about 120° C. Generally, higher temperatures require shorter reaction times to achieve a desirable concentration of sulfonic acid groups on the surface of carbon black. For example, the desired sulfonation at a reaction temperature of 140° C. may take about two hours, whereas the same degree of sulfonation at 80° C. would be expected to take more than two hours. In some embodiments, a suitable reaction time may be at least about 12 hours, in others at least about 24 hours, and in yet others at least about 40 hours. In other embodiments, the suitable reaction time may be less than or equal to about 48 hours, in others less than or equal to about 30 hours, and in yet others less than or equal to about 20 hours. This includes embodiments where the suitable reaction time is from about 2 hours to about 48 hours. The contents of the reaction vessel are stirred during sulfonation to insure adequate mixing.
After sulfonation, the reaction mixture may be quenched in water. In some embodiments, the reaction mixture may be cooled to a temperature less than about 100° C. prior to quenching, in others to a temperature of less than about 80° C. prior to quenching, and in yet others to a temperature less than about 60° C. prior to quenching. This includes embodiments where the reaction mixture is cooled to a temperature of about 60° to about 65° C. prior to quenching. The water into which the reaction mixture is added may be at or below a temperature of about 10° C. using, for example, ice, a cooling device or combination thereof. The sulfonated product, referred to as a carbon sulfonation cake, may be isolated from the water by filtration and washed free of excess reactants and water soluble products.
Oxidation
The carbon sulfonation cake is subsequently oxidized with oxidizing agents known to modify the carbon surface by attaching hydrophilic groups such as carboxyl groups, lactone groups, phenolic groups, quinone groups and combinations thereof. The oxidation method may include, but is not limited to, contact with air, a gas phase oxidation method using reaction with a nitrogen oxide or ozone, a liquid phase oxidation method using an oxidizing agent such as nitric acid, potassium permanganate, potassium dichromate, perchloric acid, a hypohalite, hydrogen peroxide, a bromine aqueous solution or an ozone aqueous solution. In one embodiment, oxidation of the carbon black is carried out using a hypohalogenous acid and/or its salt. Suitable hypohalogenous acids or salts thereof include, but are not limited to, sodium hypochlorite (NaOCl), potassium hypochlorite (KOCl), sodium hypobromite (NaOBr), and potassium hypobromite (KOBr). More particularly, the oxidizing agent comprises NaOCl.
In some embodiments, oxidation of the carbon sulfonation cake includes reacting carbon black with hypohalite salts in an aqueous medium. The carbon sulfonation cake may be dispersed in deionized water prior to the addition of hypohalite salts. The initial concentration (by weight) of hypohalite salt in the reaction mixture is at least about 1%, particularly at least about 5%, and more particularly at least about 10%. Furthermore, the concentration of hypohalite salt may be less than or equal to about 14%, particularly less than or equal to about 12% or about 10%, and more particularly less than or equal to about 7% or about 5%. This includes embodiments where the concentration of hypohalite salt is about 5% to about 10%. The proportion (by weight) of hypohalite salt to carbon sulfonation cake is about 1:20 to about 1:5, particularly about 1:15 to about 1:8, and more particularly about 1:11 to about 1:9. For pigments other than carbon black, the proportion (by weight) of hypohalite salt to sulfonation cake is about 1:5 to about 1:1.
Reaction between the carbon sulfonation cake and oxidizing agent may occur for a period of about 1 to about 2 hours with mixing. If necessary, to consume all of the hypochlorite, the oxidation reaction can be carried out at an elevated temperature of about 30° C. to about 90° C. In some embodiments, the reaction may be carried out at about 80° C. In other embodiments, the reaction may be carried out at about 60° C. The oxidation step may, but need not, be repeated one or more times.
Oxidation of the carbon black creates acidic surface groups that can lower the pH of the reaction mixture. A decrease in pH may result in a destabilization of the modified pigment dispersion during the oxidation treatment and may also result in an increase in viscosity. Therefore, the pH may be adjusted, as needed, before and during oxidation with a basic reagent. The pH of the reaction mixture prior to oxidation may be greater than or equal to about 7, particularly greater than or equal to about 10 or about 11, and more particularly greater than or equal to about 12. The pH of the reaction mixture during oxidation may be greater than or equal to about 9, particularly greater than or equal to about 10, and more particularly greater than or equal to about 11. The pH may be adjusted by any known method in the art including, for example, the addition of base. Suitable bases may include, but are not limited to, alkali hydroxides and calcium free alkali hydroxides (e.g., NaOH, KOH and LiOH), alkali carbonates and bicarbonates (e.g., NaHCO3, KHCO3), and organic bases (e.g., dimethylethanol amine and triethanol amine). In particular, a suitable pH adjuster comprises calcium free sodium hydroxide.
Isolation of Surface Modified Pigment
After oxidation, the modified pigment, such as the modified carbon black described above, may be isolated from the reaction mixture as a dry powder. The resultant modified pigment may be purified by using any number of techniques known to those skilled in the art to remove unreacted raw materials, byproduct salts and other reaction impurities. Purification techniques may include, but are not limited to, filtration, centrifugation, or a combination of the two. The modified pigment may also be isolated, for example, by evaporation or it may be recovered by filtration and drying using techniques known to those skilled in the art.
Alternatively, the modified pigment may be delivered as a concentrated aqueous pigment dispersion. Dispersions of the pigments of the present invention may be purified to remove impurities and other undesirable free species which can co-exist in the dispersion as a result of the manufacturing process. Purification techniques may include, but are not limited to, water washing, reverse osmosis, and ultrafiltration. In some embodiments, dissolved impurities may be removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample adjusted to 10% solids is less than about 150 ppm, particularly less than about 100 ppm, and more particularly less than about 10 ppm. If necessary, the pH of the dispersion may be adjusted prior to purification. A sufficient amount of acid or base may be added to adjust the pH of the dispersion to at least about 7, particularly to at least about 8, and more particularly to at least about 9. This includes embodiments where the pH of the dispersion is about 7 to about 9. The dispersion may be concentrated if desired by removal of some of the water. In some embodiments, the dispersion is concentrated to at least about 8% or about 10% solids, in others to at least about 18% solids, and in yet others to at least about 20% solids. This includes embodiments where the dispersion is concentrated to about 14% to about 16% solids.
A biocide may also be added to the dispersion to inhibit the growth of microorganisms. Examples of suitable biocides include, but are not limited to, sodium benzoate, pentachlorophenol sodium, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazolin-3-one, methylisothiazolinone and chloromethylisothiazolinone. Commercially available biocides include Proxel® CRL, Proxel® BDN, Proxel® GXL, Proxel® XL-2, and Proxel® TN (available from Arch Chemicals, Smyrna, Ga.).
The dispersion may be filtered through filter cartridges as required for the designated end use of the dispersion. In some embodiments, the nominal pore size of the filter cartridge is less than or equal to about 5 microns, particularly less than or equal to about 1 micron, and more particularly less than or equal to about 0.5 or about 0.3 micron.
In addition to powders and dispersions, the modified pigment may also be isolated as a water wet presscake. In presscake form, the modified pigment is not agglomerated to the extent that it is in dry form and thus the modified pigment does not require as much deagglomeration when used, for example, in the preparation of inks.
If desired, the counterions associated with the surface-modifying groups as a result of the sulfonation/oxidation process may be exchanged or substituted with other suitable cations using known ion-exchange techniques such as ultrafiltration, reverse osmosis, conversion to acid form as an intermediate, and the like. Examples of suitable cations that may be exchanged include, but are not limited to, alkali metal ions (e.g., K+ and Li+), alkaline earth metals (e.g., Ca2+, Mg2+ and Ba2+) and NR1R2R3H+ wherein R1, R2 and R3 may independently be H or C1-C5 alkyl groups that may be unsubstituted or substituted. Exemplary cations include, but are not limited to, tetraethylammonium, tetramethylammonium (TMA), ethanolammonium, triethanolammonium (TEA), monoethanolammonium (MEA), tetrabutylammonium (TBA), etc. In one embodiment, as represented by Example 19, the pKa differences between the surface carboxyl and sulfonyl groups can be beneficially exploited for partial exchange of counterions.
Properties of Modified Pigments
The method of modifying pigments by sulfonation and subsequent oxidation may, but need not, provide several advantages over pigments that have been treated with sulfonation or oxidation alone. For example, the modified pigments of the present invention may exhibit greater dispersability. As presented in the Examples section, Commercial pigment red 122 was modified by sulfonation and oxidation (Examples 10-13), oxidation only (Comparative Example 1) and sulfonation only (Comparative Example 2). The comparative examples are disclosed in U.S. Pat. Nos. 6,596,068 and 6,648,954, respectively. The oxidized pigment in Comparative Example 1 began to settle upon standing within three days at ambient temperature. The sulfonated pigment in Comparative Example 2 exhibited hard settling in the bottom of a container after setting for one week in an oven at 70° C. In contrast, the sulfonated/oxidized pigments of Examples 10-13 exhibited no observable settling after setting for two weeks at 70° C. More generally, the dispersions of the present invention may not settle for at least about 1 week, more particularly at least about 3 weeks, and even more particularly at least about 4 weeks when stored at 70° C.
Other advantages may include a greater concentration of surface modifying groups. Example 22 contrasts the TGA spectra for a sulfonated, carboxy modified carbon black (obtained from the procedure of Example 7) with a carboxy modified carbon black (i.e., Sensijee Black SDP 1000, available from Sensient Colors, Inc., St. Louis, Mo.). Both modified carbon blacks exhibit three distinct weight loss regions. The sulfonated, carboxy modified carbon black exhibits a weight loss equivalent to 1424 μMoles CO2 per gram of pigment from 103-313° C. In contrast, the carboxy modified carbon black exhibits a weight loss equivalent to 1239 μMoles CO2 per gram of pigment from 101-308° C. The greater weight loss equivalent over similar temperature ranges for the carboxy modified carbon black suggests a greater concentration of surface modifying groups when compared to the carboxy modified carbon black.
Modified pigments of the present invention in an aqueous dispersion take up about 0.1 to about 1.7 mMoles of HCl when titrated with 2.0 N HCl. In the case of carbon black, this range is typically about 1.4 to about 1.7 mMoles of HCl when titrated with 2.0 N HCl, as represented in Example 23.
Carbon black modified according to the present invention may comprise about 0.3 to about 1.0 mMoles of S per gram of pigment, particularly about 0.5 to about 0.8 mMoles of S per gram of pigment. Colored pigments other than carbon black (such as yellow, magenta and cyan) may comprise about 0.02 to about 0.9 mMoles of S per gram of pigment, particularly about 0.03 to about 0.2 mMoles of S per gram of pigment.
The modified carbon black may comprise about 1.0 to about 2.0 mMoles of active hydrogen per gram of pigment, particularly about 1.5 to about 1.8 mMoles of active hydrogen per gram of pigment. Colored pigments other than carbon black (such as yellow, magenta and cyan) may comprise about 0.2 to about 1.5 mMoles of active hydrogen per gram of pigment, particularly about 0.3 to about 1.0 mMoles of active hydrogen per gram of pigment.
Dispersions of the present invention may have viscosities ranging from about 1.5 to about 3.0 cP, particularly about 1.8 to about 2.6 cP. Surface tensions may range from about 60 dynes/cm to about 72 dynes/cm, particularly about 67 dynes/cm to about 72 dynes/cm. pH values may range from about 7 to about 9, particularly about 7.4 to about 8.5.
The self-dispersing pigments of the present invention may also exhibit long-term and high temperature stability, higher water and highlighter resistance than expected of a pigment with attached sulfonic or carboxylic acid groups, and have particle size distributions comparable to products typically obtained only after particle reduction processes such as “milling”.
The modified pigments according to the present invention may be used in a number of end use applications. These uses include, but are not limited to, coatings, paints, papers, adhesives, latexes, toners, textiles, fibers, plastics and inks. The modified pigments produced by the process of the invention are particularly well-suited for use in inkjet inks.
Ink Jet Inks
Another aspect of the present invention relates to inkjet ink formulations using the surface-modified pigments described above. Inkjet formulations comprising such modified pigments or dispersions comprising such modified pigments may do at least one of the following: 1) provide uniform, bleed-free images, when printed both on a plain and color background, with high resolution and high density on print media; 2) not cause nozzle clogging which typically occurs due to drying of the ink at a distal end of a nozzle; 3) rapidly dry on paper; 4) exhibit good light resistance and water resistance; 5) demonstrate good long-term storage stability; 6) demonstrate print characteristics which are independent of the paper quality; and 7) provide resistance to highlighter after printing.
The ink compositions of the present invention may be prepared by combining the above modified pigments with an aqueous vehicle and any suitable additives. The amount of modified pigment (by weight) in the ink composition is suitably at least about 0.1%, particularly at least about 1.5%, particularly at least about 2.0%, and more particularly at least about 2.5% or about 5.0%. Furthermore, the amount of modified pigment (by weight) in the ink composition is less than or equal to about 12% or about 10%, particularly less than or equal to about 10% or about 8%, and more particularly less than or equal to about 5.5% or about 5%. This includes embodiments where the amount of modified pigment (by weight) in the ink composition is present in an amount ranging from about 0.5% to about 10%, and an amount ranging from about 2% to about 5%.
The aqueous vehicle may comprise water or water in combination with one or more water-soluble organic solvents. The type of water used in the ink compositions is not limited. However, distilled water, deionized water, super pure water, and ultrafiltrate may be used to minimize the introduction of impurities. The water may also be sterilized by UV radiation and/or the addition of hydrogen peroxide. The amount of water (by weight) in the ink composition is at least about 40%, particularly at least about 50%, and more particularly at least about 60%. Furthermore, the amount of water (by weight) in the ink composition is less than or equal to about 90%, particularly less than or equal to about 85%, and more particularly less than or equal to about 80% or about 70%. This includes embodiments where the amount of water (by weight) in the ink composition is about 40% to about 85%.
Water-soluble organic solvents may be combined with water to make up the aqueous vehicle. Water-soluble organic solvents may include alcohols having 1 to 5 carbon atoms, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol and n-pentanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, butylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,2,6-hexanetriol, trimethylolpropane, glycerin, polyethyleneglycol, mesoerythritol and pentaerythritol; ketones and ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl (or monoethyl)ether, diethylene glycol monomethyl (or monoethyl)ether and triethylene glycol monomethyl (or monoethyl)ether; lower dialkyl ethers of polyhydric alcohols, such as triethylene glycol dimethyl (or diethyl)ether and tetraethylene glycol dimethyl (or diethyl)ether; nitrogen-containing solvents such as pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, cyclohexylpyrrolidone, monoethanolamine, diethanolamine, triethanolamine, dimethylformamide and dimethylacetamide; sulfur-containing solvents such as thiodiethanol, thiodiglycerol, sulfolane, and dimethylsulfoxide; propylene carbonate, and ethylene carbonate, sugars and derivatives thereof such as glucose, fructose, galactose, mannose, and xylose; sugar-alcohols; an oxyethylene adduct of glycerin; and an oxyethylene adduct of diglycerin. The water-soluble organic solvents may be used alone or in combination. If a mixture of water and a water-soluble organic solvent is used, the amount of water-soluble organic solvent (by weight) in the ink composition is at least about 1% or about 5%, particularly at least about 15%, and more particularly at least about 20% or about 25%. Furthermore, the amount of water-soluble organic solvent (by weight) in the ink composition is less than or equal to about 80% or about 50%, particularly less than or equal to about 60% or about 30%, and more particularly less than or equal to about 40% or about 15%. This includes embodiments where the amount of water-soluble organic solvent (by weight) in the ink composition is about 5% to about 30%, and more preferably about 1% to about 25%.
Additives may be incorporated into the aqueous vehicle to impart any number of desired properties, such as might be needed to adapt the ink to the requirements of a particular inkjet printer or to provide a balance of light stability, smear resistance, viscosity, surface tension, coating penetration, optical density, adhesion, highlighter resistance or crust resistance. Penetrants, for example, may be added to reduce bleed, improve wetting of the print media, and otherwise improve overall performance of the print image. Examples of penetrants may include, but are not limited to, alkyl alcohols having 1 to 4 carbon atoms, such as ethanol, methanol, butanol, propanol and isopropanol; glycol ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether, ethylene glycol mono isopropyl ether, diethylene glycol mono isopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono t-butyl ether, diethylene glycol mono t-butyl ether, 1-methyl-1-methoxy butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono t-butyl ether, propylene glycol mono n-propyl ether, propylene glycol mono isopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, and dipropylene glycol mono isopropyl ether, diethylene glycol butyl ether, butyl oxitol glycol ether; diols, such as 1,2-alkyl diols; formamide; acetamide; dimethylsulfoxide; sorbitol; sorbitan; acetin; diacetin; triacetin; and sulfolane. The penetrants may be used alone or in combination. The amount of penetrant (by weight) in the ink composition ranges from 0% to about 60%, particularly from about 0% or about 2% to about 40%, and more particularly from about 0.5% to about 15%, or from about 5% to about 20%, or from about 10% to about 15%.
Surfactants may be added to the aqueous medium to reduce the surface tension of the ink composition. The surfactants may be anionic surfactants, non-ionic surfactants and/or cationic surfactants. Suitable surfactants may include those listed below and in U.S. Pat. No. 5,116,409 issued May 26, 1992, U.S. Pat. No. 5,861,447 issued Jan. 19, 1999, and U.S. Pat. No. 6,849,111 issued Feb. 1, 2005, each of which is hereby incorporated by reference.
The anionic surfactants may include alkylbenzene sulfonate, an alkylphenyl sulfonate, an alkylnaphthalene sulfonate, a higher fatty acid salt, a sulfate ester of a higher fatty acid ester, a sulfonate of a higher fatty acid ester, a sulfate ester and a sulfonate of a higher alcohol ether, a higher alkylsulfosuccinate, a polyoxyethylene alkylether carboxylate, a polyoxyethylene alkylether sulfate, an alkylphosphate, and a polyoxyethylene alkylether phosphate. Specific examples of the anionic surfactant include dodecylbenzene sulfonate, isopropylnaphthalene sulfonate, monobutylphenylphenol sulfonate, monobutylbiphenyl sulfonate, monobutylbiphenyl sulfonate, and dibutylphenylphenol disulfonate.
The nonionic surfactants may include a polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether, a polyoxyethylene fatty acid ester, a sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene sorbitol fatty acid ester, a glycerin fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyglycerin fatty acid ester, a cane sugar fatty acid ester, a polyoxyethylene alkylamine, a polyoxyethylene fatty acid amide, an alkylalkanolamide, a polyethylene glycol polypropylene glycol block copolymer, acetylene glycol, and a polyoxyethylene adduct of acetylene glycol, and specific examples of the nonionic surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene fatty acid ester, a sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, fatty acid alkylolamide, a polyethylene glycol/polypropylene glycol block copolymer, acetylene glycol, and a polyoxyethylene adduct of acetylene glycol.
Specific examples of the water-soluble cationic surfactants used in the present invention may include inorganic or organic acid salts of an aliphatic primary amine such as octylamine, laurylamine, stearylamine, oleylamine, tetradecylamine, hexadecylamine, coconut amine, coconut alkylamine, tallow amine, cured tallow alkylamine, soybean alkylamine and the like; inorganic or organic acid salts of an aliphatic secondary amine such as distearylamine, dioleylamine, di-coconut alkylamine, di-cured tallow alkylamine and the like; inorganic or organic acid salts of aliphatic tertiary amine such as dimethyloctylamine, dimethyldecylamine, dimethylaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethylamine, dioleylmonomethylamine, trioctylamine, dimethyl coconut amine, coconut alkyldimethylamine, tallow alkyldimethylamine, cured tallow alkyldimethylamine, soybean alkyldimethylamine, di-coconut alkylmonomethylamine, di-cured tallow alkylmonomethylamine and the like; aliphatic quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, lauryltrimethylammonium chloride, trioctylmethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, docosenyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, coconut alkylrimethylammonium chloride, tallow alkyltrimethylammonium chloride, octadecyldimethyl (3-trimethoxysilylpropyl)ammonium chloride and the like; aromatic quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, benzyltrimethylammonium chloride, phenyltrimethylammonium chloride, cetyldimethylbenzylammonium chloride and the like; pyridinium salt type compounds (e.g., octylpyridinium chloride, cetylpicolinium chloride), imidazoline type cationic compounds (e.g., 2-heptadecenyl-hydroxyethylimidazolium chloride), benzotonium chloride, ethylene oxide added type quaternary ammonium salts (e.g., polyoxyethylenetrimethylammonium chloride), hydrochloride or acetate of aliphatic amides; salt of polyethylenepolyamine aliphatic amides; salt of urea condensate of polyethylenepolyamine aliphatic amides; quaternary ammonium salt of urea condensate of polyethylenepolyamine aliphatic amides; and N,N-dialkylmorphonium salts; and the like.
Other surfactants include a silicone surfactant such as an oxyethylene adduct of polysiloxane, a fluorinated surfactant such as a perfluoroalkylcarboxylate, a perfluoroalkylsulfonate, or an oxyethyleneperfluoroalkyl ether. A biosurfactant such as spicrispolic acid, rhamnolipid, or lysolecithin can also be used.
Among the above described surfactants, surfactants each having an unsaturated bond and surfactants each having a secondary or tertiary alkyl group may be used. Examples of the surfactant each having an unsaturated bond include alkyl ether derivatives of unsaturated alcohols such as oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, 2-heptanedecene-1-ol, and acetylene alcohol; and alkyl ester derivatives of unsaturated fatty acids such as lauroleic acid, myristoleic acid, oleic acid, linoleic acid, linolenic acid, dodecynoic acid, and octadecynoic acid.
Examples of the surfactant each having secondary or tertiary alkyl group include alkyl ether derivatives of branched alcohols such as 2-ethylhexyl alcohol, 2-octanol, 2-hexadecanol, and 2-octadecanol; and alkyl esters of branched fatty acids such as methylheptadecanoic acid, methylpentadecanoic acid, and methyloctadecanoic acid.
Surfactants are commercially available under various well-known tradenames, such as the PLURONIC® series (BASF Corporation, Parsippany, N.J.), the TETRONIC® series (BASF Corporation, Parsippany, N.J.), the ARQUAD® series (Akzo Chemical Inc., Chicago, Ill.), the TRITON® series (Union Carbide Corp., Danbury, Conn.), the SURFONIC® series (Texaco Chemical Company, Houston, Tex.), the ETHOQUAD® series (Akzo Chemical Inc., Chicago, Ill.), the ARMEEN® series (Akzo Chemical Inc., Chicago, Ill.), the ICONOL® series (BASF Corporation, Parsippany, N.J.), the SURFYNOL® series (Air Products and Chemicals, Inc. Allentown, Pa.), and the ETHOMEEN® series (Akzo Chemical Inc., Chicago, Ill.), to name a few.
The surfactants may be used alone or in combination. The amount of surfactant (by weight) in the ink composition may range from 0% to about 10%, particularly from about 0.1% to about 3%, and more particularly from about 0.05 or about 1.5% to about 3% or about 5%. This includes embodiments where the amount of surfactant (by weight) in the ink composition may range from about 0% or about 0.1% to about 8%.
One or more humectants may be added to the aqueous vehicle to prevent clogging, caused by drying out during periods of latency, of inkjet nozzles. Humectants may be selected from materials having high hygroscopicity and water-solubility. Examples of humectants include, but are not limited to, polyols such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2,4-butenetriol, 1,2,6-hexanetriol and pentaerythritol; lactams such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone and F-caprolactam; urea compounds such as urea, thiourea, ethyleneurea and 1,3-dimethylimidazolidinone; saccharides such as maltitol, sorbitol, gluconolactone and maltose; 1,4-cyclohexanedimethanol; 1-methyl-2-piperidone; N-ethylacetamide; N-methylpropionamide; N-acetyl ethanolamine; N-methylacetamide; formamide; 3-amino-1,2-propanediol; 2,2-thiodiethanol; 3,3-thiodipropanol; tetramethylene sulfone; butadiene sulfone; ethylene carbonate; butyrolacetone; tetrahydrofurfuryl alcohol; trimethylpropane; pantothenol and Liponic EG-1. There are no particular limitations on the amount used of the humectant, but in general the amount of humectant (by weight) in the ink composition may range from 0% to about 30%, particularly from about 1% to about 15% or about 20%, and more particularly from about 4% or about 5% to about 10% or about 15%.
Polymers may be added to the ink composition to improve the water resistance, rub resistance and highlighter resistance of the images on print media. Suitable polymers may include, but are not limited to, polyvinyl alcohol, polyester, polyestermelamine, styrene-acrylic acid copolymers, styrene-maleic acid copolymers, styrene-maleic acid-alkyl acrylate copolymers, styrene-metacrylic acid copolymers, styrene-metacrylic acid-alkyl acrylate copolymers, styrene-maleic half ester copolymers, vinyl-naphthalene-acrylic acid copolymers, vinyl naphthalene-maleic acid copolymers and salts thereof. Additional polymers include polyvinylimidazole, derivatives of polyvinylimidazole, copolymers of vinylimidazole, copolymers of vinylimidazole derivatives, polyvinylpyridine, derivatives of polyvinylpyridine, copolymers of vinylpyridine, copolymers of vinylpyridine derivatives, polyethyleneimine, and derivatives of polyethyleneimine. The polymers may be used alone or in combination. The amount of polymer (by weight) in the ink composition may range from 0% to about 5%, particularly from about 0.1% to about 3%, and more particularly from about 0.2% to about 2.5%. This includes embodiments where the amount of polymer (by weight) in the ink composition may range from about 0% or about 0.1% to about 3.0%.
Ink compositions of the present invention may be buffered to a desired pH using any number of pH modifiers. Suitable pH modifiers may include alkali hydroxides (e.g., sodium hydroxide, lithium hydroxide and potassium hydroxide), alkali carbonates and bicarbonates (e.g., sodium carbonate and sodium bicarbonate), ammonium hydroxide, potassium hydrogenphthalate, potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium tetraborate, potassium hydrogen tartrate, sodium hydrogen carbonate, tris(hydroxymethyl)aminomethane, and tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, dimethylethanolamine, triethanolamine, mineral acids, hydrochloric acid, and sulfuric acid. The pH modifiers may be used alone or in combination. The amount of pH modifier (by weight) in the ink composition may range from 0% to about 3.0%, particularly from about 0.1% to about 2.0%, and more particularly from about 0.05% or about 0.5% to about 1.0% or about 1.5%. This includes embodiments where the amount of pH modifier (by weight) in the ink composition ranges from about 0.05% or about 0.2% to about 1.5% or about 2.5%.
Preservatives, such as biocides and fungicides, may also be added to the ink composition. Examples of suitable preservatives include sodium benzoate, pentachlorophenol sodium, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazolin-3-one, methylisothiazolinone and chloromethylisothiazolinone. Commercially available biocides include UCARCIDE® 250 (available from Union Carbide Company), Proxel® CRL, Proxel® BDN, Proxel® GXL, Proxel® XL-2, Proxel® TN (available from Arch Chemicals, Smyrna, Ga.), Dowicides®(Dow Chemical, Midland, Mich.), Nuosept® (Huls America, Inc., Piscataway, N.J.), Omidines® (Olin Corp., Cheshire, Conn.), Nopcocides® (Henkel Corp., Ambler, Pa.), XBINX® 19G (PMC Specialties Group, Inc., Cincinnati, Ohio), Bioban™ (available from Dow Chemical, Midland, Mich.), and Troysans® (Troy Chemical Corp., Newark, N.J.). The preservatives may be used alone or in combination. The amount of preservatives (by weight) in the ink composition may range from 0% to about 1.5%, particularly from about 0.05% to about 1.0%, and more particularly from about 0.1% to about 0.3%. This includes embodiments where the amount of preservative (by weight) in the ink composition may range from about 0.05% to about 0.5%.
The ink composition may contain one or more viscosity modifiers. Viscosity modifiers may include rosin compounds, alginic acid compounds, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, salts of polyacrylic acid, polyvinyl pyrrolidone, gum Arabic and starch. The amount of viscosity modifier (by weight) in the ink composition may range from 0% to about 10%, particularly from about 0.5% to about 8%, and more particularly from about 1% to about 5%. This includes embodiments where the amount of viscosity modifier (by weight) in the ink composition may range from about 0% or about 1% to about 7%.
Other additives which may be incorporated into the aqueous vehicle may also include antioxidants, ultraviolet absorbers, chelating agents, corrosion inhibitors, electric conductivity adjusters, viscosity modifiers, oxygen absorbers, anti-kogation agents, anti-curling agents, anti-bleed agents, defoamers, and buffers.
Examples of suitable corrosion inhibitors may include, without limitation, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite, benzotriazole, tolyltriazole, carboxybenzotriazole, and sodium tolytriazole. The corrosion inhibitors may be used alone or in combination. The amount of corrosion inhibitor (by weight) in the ink composition may range from 0% to about 1.0%, particularly from about 0.05% to about 0.5%, and more particularly from about 0.1% to about 0.3%.
The ink compositions of the present invention may contain one or more colorants in addition to the pigment dispersion of the present invention. Such colorants can be selected from the group of pigments and dyes generally useful in inkjet printing. Examples of such dyes may include, but are not limited to, C. I. Direct Black 17, 19, 32, 51, 71, 108, 146, 154, 168; C. I. Direct Blue 6, 22, 25, 71, 86, 90, 106, 199; C. I. Direct Red 1, 4, 17, 28, 83, 227; C. I. Direct Yellow 12, 24, 26, 86, 98, 132, 142; C. I. Direct Orange 34, 39, 44, 46, 60; C. I. Direct Violet 47, 48; C. I. Direct Brown 109; C. I. Direct Green 59; C. I. Acid Black 2, 7, 24, 26, 31, 52, 63, 112, 118; C. I. Acid Blue 9, 22, 40, 59, 93, 102, 104, 113, 117, 120, 167, 229, 234; C. I. Acid Red 1, 6, 32, 37, 51, 52, 80, 85, 87, 92, 94, 115, 181, 256, 289, 315, 317; C. I. Acid Yellow 11, 17, 23, 25, 29, 42, 61, 71; C. I. Acid Orange 7, 19; and C. I. Acid Violet 49. The dyes as described above may be used singly. Alternatively, two or more of the dyes as described above may be used in combination.
Any one of the organic pigments may be used as a colorant. The pigment is not specifically limited. Examples of such pigments may include, but are not limited to, carbon black, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, thioindigo pigment, triphenylmethane lake pigment, and oxazine lake pigment. Specifically, those having yellow colors include, for example, C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 19, 65, 74, and 83 and Solvent Yellow 33. Those having red colors include, for example, C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 49, 50, 51, 52, 53, 55, 60, 64, 83, 87, 88, 89, 90, 112, 114, 122, 123, and 163. Those having blue colors include, for example, C. I. Pigment Blue 2, 3, 15, 16, 22, and 25. Those having black colors include, for example, C. I. Pigment Black 1 and 7. Those capable of self dispersion, which are subjected to the surface-modifying treatment and which can be stably dispersed even when no dispersing agent is used, are preferred as the pigment.
The ink compositions of the present invention may be formulated using a variety of methods known in the art. In one embodiment, the inks may be formulated using a two vessel method. In this method, a first vessel is used to make the ink base or diluent. A second vessel is used to slowly dilute the pigmented dispersion during a process commonly called a “letdown.” The equipment used in the method of making the ink may be glass, polypropylene, polyethylene, or stainless steel. Other materials that are inert to the ink ingredients may also be used.
First, the appropriate amount of water is added to the first vessel. A mixing device is then placed inside the vessel to agitate the water and provide mixing while the other ingredients are added. Mixing may be achieved either by a magnetic stirring mechanism or a motor driven stirring blade. Any chelating agents are then added to the first vessel and allowed to dissolve prior to the addition of any co-solvents. Next, any desired co-solvents are added and allowed to dissolve. Any desired pH modifiers may then be added and are allowed to dissolve. Finally, any other functional ingredients that may be desired, including, without limitation, surfactants and corrosion inhibitors, may be added and are allowed to dissolve.
The second vessel is prepared by adding the appropriate amount of the pigment dispersion to the vessel. A mixing device is then placed into the vessel. After all of the ingredients in the diluent have dissolved, the diluent is slowly added to the pigment dispersion in the second vessel. The dispersion is mixed during this process. In another embodiment, the pigment dispersion is slowly added to the diluent. After all of the diluent or dispersion has been added, the ink is mixed for about 15 minutes to about 1 hour, or until it is completely homogenous. After mixing, the ink is filtered.
The ink compositions of the present invention are particularly suited for use as an ink composition for inkjet printing wherein droplets of the ink composition are ejected from a printing apparatus and deposited onto a substrate to generate an image. Suitable printing apparatus include, but are not limited to, Continuous Ink Jet (CIJ), prop-on-Demand Valve (DoD Valve), Drop-on-Demand Piezo-Electric (DoD Piezo), Memjet and Thermal Ink Jet (TIJ). Similarly, any suitable substrate may be employed including plain papers, bonded papers, coated papers, transparency materials, textile materials, plastics, polymeric films and inorganic substrates. However, it should be recognized by those skilled in the art that the above ink compositions may also have use in other applications including, but not limited to, general writing utensil applications and stamp applications.
The black ink compositions of the present invention may be used alone, or with a color underlay, to produce a black image or in combination with other ink compositions to produce a color image. In some embodiments, the ink composition of the present invention is used in combination with other ink composition(s), such as a black ink, a cyan ink, a magenta ink and/or a yellow ink. In other embodiments, a cyan ink, a magenta ink and a yellow ink are overprinted to form a black image and this printing is used in combination with the printing of the black ink of the present invention.
The ink compositions of the present invention may have certain print performance characteristics. These print performance characteristics are measured in the following manner.
Print Performance Testing:
Water Resistance Procedure. Spectrodensitometer Procedure.
To test water resistance, a sample that is one half inch wide by three inches long is prepared. The top half is left unprinted while the bottom half is printed with the ink of interest. Using an X-Rite 938 spectrodensitometer with a D65 illuminant and 10 degrees standard observer (available from X-Rite Inc., Grand Rapids, Mich.), the printed block portion of the sample is scanned for initial optical density reading. The printer block half of the sample is submerged under DI water for 60 seconds. The sample is removed and laid down to dry completely on a hard surface. The sample is rescanned for soaked optical density reading. The data is recorded as the difference in optical density readings.
The black and color ink compositions of the present invention may have a water resistance value (measured as the difference in optical density) of about 0.00 to about 2.00, preferably a value of about 0.00 to about 0.20, and more preferably a value of less than about 0.05.
Highlighter Resistance Procedure. Spectrodensitometer Procedure.
A printed test image with a black or colored box two inches wide is prepared. Even pressure is applied on the highlighter and moved back and forth in blank portion of the page to create a baseline highlighted section. The procedure is repeated moving back and forth in and out of the black or colored box. An X-Rite 938 spectrodensitometer with a D65 illuminant and 10 degrees standard observer is used, scanning both in the highlighter baseline area and next to the black or colored box where the highlighter is passing. The data is recorded as the difference in optical density readings.
The black ink compositions of the present invention may have a highlighter resistance value (measured as the difference in optical density) of about 0.00 to about 2.00, preferably a value of about 0.00 to about 0.10, and more preferably a value of less than about 0.04.
The color ink compositions of the present invention may have a highlighter resistance value (measured as the difference in optical density) of about 0.00 to about 0.10, and more preferably a value of less than about 0.04.
Rub Resistance Procedure: Sutherland Rub Tester 2000 (available from Danilee Company, San Antonio, Tex.), 100 cycles, Speed 1, 8 Samples, 41b, Test Pattern 9 from RFver1.4 test file. Spectrodensitometer Procedure.
A printed test image with a black or colored box two inches wide is prepared. A wadded up delicate lab tissue is used to apply even pressure and is rubbed back and forth in and out of the black or colored box. An X-Rite 938 spectrodensitometer with a D65 illuminant and 10 degrees standard observer is used to scan both a blank section of the page as a baseline and next to the black or colored box where the rubbing occurred. The data is recorded as the difference in optical density readings.
The black and color ink compositions of the present invention may have a rub resistance value (measured as the difference in optical density) of about 0.00 to about 2.00, preferably a value of about 0.00 to about 0.25, and more preferably a value of less than about 0.10.
ImageXpert Instrument Procedure [Line Width, Edge Acuity, Intercolor Bleed, Mottle].
The ImageXpert SN1 test image is printed. ImageXpert Xaminer JR software (available from ImageXpert, Nashua, N.H.) is used to scan horizontal and vertical line widths, edge acuity, intercolor bleed, and mottle. The line widths and edge acuity are recorded in microns. Mottle is recorded as the standard deviation from the gray average density from the solid color block of interest.
The black and color ink compositions of the present invention may have an edge acuity value of about 0 microns to about 50 microns, and more preferably a value of less than about 25 microns.
The black and color ink compositions of the present invention may have a line width value of about 200 microns to about 350 microns, and more preferably a value of about 225 microns to about 300 microns.
The black and color ink compositions of the present invention may have a bleed value of about 0 microns to about 100 microns, and more preferably a value of less than about 25 microns.
The black ink compositions of the present invention may have a mottle value of about 0.00 to about 3.00, and more preferably a value of less than about 1.75.
The color ink compositions of the present invention may have a mottle value of about 0.00 to about 6.00, and more preferably a value of less than about 2.00.
Optical Density Procedure
Optical density (OD) is recorded using an X-Rite 938 spectrodensitometer. The OD is measured by supplying the standard illuminant D65 at 0 degrees from the ink sample. Reflectance is measured at 45 degrees from the ink sample. OD is calculated as the negative log of the percent reflected from the ink sample. D65 standard illuminant is defined under the CIE (Commission Internationale de l'eclairage).
The black and color ink compositions of the present invention may have an optical density (measured as the negative log of reflectance) of about 1.00 to about 3.00, and more preferably a value of about 1.30 to about 2.00.
CIE L*a*b* Color Space Coordinates Procedure
An X-Rite 938 spectrodensitometer is used to measure the color space coordinates. The D65 illuminant is used, and 0/45 degree angles from the light source to the sensor are used. In addition, when taking these measurements using the spectrodensitometer, the “CIE 1964 10 degree standard observer” is used in the color translation.
Cartridge Start-up Procedure
Cartridge start-up is used to assess the printability of the ink in the cartridge. The ink is initially printed. Next, the cartridge is allowed to sit in ambient conditions for 3 days, without protecting the print head. The cartridge is then placed back into the printer and the ink is again printed. The prints are visually assessed for feathering, mottle, banding, or lining that appears.
Light Resistance Procedure
Light resistance is a measure of a sample before and after some exposure for an amount of time. The length of time is the same for each sample measured in the experiment. The length of time between experiments can vary from 120 hours to 168 hours of exposure. The samples are exposed to a 765 watts/m2 xenon arc lamp in the Suntest CPS+ fadeometer (available from Atlas Material Testing Technology, Chicago, Ill.). The spectral distribution of the xenon arc lamp is altered using Atlas' Indoor Light filter to simulate indoor light spectral distribution.
A CPS+ fadeometer (available from Atlas Material Testing Technology, Chicago, Ill.) is used to measure the CIE L*a*b* coordinates of the samples before and after exposure. The distance between the two color space coordinates (×E) is calculated by the Pythagorean theorem and expanded for three dimensions.
ΔE=√{square root over ((L1+L2)2+(a1+a2)2+(b1+b2)2)}{square root over ((L1+L2)2+(a1+a2)2+(b1+b2)2)}{square root over ((L1+L2)2+(a1+a2)2+(b1+b2)2)}, where L1, a1, and b1 refer to the first set of L*a*b* coordinates, and L2, a2, and b2 refer to the second set of L*a*b* coordinates.
Heat at 70° C.—Particle Count Procedure
The ink sample is heated to 70° C. and the particles are counted initially, at one week, and at 23 days. The particle size is measured using an Accusizer 780A instrument (available from Partical Sizing Systems, Santa Barbara, Calif.). Pigmented ink flows through a small “photozone.” A “photozone” is a narrow region of uniform illumination produced by light from a laser diode.
0.3 mL of the ink is dispensed into a 100 mL volumetric flask and diluted to the mark with DI water. 0.2 mL of the product of the sample dilution is added to the sample vessel, which contains 60 mL of DI water. The product of the sample dilution is well mixed with a stir bar contained in the sample vessel. The number of particles is calculated using the following formula:
Freeze/Thaw/Heat Cycles Procedure
A 100 gram sample of the pigmented ink is prepared. First, the sample is frozen at −15° C. for 8 hours. It is then thawed at room temperature for another 8 hours. Finally, the sample was heated in an oven at 70° C. for 8 hours. These three steps constitute a single cycle. The cycle is repeated three times. The change in the particle size between the initial sample and the sample after three cycles was measured using an Accusizer 780A instrument.
Examples of papers on which the above-identified tests can be conducted are HP Multipurpose (20 lb weight, 92 brightness value), HP Multipurpose ColorLok (20 lb weight, 96 brightness value), Office Depot 104, Xerox 4200 (20 lb weight, 92 brightness value), Epson Photo Paper Glossy 5041649, Epson Premium Photo Paper Glossy 2041667 (68 lb weight), Office Depot Premium White Copy (20 lb weight, 92 brightness value), and Hammerill Great White Copy (20 lb weight, 92 brightness value).
Paper Independence
The inks of the present invention work on a wide variety of papers. In other words, the inks may work well independent of the particular paper being used. These inks exceed other inks containing polymer stabilized dispersions and other dispersions containing modified pigments. For example, the inks may fall within the following tolerances for specified print quality attributes across a wide range of plain paper, contrary to other inks:
In one embodiment, the invention provides a method of making an ink, the method comprising: sulfonating a pigment; oxidizing the pigment to form a modified pigment; and incorporating the pigment into an ink, wherein prints made from the ink will fall within at least one of the following tolerances with a 95 percent confidence level, regardless of the type of paper on which the print is printed: an optical density of 0.16 (±0.08); line width of 22.88 microns (±11.44); mottle of 0.70 0.35); and bleed of 6.6 microns (±3.3).
Particle size for the below examples was determined according to the following procedure. Samples comprising 8-15% solids were prepared by diluting one drop of sample to 15 ml deionized water and loading into 1 cm disposable cuvette, avoiding air bubbles. Malvern Zetasizer Nano series Model ZEN3600 was then used to measure mean particle size in the sample.
40 g of commercial furnace carbon black (available from Columbian Chemicals, Marietta, Ga.), with a primary particle size of 13 nm and CTAB surface area of 206 m2/g, were sulfonated with 20% oleum (200 g) at 120° C. for 20 hours. The reaction mixture was cooled to 90° C. and quenched in water and ice, allowing the quench temperature to rise to 65° C. The precipitated product was isolated by filtration and washed free of dissolved material. The product cake (108 g) was then oxidized with sodium hypochlorite (lab grade from Fisher, 13% solution, 378 g) allowing the temperature due to exotherm to rise to 60° C. After holding the oxidation mixture at 60° C. for one hour, an additional 377 g of sodium hypochlorite (13% solution) were added and the reaction mixture was held at 60° C. for an additional hour. The reaction mixture was allowed to settle and then filtered to obtain 86 g of cake. The cake was re-dispersed in deionized water, and the pH of the dispersion was adjusted to 9.0. The dispersion was milled with a Hockmeyer media mill (available from Hockmeyer Equipment Corp., Elizabeth City, N.C.) with 0.3 mm YTZ media (available from Quackenbush Co., Inc., Crystal Lake, Ill.). The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 8% solids and mixed with 0.3%, wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through 0.7 micron GF filter.
The resulting dispersion had a solids content of 8.3% and a pH of 9.0. An analysis of the components in the dispersion showed 3 ppm Cl, 38 ppm SO4, 13 ppm Ca, 38 ppm Fe, 2 ppm Mg and 4249 ppm Na. The average particle size was 95.6 nm.
160 g of commercial gas carbon black (available from Degussa, Akron, Ohio), with a primary particle size of 20 nm and B.E.T surface area of 150 m2/g, were sulfonated with 800 g of lab grade (95%) sulfuric acid and 800 g of 20% reagent grade oleum at 120° C. for 21 hours. The reaction mixture was cooled to 60° C. and quenched in water and ice. The precipitated product was isolated by filtration and washed free of dissolved material. The product cake (826 g) was then oxidized with approximately 10.9% sodium hypochlorite solution (1461 g) for one hour at 80° C. to get a fine carbon suspension. The dissolved impurities were removed by ultrafiltration until each of the chloride content and sulfate content of the feed sample adjusted to 10% solids was less than 100 ppm. The pH was adjusted to 7.5 with the addition of either hydrochloric acid or sodium hydroxide prior to completion of the above noted purification step. The product was then concentrated to 16% solids and mixed with 0.3% wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through a 0.7 micron GF filter.
The resulting dispersion had a solids content of 16.1%, a viscosity of 3.2 cP and a pH of 8.2. An analysis of the components in the dispersion showed 6 ppm Cl, 71 ppm SO4, 2.1 ppm Ca, 3.6 ppm Fe, 0.9 ppm Mg and 6571 ppm Na. The average particle size was 116.5 nm.
330 lbs of 99.4% sulfuric acid and 22 lbs of gas carbon black (available from Degussa, Akron, Ohio), with 150 m2/g surface area and primary particle size of 20 nm, were combined in a 30 gallon Pfaudler reactor with good mixing. Once the carbon was dispersed in the sulfuric acid, the mixture was heated to about 120° C. The reaction mixture was stirred for about 20-24 hours while maintaining the temperature of the reaction mixture at about 120-125° C. Stirring was stopped and the reactor was allowed to cool to about 60-65° C.
While the reactor was cooling, a quench tank was filled with about 100 gallons deionized water and about 50 gallons ice to produce a deionized water/ice mixture. The quench tank was cooled to less than 10° C.
Once the reactor temperature reached about 60-65° C., the contents of the reactor were transferred to the quench tank slowly to avoid splashing. The reactor was rinsed with deionized water and the rinsings were added to the mixture in the quench tank. The mixture in the quench tank was heated to about 20-25° C. The material from the quench tank was filtered through a filter press. The filtrate was recycled back to the quench tank until the quench tank was free of solids. The filtered carbon sulfonation cake was washed with about 100 gallons of deionized water and the carbon sulfonation cake was dropped from the press. The carbon sulfonation cake at this point could be stored until ready for use.
32.5 lbs of wet carbon sulfonation cake were combined with 60 lbs of deionized water and mixed overnight. The next day, the mixture was cooled to 30° C. and 16.5 lbs of sodium hydroxide (25% solution) were added to bring the pH up to about 11.9. The mixture was further cooled to 28° C., and 119 lbs of sodium hypochlorite were added to the mixture. An additional 19.5 lbs of sodium hydroxide (25% solution) were added, bringing the pH up to 13.3. The mixture was heated at about 80° C. closed lid for about 1 hour and then cooled to a temperature of 17° C. The mixture was then transferred to an ultrafiltration feed tank. About 0.5 L of 6.3% hydrochloric acid was added to the mixture in the feed tank to bring the pH down to about 7.8. The ultrafiltration was completed in about 13 hours when the desired salt levels and concentration were achieved. The solution was then filtered at 15.6% solids through 1.0 GF and 0.45 μGF filters and diluted to 41.3 lbs for a solids content of 14.8%. Finally, 3 lbs deionized water and 55.8 g of Proxel GXL (available from Arch Chemicals, Smyrna, Ga. and Avecia, Billingham, UK) were added to the mixture.
The resulting dispersion had a solids content of 14.9%, a surface tension of 69 dynes/cm, a pH of 8.1, a conductivity of 1.45 mS and a viscosity of 3.0 cP. The changes in viscosity, pH and surface tension of the dispersion stored at 70° C. for three weeks are summarized below.
An analysis of the components in the dispersion showed 14 ppm Cl, 151 ppm SO4, 4.2 ppm Ca, 4.8 ppm Fe, 1.8 ppm Mg and 5035 ppm Na. The average particle size was 119.3 nm.
The procedure of Example 2 was repeated using 40 g of furnace carbon black (available from Cabot Corporation, Billerica, Mass.), with a primary particle size of 16 nm and a CTAB surface area of 255 m2/g. The carbon black was sulfonated with a 1:1 mixture of commercial grade (93-98%) sulfuric acid (200 g) and 20% oleum (209 g) at 120° C. for a minimum of 18 hours. The oxidation with sodium hypochlorite (˜8% solution, 406 g) took place using the mill described in Example 1, and was then driven to completion by heating to 80° C. with good mixing, for one hour. The product of the reaction was worked up as detailed in Example 1. The carbon dispersion so obtained was filtered through a 0.7 micron GF filter disk and was found to be a stable dispersion at room temperature.
The resulting dispersion had a solids content of 11.3% solids and a pH of 8.42. An analysis of the components in the dispersion showed 11 ppm Cl, 173 ppm SO4, 2.6 ppm Ca, 16 ppm Fe and 5320 ppm Na. The average particle size was 129 nm.
Example 4 was repeated using 40 g of furnace carbon black (available from Columbian Chemicals, Marietta, Ga.) with a primary particle size of 13 nm and CTAB surface area of 206 m2/g.
The resulting dispersion had a solids content of 12.1% solids and a pH of 7.8. An analysis of the components in the dispersion showed 10 ppm Cl, 72 ppm SO4, 2.8 ppm Ca, 17 ppm Fe and 4349 ppm Na. The average particle size was 89.1 nm.
The procedure of Example 3 was repeated except that a second oxidation step was performed before purification by adding additional sodium hydroxide in an amount equivalent to that added in the first oxidation step. In this instance after the second stage oxidation the mixture was heated at 80° C., and the temperature and pH of the mixture were maintained at 80° C. and greater than 9.0, respectively, for a total of 48 hours.
The resulting dispersion had a solids content of 10.56% solids, a surface tension of 68.7 dynes/cm, a viscosity of 1.92 cP, and a conductivity of 1.23 mS. An analysis of the components in the dispersion showed 10 ppm Cl, 56 ppm SO4, 9.9 ppm Ca, 6.4 ppm Fe, 1.0 ppm Mg, and 4330 ppm Na. The average particle size was 106.8 nm.
Example 6 was repeated using the two step oxidation, each step being carried out at 80° C. for a one hour period. After the second oxidation and heat period the reaction mixture was cooled to 60° C. and purified by ultrafiltration. The ultrafiltration was run at a temperature of 50-60° C. until the chloride and sulfate content of the feed sample was less than 100 ppm. The product was then concentrated to 14.1% solids and mixed with 0.3% wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through a 0.7 micron GF filter.
The resulting dispersion had a solids content of 14.1%, a pH of 7.6, a surface tension of 68.8 dynes/cm, a conductivity of 1.20 mS, and a viscosity of 2.45 cP. The changes in viscosity, pH and surface tension of the dispersion stored at 70° C. for three weeks are summarized below.
An analysis of the components in the mixture showed 20 ppm Cl, 33 ppm SO4, 8.4 ppm Ca, 12.5 ppm Fe, 4875 ppm Na, and 2584 ppm sulfur. The particle size of the dispersion was 119 nm.
The sulfonation cake from Example 3 (676.4 g) was re-dispersed in deionized water to a volume of ˜1800 ml. To this slurry was added NaOH to reach a pH of >10.5. The cake slurry was then milled using a media mill (Hockmeyer Basket Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) for 2 hours. During the milling process the volume increased to ˜3500 ml with added deionized water. After the two hour milling period, the dispersion was split in half for the oxidation. Each half of the dispersion was oxidized with 954 g of sodium hypochlorite (10% solution). The pH of each was maintained above 9.0 with the addition of sodium hydroxide (25% solution). The dispersions were then heated at 80° C. for one hour then cooled to 35° C. After cooling, a second portion of sodium hypochlorite (954g at 10%) was added to each dispersion. Again, the pH was kept above 9.0 with the addition of sodium hydroxide. The dispersions were then heated to 80° C. for an additional hour.
This process was repeated a total of 3 times to gain a larger amount of product. All of the oxidized products (6 total) were combined for ultrafiltration. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample is less than 100 ppm. The dispersion was taken and then heated to 80° C. overnight. After the overnight stir period the dispersion was again purified by ultrafiltration to remove the salts. The dispersion was again heated overnight at a temperature of 80° C. After the second heat step the dispersion was purified by ultrafiltration running at a elevated temperature of 50-60° C. until each of the chloride content and the salt content of the feed sample was less than 50 ppm. The product was then concentrated to 15.9% solids and mixed with 0.3% wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through a 0.3 micron depth polypropylene filter (available from Ball Corporation, Port Washington, N.Y.).
The resulting dispersion had a solids content of 15.91% solids, a pH of 8.5, a surface tension of 70.5 dynes/cm, a viscosity of 2.65 cP, and a conductivity of 1.22 mS. The changes in viscosity, pH and surface tension of the dispersion stored at 70° C. for three weeks are summarized below.
An analysis of the components in the dispersion showed 4 ppm Cl, 7 ppm SO4, 8.3 ppm Ca, 16.1 ppm Fe, 1.0 ppm Mg, and 5065 ppm Na. The average particle size was 97.8 nm.
Example 6 was repeated except that a mill (Hockmeyer Basket Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) was used during the first oxidation step with the sulfonation cake.
The resulting dispersion had a solids content of 16.9%, a surface tension of 69.9 dynes/cm, a conductivity of 1.53 mS and a viscosity of 3.0 cP. An analysis of the components in the dispersion showed 12 ppm Cl, 65 ppm SO4, 7.8 ppm Ca, 0.6 ppm Mg, 9.7 ppm Fe and 6096 ppm Na. The average particle size was 98.1 nm.
80 g of commercial pigment red 122 (available from Lansco Colors, Montvale, N.J.) were sulfonated with 95% sulfuric acid (394 g) at 60° C. for 20 minutes. The reaction mixture was cooled to 41° C. and quenched in water and ice. The final quench temperature was 0° C. The precipitated product was isolated by filtration and washed free of dissolved material. A part (55 g, 14.3%) of the product cake was oxidized in the lab using a media mill (Hockmeyer Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) at 2800 rpm, with sodium hypochlorite (commercial grade, 12% solution, 56 g diluted to 120 g with deionized water). The pH was maintained above 10 with the addition of 2.92 g calcium free sodium hydroxide (25% solution). After three hours, additional sodium hypochlorite (20 g diluted to 55 g, as before) was added and milled for an additional 135 minutes. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 4.8% solids and mixed with 0.3%, wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally the product was filtered through 0.7 micron GF filter.
The resulting dispersion had a solids content of 4.8% and a viscosity of 1.34 cP. An analysis of the components in the dispersion showed 82 ppm Cl, 538 ppm SO4, 10.0 ppm Ca, 3.5 ppm Mg, 8.2 ppm Fe and 539 ppm Na.
60 g of commercial pigment red 122 (available from Lansco Colors, Montvale, N.J.) were sulfonated with 90% sulfuric acid (525 g) at 80° C. for 5 hours. The reaction mixture was quenched in water and ice. The final quench temperature was 0° C. The precipitated product was isolated by filtration and washed free of dissolved material. The product cake was slurried in deionized water and oxidized in the lab using a media mill (Hockmeyer Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) at 2800 rpm, with 240 g sodium hypochlorite (commercial grade, 12% solution). The pH was maintained above 9 with the addition of 2.97 g calcium free sodium hydroxide, 25% solution. After three hours, 10.36 g of additional sodium hydroxide was added and milled for an additional 2 hours. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 10 ppm. The product was then concentrated to 11% solids and mixed with 0.3%, wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through a 0.7 micron GF filter.
The resulting dispersion had a solids content of 11.70% and a viscosity of 2.88 cPs. An analysis of the components in the dispersion showed 9 ppm Cl, 6 ppm SO4, 4.1 ppm Ca, 1.2 ppm Mg, 2.7 ppm Fe, 179 ppm S and 568 ppm Na. The dispersion pH was 8.51.
60 g of commercial pigment red 122 (available from BASF Colors, Charlotte, N.C.) were sulfonated with 90% sulfuric acid (524 g) at 80° C. for 5 hours. The reaction mixture was quenched in water and ice. The final quench temperature was 0° C. The precipitated product was isolated by filtration and washed free of dissolved material. The product cake was slurried in deionized water and oxidized in the lab using a media mill (Hockmeyer Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) at 2800 rpm, with 350g sodium hypochlorite (commercial grade, 12% solution). The pH was maintained above 9 with the addition of 2.9 g calcium free sodium hydroxide, 25% solution. After three hours, 14.9 g of additional sodium hydroxide were added and milled for additional 2 hours. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 10 ppm. The product was then concentrated to 10% solids and mixed with 0.3%, wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through a 0.7 micron GF filter.
The resulting dispersion had a solids content of 9.81% and a viscosity of 2.01 cPs. An analysis of the components in the dispersion showed 16 ppm Cl, 7 ppm SO4, 3.2 ppm Ca, 1 ppm Mg, 1 ppm Fe, 239 ppm S and 605 ppm Na. The dispersion pH was 8.19.
60 g of commercial pigment red 122 (available from Clariant Colors, Charlotte, N.C.) were sulfonated with 90% sulfuric acid (475 g) at 80° C. for 5 hours. The reaction mixture was quenched in water and ice. The final quench temperature was 0° C. The precipitated product was isolated by filtration and washed free of dissolved material. The product cake was slurried in deionized water and oxidized in the lab using a media mill (Hockmeyer Basket Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) at 2800 rpm, with 350 g sodium hypochlorite (commercial grade, 12% solution). The pH was maintained above 9 with the addition of 2.6 g calcium free sodium hydroxide, 25% solution. After three hours, 12.6 g of additional sodium hydroxide were added and milled for additional 2 hours. The dissolved impurities were removed by ultrafiltration until each of the chloride and sulfate content of the feed sample was less than 10 ppm. The product was then concentrated to 11% solids and mixed with 0.3%, wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through 0.7 micron GF filter.
The resulting dispersion had a solids content of 11.07% and a viscosity of 2.1 cP. An analysis of the components in the dispersion showed 7 ppm Cl, 5 ppm SO4, 3.4 ppm Ca, 0.9 ppm Mg, 1.2 ppm Fe, 133 ppm S and 777 ppm Na. The dispersion pH was 8.09. The introduction of S (0.344 mMoles of S per gram of sample) via sulfonation was confirmed by elemental analysis of a dried sample (by Schwarskopf Microanalytical Laboratory, Woodside, N.Y.).
60 g of commercial pigment red 122 (available from Sun Chemical, Cincinnati, Ohio) were sulfonated with 90% sulfuric acid (525 g) at 80° C. for 5 hours. The reaction mixture was quenched in water and ice. The final quench temperature was 0° C. The precipitated product was isolated by filtration and washed free of dissolved material. The product cake was slurried in deionized water and oxidized in the lab using a media mill (Hockmeyer Basket Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) at 2800 rpm, with 280 g sodium hypochlorite (commercial grade, 12% solution). The pH was maintained above 9 with the addition of 1.78 g calcium free sodium hydroxide, 25% solution. After three hours, 10 g of additional sodium hydroxide were added and milled for an additional 2 hours. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 10 ppm. The product was then concentrated to 11% solids and mixed with 0.3%, wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through 0.7 micron GF filter.
The resulting dispersion had a solids content of 11.70% and a viscosity of 2.88 cP. An analysis of the components in the dispersion showed 9 ppm Cl, 5 ppm SO4, 1.8 ppm Ca, 0.4 ppm Mg, 0.6 ppm Fe, 71.3 ppm S and 460 ppm Na. The dispersion pH was 8.75
25 g of commercial pigment red 122 (available from Lansco Colors, Montvale, N.J.) were added to 500 ml deionized water and mixed at 1000 rpm to wet the pigment. Then the mixture was milled for 1.5 hours using a media mill (Hockmeyer Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) at 3000 rpm. Milling was continued for another hour after adding sodium hypochlorite (125 g, commercial grade, 10% solution). The milled product was stirred overnight and then isolated as a wet cake. The dissolved impurities were removed first by washing the cake with deionized water and then by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 7.74% solids and mixed with 0.3%, wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). The product was not a stable dispersion, settling was noticed on standing three days at ambient temperature.
The resulting dispersion had a solids content of 7.74% solids, a surface tension of 70.9, a viscosity of 1.91 cP, and a conductivity of 0.980 mS. An analysis of the components in the dispersion showed 57 ppm Cl, 474 ppm SO4, 24 ppm Ca, 2.3 ppm Mg, 8.3 ppm Fe and 335.7 ppm Na.
20 g of commercial pigment red 122 (available from Lansco Colors, Montvale, N.J.) were added to 95% sulfuric acid (200 g) and heated to 80° C. After 2 hours at 80° C., it was quenched into an ice/water mixture. The isolated wet cake was washed with deionized water to remove excess acid and then re-dispersed in 200 g deionized water. A sufficient amount of calcium free sodium hydroxide was added to bring the pH to about 10. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 7.35% solids and mixed with 0.3%, wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). The product could not be filtered through 0.7 micron GF filter. After 1 week in an oven at 70° C., the material showed hard settling in the bottom of the container.
The resulting dispersion had a solids content of 7.35%, a surface tension of 70.5 dynes/cm, a viscosity of 2.27 cP, and a conductivity of 0.39 mS. An analysis of the components in the dispersion showed 10 ppm Cl, 50 ppm SO4, 0.9 ppm Ca, 3.9 ppm Fe, 0.2 ppm Mg and 324.7 ppm Na.
80 g of commercial pigment blue 15:1 (available from Fanwood Chemical, Fanwood, N.J.) were sulfonated with 99.5% sulfuric acid (424 g) at 114-120° C. for 160 minutes. The reaction mixture was cooled to 100° C. and quenched in water and ice. The final quench temperature was 25° C. The precipitated product was isolated by filtration and washed free of dissolved material. A part (160 g, 48%) of the product cake was dispersed in the lab using a media mill (Hockmeyer Baske Mill) charged with 0.4 mm YTZ® beads (available from Quackenbush Co., Inc., Crystal Lake, Ill.) at 2800 rpm. The pH was maintained above 10 with the addition of 47.4 g calcium free sodium hydroxide, 25% solution. After three and a half hours, one half of this dispersion was oxidized with sodium hypochlorite (commercial grade, 12% solution, 56 g diluted to 126 g with deionized water) in the mill for additional hour. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 4.8% solids and mixed with 0.3% wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through 0.7 micron GF filter.
The resulting dispersion had a solids content of 4.8% and a viscosity of 1.34 cP. An analysis of the components in the dispersion showed 82 ppm Cl, 538 ppm SO4, 10.0 ppm Ca, 3.5 ppm Mg, 8.2 ppm Fe and 539 ppm Na.
120 g of commercial pigment blue 15:3 (available from BASF Corporation, Charlotte, N.C.) were sulfonated with a mixture of 300 g of sulfuric acid (95%) and 300 g of 20% oleum at 120° C. for 6 hours. The reaction mixture was cooled to 100° C. and quenched in water and ice. The solid product was isolated by filtration and washed free of dissolved material. The cake was dispersed using a media mill (Hockmeyer Basket Mill) charged with 0.4 mm YTZ beads (available from Quackenbush Co. Inc., Crystal Lake, Ill.) at 3000 rpm. The pH was maintained above 9.0 with the addition of 60 g calcium free sodium hydroxide, 25% solution. After 2 hours on the mill the dispersion was oxidized with 371.6 g of sodium hypochlorite (10.9%) in the mill for an additional 3 hours. The resulting product was then heated to 80° C. for a period of 1 hour. The dissolved impurities were then removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 100 ppm. The product was concentrated to 7.7% solids and mixed with 0.3% wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through a 0.7 micron GF filter.
The resulting dispersion had a solids content of 7.73% solids and a pH of 8.24. An analysis of the components in the dispersion showed 23 ppm Cl, 21 ppm SO4, 1.7 ppm Ca, 1.5 ppm Fe, 1830 ppm Na and 1560 ppm sulfur. The dispersion also had a viscosity of 2.10 cP, a surface tension of 69.1 dynes/cm, and a conductivity of 2.4 mS. The introduction of S (0.894 mMoles of S per gram of sample) via sulfonation was confirmed by elemental analysis of a dried sample (by Schwarskopf Microanalytical Laboratory, Woodside, N.Y.).
40 g of commercial pigment blue 15:3 (available from BASF Corporation, Charlotte, N.C.) were sulfonated with 200 g sulfuric acid (95%) at 120° C. for 24 hours. The reaction mixture was cooled to 100° C. and quenched in water and ice. The solid product was isolated by filtration and washed free of dissolved material. The acidic cake was brought to a pH of 8.0 and re-dispersed in deionized water. The resulting mixture was filtered to isolate the cake. The cake was dispersed using a media mill (Hockmeyer Basket Mill) charged with 0.4 mm YTZ beads (available from Quackenbush Co. Inc., Crystal Lake, Ill.) at 3000 rpm. After 2 hours on the mill the dispersion was oxidized with 55 g of 10.9% sodium hypochlorite in the mill for an additional 2 hours. The resulting product was then heated to 65° C. for 1 hour. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 100 ppm. The product was concentrated to 7% solids and mixed with 0.3% wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through a 9-0.8 micron depth GF filter.
The resulting dispersion had a solids content of 6.38% and a pH of 7.5. An analysis of the components in the dispersion showed 160 ppm Cl, 21 ppm SO4, 2.7 ppm Ca, 2.9 ppm Fe, 713 ppm Na and 1529 ppm sulfur. The dispersion also had a viscosity of 6.9 cP, a surface tension of 68.8 dynes/cm, and a conductivity of 1.38 mS.
40 g of commercial solvent yellow 33 (available from Rainbow Chemicals Co., Northbrook, Ill.) were sulfonated using 200 g sulfuric acid (95%) at 120° C. for 6 hours. The reaction mixture was cooled to 100° C. and quenched in ice and water. The solid product was isolated by filtration and washed free of dissolved material. The resulting mixture was filtered to isolate the cake. The cake was dispersed using a media mill (Hockmeyer Basket Mill) charged with 0.4 mm YTZ beads (available from Quackenbush Co. Inc., Crystal Lake, Ill.) at 3000 rpm. After 3 and a half hours on the mill, the dispersion was oxidized with 65 g of 10.9% sodium hypochlorite in the mill for an additional hour. The resulting product was then heated to 60° C. for one hour. The dissolved impurities were removed by ultrafiltration until each of the chloride content and the sulfate content of the feed sample was less than 100 ppm. The product was concentrated to 2.17% solids and mixed with 0.3% wt/wt Proxel GXL (available from Arch Chemicals, Smyrna, Ga.). Finally, the product was filtered through a 9-0.8 micron depth GF filter.
The resulting dispersion had a solids content of 2.17% and a pH of 6.99. An analysis of the components in the dispersion showed 4 ppm Cl, 68 ppm SO4, 2.3 ppm Ca, 15.2 ppm Fe, 187 ppm Na and 278 ppm sulfur. The dispersion had a viscosity of 1.55 Cp, a surface tension of 57.7 dynes/cm, and a conductivity of 0.578 mS.
Counterions associated with surface modifying groups of a pigment may be substituted with other suitable cations as exemplified by the following procedure.
The dispersion obtained from Example 3 (3200 g, 14.85% solids, pH=8.1) was further purified by ultrafiltration while the pH of the product was adjusted slowly downward with dilute hydrochloric acid (1 pH unit at a time over several hours) without shocking the pigment dispersion. A total of 34.7 g of 25% HCl was used to lower the pH to 5.5. When the product was found to be free of dissolved impurities, it was concentrated to 2693.1 g (14% solids, 12 ppm Cl and 45 ppm SO4).
Different mixed salts (˜50% sodium) with monoethanolammonium (MEA), triethanolammonium (TEA), tetramethylammonium (TMA), tetrabutylammonium (TBA), lithium, potassium, and ammonium were formed in 300 g portions by adjusting the pH to about 8.0 with corresponding base (e.g., KOH, NH4OH, etc.). The properties of the resulting dispersions are summarized in Table 1.
Mixed salts (<20% sodium) were prepared in a similar manner to the mixed salts (˜50% sodium) except that the pH was adjusted downward with dilute hydrochloric acid to a stable pH of 2.0 without shocking. The properties of the resulting dispersions are summarized in Table 2.
XPS data were collected and analyzed for Samples 1-4 (Table 3).
The XPS data were acquired by EAG Labs (in Chanhassen, Minn.) using a Physical Electronics Quantum 2000 Scanning XPS instrument with a probe beam of focused, monochromatic Al Kα 1486.6 eV radiation. Analyses were conducted in a 1.5 mm×0.3 mm analysis area with a 45° correction angle and no charge correction or charge neutralization. The x-rays generated photoelectrons that were energy analyzed and counted to reveal the atomic composition and chemistry of the sample surfaces. The escape depth of the photoelectrons limited the depth of analysis to the outer ˜50 Å.
Samples 1 and 3 were mounted directly in powder form. Samples 2 and 4 (dispersed liquids) were prepared by drying down a small amount of the liquid under a nitrogen atmosphere and then grinding the resultant films to powders.
Elements detected on all samples included C, O, S and Cl. Samples 2 and 4 also had Na present. A trace of organic N was present on Sample 4.
As shown in
As shown in
Nitrogen was only detected at low level on sample 4 and no high resolution spectrum was acquired. Its binding energy in the survey spectrum suggests an organic form.
As shown in
The high resolution spectra were used to obtain surface composition by integrating the areas under the photoelectron peaks and applying empirical sensitivity factors. The Atomic % (Table 4), % of Elements Detected (Table 5) and Atomic % by Chemical State (Table 6) for each sample are presented below.
1Normalized to 100% of the elements detected. XPS does not detect H or He.
2Detection limits are typically between 0.05% and 1.0% for other elements.
3A dash “—” indicates the element was not detected.
SEM analyses were performed on base carbon black (Sample 1, Table 3), carboxy modified carbon black (oxidized) (Sample 2, Table 3) and sulfonated, carboxy modified carbon black (Sample 4, Table 3) using a Hitachi S-4500 Field Emission Scanning Electron Microscope. The samples were dried at room temperature prior to analysis.
The SEM Images (15.0 kV×500 K 60 nm) of (a) carbon black with an average diameter of ˜39.3±3 nm, (b) carboxy modified carbon black with an average diameter of ˜31.1±3 nm, and (c) sulfonated carboxy modified carbon black with an average diameter of ˜38.7±2 nm, are provided in
TGA was performed on TA Instruments' TGA instrument under nitrogen atmosphere, heating from 30° C. to 800° C. at a rate of 10° C. per minute. As shown in
Each of the modified carbon blacks exhibit three distinct weight loss regions. It is possible to calculate the weight loss over these regions as equivalent to CO2 gas released. As shown in
As shown in
By comparison, as shown in
The samples (as aqueous dispersions) were titrated with undiluted 2.000 N HCl from a 50 ml burette calibrated to 0.1 ml. The samples and the titrant were not diluted so that the pH of 2.0 could be achieved using a reasonable quantity of titrant, and so that the volume change over the course of the titration would be less (ca. 10% increase in volume during the course of the titration). Data are summarized in Table 10 for the acid uptake over the pH interval 10.2 to 2.0 for the carbon dispersions and for deionized water. The first column shows the total uptake of HCl in mMoles over this pH interval, and the second column shows the uptake converted to mMoles/g based upon the % solids. As expected, the uptake per gram is largest for the product described in Example 7. Examples with oxidation and the carbon black raw material are included for comparison.
The surface modified carbon black dispersion (sulfonated, carboxy modified carbon black) made according to Examples 2 and 8 were analyzed as a dry powder (dried in the oven at 70° C. to constant weight) by Schwarskopf Microanalytical Laboratory, Woodside, N.Y. and compared with the original carbon black powder and oven dried, thoroughly washed sulfonated acid cake. The surface modified pigment blue 15 (Example 16) and pigment red 122 (Example 13) were similarly analyzed as a dry powder. The results of the elemental analysis are summarized in Table 11.
1The sodium was calculated @100% solids from ICP metal analysis of the original dispersion.
The results of the elemental analysis indicate that Example 8 yields a modified carbon black with 0.478 mMoles of S and 1.51 mMoles of active hydrogen per gram of carbon.
The results of the elemental analysis indicate that Example 2 yields a modified carbon black with 0.738 mMoles of S and 1.77 mMoles of active hydrogen per gram of carbon.
The results of the elemental analysis indicate that Example 16 yields a modified pigment blue 15 with 0.894 mMoles of S and 1.03 mMoles of active hydrogen per gram of pigment.
The results of the elemental analysis indicate that Example 13 yields a modified pigment red 122 with 0.034 mMoles of S and 0.304 mMoles of active hydrogen per gram of pigment.
In the following examples, the print performance characteristics of the inks were analyzed according to the aforementioned water resistance procedure, highlighter resistance procedure, rub resistance procedure, ImageXpert instrument procedure (line width, edge acuity, intercolor bleed, mottle), optical density procedure, L*a*b* color space coordinates procedure, cartridge start-up procedure, and light resistance procedure.
The following composition is an ink formulation incorporating the self-dispersing pigment made according to Example 7.
The ink composition was formulated using a two vessel method. A first vessel was used to make the ink base or diluent. A second vessel was used to slowly dilute the pigmented dispersion during a process commonly called a “letdown.” The equipment used in the method of making the ink was glass.
First, the water was added to the first vessel. A mixing device was then placed inside the vessel to agitate the water and provide mixing while the other ingredients are added. Mixing was achieved using a magnetic stirring device. Next, 2-pyrrolidone, diethylene glycol, and IPA anhydrous were added to the vessel. These were allowed to dissolve. Then, PEG 600 and Proxel GXL were added and allowed to dissolve.
The second vessel was prepared by adding the pigment dispersion made according to Example 7 to the vessel. A magnetic stirring device was then placed into the vessel. After all of the ingredients in the diluent had dissolved, the dispersion and the diluent were mixed together. After the diluent and dispersion were combined, the ink was mixed for about 1 hour, or until it was homogenous. After mixing, the ink was filtered using a 1 micron glass filter (available from Whatman, Kent, England).
Print Performance Testing
The print performance of the above-identified ink was compared to inks comprising Sensijet® Black SDP 100 and 1000 available from Sensient Colors Inc. (St. Louis, Mo.). The comparison inks were prepared using Sensijet® Black SDP 100 and 1000 in the Ink A formulation. The carbon black inks were printed on three commonly used copy papers—Hewlett Packard Multipurpose Paper, Office Depot 104 paper, and Xerox 4200 multipurpose paper. In the highlighter test two highlighters were used—Sharpie Accent (H1) and Eberhard Faber 4009 (H2).
The analysis of the prints showed Ink A to be superior in all tests compared to the comparative inks containing Sensijet® Black SDP 100 and 1000.
The following are different salt forms of the black dispersion prepared according to Example 3, converted to a mixed salt containing <50% Na salt, and incorporated into the following ink formulations using the procedure described below.
The ink compositions described in the table above were formulated using a two vessel method. A first vessel was used to make the ink base or diluent. A second vessel was used to slowly dilute the pigmented dispersion during a process commonly called a “letdown.” The equipment used in the method of making the ink was glass.
First, the appropriate amount of water was added to the first vessel. A mixing device was then placed inside the vessel to agitate the water and provide mixing while the other ingredients are added. Mixing was achieved by using a magnetic stirring device. Next, the appropriate amounts of 2-pyrrolidone, PEG 400,1,2-hexanediol, and butyl oxitol glycol ether were added to the vessel. These were allowed to dissolve. Then, the appropriate amount of triethanolamine was added and allowed to dissolve. Finally, the appropriate amounts of Cobratec solution and Bioban were added and allowed to dissolve.
The second vessel was prepared by adding the appropriate amount of the pigment dispersion made according to Example 3 to the vessel. A magnetic stirring device was then placed into the vessel. After all of the ingredients in the diluent had dissolved, the dispersion and the diluent were mixed together. After the diluent and dispersion were combined, the ink was mixed for about 1 hour, or until it was homogenous. After mixing, the ink was filtered using a 1 micron glass filter (available from Whatman, Kent, England).
The print performance characteristics of the above inks on Xerox 4200 paper are given below.
Ink formulations comprising the color pigment dispersions prepared according to Examples 13 (Ink I) and 16 (Ink J) are given below:
The ink compositions described in the table above were formulated using a two vessel method. A first vessel was used to make the ink base or diluent. A second vessel was used to slowly dilute the pigmented dispersion during a process commonly called a “letdown.” The equipment used in the method of making the ink was glass.
First, water was added to the first vessel. A mixing device was then placed inside the vessel to agitate the water and provide mixing while the other ingredients are added. Mixing was achieved by using a magnetic stirring device. Next, glycerine, PEG 600, butyl carbitol, ethanol, and butanol were added to the vessel. These were allowed to dissolve. Then, triethanolamine was added and allowed to dissolve. Finally, Cobratec solution and Xbinx 19G were added and allowed to dissolve.
The second vessel was prepared by adding the pigment dispersion made according to Example 13 or Example 16 to the vessel. A magnetic stirring device was then placed into the vessel. After all of the ingredients in the diluent had dissolved, the dispersion and the diluent were mixed together. After the diluent and dispersion were combined, the ink was mixed for about 1 hour, or until it was homogenous. After mixing, the ink was filtered using a 1 micron glass filter (available from Whatman, Kent, England).
The print performance characteristics of these inks on HP Multipurpose paper are provided below.
The following ink formulation was made as described below and incorporated the self-dispersing pigment made according to Example 16.
The ink composition described in the table above was formulated using a two vessel method. A first vessel was used to make the ink base or diluent. A second vessel was used to slowly dilute the pigmented dispersion during a process commonly called a “letdown.” The equipment used in the method of making the ink was glass.
First, water was added to the first vessel. A mixing device was then placed inside the vessel to agitate the water and provide mixing while the other ingredients are added. Mixing was achieved by using a magnetic stirring device. Next, glycerine, PEG 600, butyl carbitol, ethanol, and butanol were added to the vessel. These were allowed to dissolve. Then, triethanolamine was added and allowed to dissolve. Finally, Cobratec solution and Xbinx 19G were added and allowed to dissolve.
The second vessel was prepared by adding the pigment dispersion made according to Example 16 to the vessel. A magnetic stirring device was then placed into the vessel. After all of the ingredients in the diluent had dissolved, the dispersion and the diluent were mixed together. After the diluent and dispersion were combined, the ink was mixed for about 1 hour, or until it was homogenous. After mixing, the ink was filtered using a 1 micron glass filter (available from Whatman, Kent, England).
The print performance characteristics of this ink on HP Multipurpose paper are identified below.
The following ink formulation was made according to Example 28 and incorporated the self-dispersing pigment made according to Example 13.
The print performance characteristics of this ink on HP Multipurpose paper are identified below.
The following ink formulation was made according to the procedure described below and incorporated the self-dispersing pigment made according to Example 10.
The ink composition described in the table above was formulated using a two vessel method. A first vessel was used to make the ink base or diluent. A second vessel was used to slowly dilute the pigmented dispersion during a process commonly called a “letdown.” The equipment used in the method of making the ink was glass.
First, water was added to the first vessel. A mixing device was then placed inside the vessel to agitate the water and provide mixing while the other ingredients are added. Mixing was achieved by using a magnetic stirring device. Next, glycerine, PEG 600, glycol ether DB, IPA anhydrous, and N-Butanol Eastman were added to the vessel. These were allowed to dissolve. Then, triethanolamine 85 was added and allowed to dissolve. Finally, Cobratec solution and Nipacide BIT 20 were added and allowed to dissolve.
The second vessel was prepared by adding the pigment dispersion made according to Example 10 to the vessel. A magnetic stirring device was then placed into the vessel. After all of the ingredients in the diluent had dissolved, the dispersion and the diluent were mixed together. After the diluent and dispersion were combined, the ink was mixed for about 1 hour, or until it was homogenous. After mixing, the ink was filtered using a 1 micron glass filter (available from Whatman, Kent, England).
The physical parameters of this ink are identified below.
The print performance characteristics of this ink are identified below.
The following ink formulation was made according to the procedure described below and incorporated the self-dispersing pigment made according to Example 7.
The ink composition described in the table above was formulated using a two vessel method. A first vessel was used to make the ink base or diluent. A second vessel was used to slowly dilute the pigmented dispersion during a process commonly called a “letdown.” The equipment used in the method of making the ink was glass.
First, water was added to the first vessel. A mixing device was then placed inside the vessel to agitate the water and provide mixing while the other ingredients are added. Mixing was achieved by using a magnetic stirring device. Next, 2-pyrrolidone, PEG 600, and IPA anhydrous were added to the vessel. These were allowed to dissolve. Then, triethanolamine 85 was added and allowed to dissolve. Finally, Nipacide BIT 20 was added and allowed to dissolve.
The second vessel was prepared by adding the pigment dispersion made according to Example 7 to the vessel. A magnetic stirring device was then placed into the vessel. After all of the ingredients in the diluent had dissolved, the dispersion and the diluent were mixed together. After the diluent and dispersion were combined, the ink was mixed for about 1 hour, or until it was homogenous. After mixing, the ink was filtered using a 1 micron glass filter (available from Whatman, Kent, England).
The physical parameters of this ink are identified below.
The print performance characteristics of this ink are identified below.
The following ink formulation was made according to the procedure described below and incorporated the self-dispersing pigment made according to Example 7.
The ink composition described in the table above was formulated using a two vessel method. A first vessel was used to make the ink base or diluent. A second vessel was used to slowly dilute the pigmented dispersion during a process commonly called a “letdown.” The equipment used in the method of making the ink was glass.
First, water was added to the first vessel. A mixing device was then placed inside the vessel to agitate the water and provide mixing while the other ingredients are added. Mixing was achieved by using a magnetic stirring device. Next, 2-pyrrolidone, 1,5-pentanediol, PEG 600, and 1,2-hexanediol were added to the vessel. These were allowed to dissolve. Then, Surfynol 104E solution and Nipacide BIT 20 were added and allowed to dissolve.
The second vessel was prepared by adding the pigment dispersion made according to Example 7 to the vessel. A magnetic stirring device was then placed into the vessel. After all of the ingredients in the diluent had dissolved, the dispersion and the diluent were mixed together. After the diluent and dispersion were combined, the ink was mixed for about 1 hour, or until it was homogenous. After mixing, the ink was filtered using a 1 micron glass filter (available from Whatman, Kent, England).
The physical parameters of this ink are identified below.
The print performance characteristics of this ink are identified below.
Thus, the invention provides, among other things, surface modified pigments and inks and methods of making and using the same. Various features and advantages of the invention are set forth in the following claims.
This application is a continuation of U.S. patent application Ser. No. 11/933,116, now U.S. Pat. No. 7,927,416, filed Oct. 31, 2007, which claims benefit of U.S. Provisional Application No. 60/855,573, filed Oct. 31, 2006, now expired. The entire contents of each of these applications are hereby incorporated by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 630868 | Dorman | Aug 1899 | A |
| 1901861 | Baker | Mar 1933 | A |
| 2034508 | Boer et al. | Mar 1933 | A |
| 2178383 | Wiegand | Oct 1939 | A |
| 2281261 | Bjorksten et al. | Apr 1942 | A |
| 2439442 | Amon et al. | Apr 1948 | A |
| 2439443 | Aske | Apr 1948 | A |
| 2641533 | Cines | Jun 1953 | A |
| 2811501 | Stedry | Oct 1957 | A |
| 2816046 | Damusis | Dec 1957 | A |
| 2867540 | Melvin | Jan 1959 | A |
| 2993903 | Kraus | Jul 1961 | A |
| 3023118 | Donnet | Feb 1962 | A |
| 3025259 | Watson et al. | Mar 1962 | A |
| 3043708 | Edwin et al. | Jul 1962 | A |
| 3243752 | Lawrence | Mar 1966 | A |
| 3271383 | Yamaya et al. | Sep 1966 | A |
| 3291788 | Yamaya et al. | Dec 1966 | A |
| 3306761 | Johnson | Feb 1967 | A |
| 3323932 | Aboytes et al. | Jun 1967 | A |
| 3347632 | Parker | Oct 1967 | A |
| 3368990 | Goulston | Feb 1968 | A |
| 3412054 | Milligan et al. | Nov 1968 | A |
| 3442679 | Rivin et al. | May 1969 | A |
| 3519452 | Rivin et al. | Jul 1970 | A |
| 3528840 | Aboytes | Sep 1970 | A |
| 3565657 | Dannenberg et al. | Feb 1971 | A |
| 3623899 | Lagally | Nov 1971 | A |
| 3697425 | Lagally | Oct 1972 | A |
| 3755287 | Hegar et al. | Aug 1973 | A |
| 3895004 | de Montmollin et al. | Jul 1975 | A |
| 3901818 | Durand et al. | Aug 1975 | A |
| 3971849 | Prasad et al. | Jul 1976 | A |
| 3992218 | Suetsugu et al. | Nov 1976 | A |
| 4003981 | Turk | Jan 1977 | A |
| 4069218 | Hegar | Jan 1978 | A |
| 4156616 | Dietz et al. | May 1979 | A |
| 4197221 | Eisenmenger et al. | Apr 1980 | A |
| 4201647 | Spaziante et al. | May 1980 | A |
| 4243772 | Paul et al. | Jan 1981 | A |
| 4298526 | Sappok et al. | Nov 1981 | A |
| 4343767 | Long et al. | Aug 1982 | A |
| 4386851 | Eidorff | Jun 1983 | A |
| 4388115 | Sugiyama et al. | Jun 1983 | A |
| 4406662 | Beran et al. | Sep 1983 | A |
| 4425162 | Sugiyama et al. | Jan 1984 | A |
| 4435717 | Eida et al. | Mar 1984 | A |
| 4477621 | Sato et al. | Oct 1984 | A |
| 4485041 | Hoyer et al. | Nov 1984 | A |
| 4500672 | Suzuki et al. | Feb 1985 | A |
| 4507236 | Seiler et al. | Mar 1985 | A |
| 4508570 | Fujii et al. | Apr 1985 | A |
| 4530961 | Nguyen et al. | Jul 1985 | A |
| 4532296 | Gardner | Jul 1985 | A |
| 4533776 | Baasner et al. | Aug 1985 | A |
| 4581445 | Ramanathan | Apr 1986 | A |
| 4597794 | Ohta et al. | Jul 1986 | A |
| 4609404 | Marraccini et al. | Sep 1986 | A |
| 4624709 | Otsuka | Nov 1986 | A |
| 4624773 | Hettinger | Nov 1986 | A |
| 4627875 | Kobayashi et al. | Dec 1986 | A |
| 4631085 | Kawanishi et al. | Dec 1986 | A |
| 4647310 | Shimada et al. | Mar 1987 | A |
| 4666519 | Akiyama et al. | May 1987 | A |
| 4666993 | Urano et al. | May 1987 | A |
| 4670059 | Hackleman et al. | Jun 1987 | A |
| 4680332 | Hair et al. | Jul 1987 | A |
| 4683002 | Mirua et al. | Jul 1987 | A |
| 4685968 | Palmer | Aug 1987 | A |
| 4689078 | Koike | Aug 1987 | A |
| 4694302 | Hackleman | Sep 1987 | A |
| 4695824 | Tazaki | Sep 1987 | A |
| 4711668 | Shimada et al. | Dec 1987 | A |
| 4713081 | Becker | Dec 1987 | A |
| 4713113 | Shimada et al. | Dec 1987 | A |
| 4732613 | Shioya et al. | Mar 1988 | A |
| 4737190 | Shimada et al. | Apr 1988 | A |
| 4761180 | Askeland et al. | Aug 1988 | A |
| 4765838 | Ohata et al. | Aug 1988 | A |
| 4786327 | Wenzel et al. | Nov 1988 | A |
| 4790880 | Miller | Dec 1988 | A |
| 4793860 | Murakami et al. | Dec 1988 | A |
| 4798856 | Ayala et al. | Jan 1989 | A |
| 4810292 | Palmer | Mar 1989 | A |
| 4836851 | Pawlowski et al. | Jun 1989 | A |
| 4836852 | Knirsch et al. | Jun 1989 | A |
| 4838938 | Tomida | Jun 1989 | A |
| 4844569 | Wada et al. | Jul 1989 | A |
| 4846851 | Guro et al. | Jul 1989 | A |
| 4853036 | Koike et al. | Aug 1989 | A |
| 4853037 | Johnson et al. | Aug 1989 | A |
| 4855762 | Suzuki | Aug 1989 | A |
| 4914562 | Abe et al. | Apr 1990 | A |
| 4931950 | Isle et al. | Jun 1990 | A |
| 4952551 | Buehler | Aug 1990 | A |
| 4952617 | Ayala et al. | Aug 1990 | A |
| 4957553 | Koike | Sep 1990 | A |
| 4959661 | Buxton | Sep 1990 | A |
| 4973499 | Iwata et al. | Nov 1990 | A |
| 4978969 | Chieng | Dec 1990 | A |
| 4994110 | Stoffel et al. | Feb 1991 | A |
| 5013361 | Case et al. | May 1991 | A |
| 5017224 | Tomita | May 1991 | A |
| 5017227 | Koike et al. | May 1991 | A |
| 5017644 | Fuller et al. | May 1991 | A |
| 5026425 | Hindagolla et al. | Jun 1991 | A |
| 5026426 | Russell | Jun 1991 | A |
| 5026427 | Mitchell et al. | Jun 1991 | A |
| 5053078 | Koike | Oct 1991 | A |
| 5059248 | Signorino et al. | Oct 1991 | A |
| 5061316 | Moffatt | Oct 1991 | A |
| 5062892 | Halko | Nov 1991 | A |
| 5067980 | Koike | Nov 1991 | A |
| 5075699 | Koike | Dec 1991 | A |
| 5082496 | Yamamoto et al. | Jan 1992 | A |
| 5085698 | Ma et al. | Feb 1992 | A |
| 5102459 | Ritter et al. | Apr 1992 | A |
| 5103361 | Nagatsuka | Apr 1992 | A |
| 5106417 | Hauser | Apr 1992 | A |
| 5108501 | Moffatt | Apr 1992 | A |
| 5108503 | Hindagolla et al. | Apr 1992 | A |
| 5108504 | Johnson | Apr 1992 | A |
| 5110355 | Pendleton | May 1992 | A |
| 5114479 | Keaveney | May 1992 | A |
| 5116409 | Moffatt | May 1992 | A |
| 5118351 | Shirota et al. | Jun 1992 | A |
| 5124201 | Kurabayashi et al. | Jun 1992 | A |
| 5125969 | Nishiwaki et al. | Jun 1992 | A |
| 5133803 | Moffatt | Jul 1992 | A |
| 5142393 | Okumura et al. | Aug 1992 | A |
| 5145518 | Winnik et al. | Sep 1992 | A |
| 5156470 | Suzuki et al. | Oct 1992 | A |
| 5156472 | Suzuki et al. | Oct 1992 | A |
| 5156473 | Suzuki et al. | Oct 1992 | A |
| 5156675 | Breton et al. | Oct 1992 | A |
| 5158377 | Suzuki et al. | Oct 1992 | A |
| 5159009 | Wolff | Oct 1992 | A |
| 5160372 | Matrick | Nov 1992 | A |
| 5165968 | Johnson et al. | Nov 1992 | A |
| 5172133 | Suga et al. | Dec 1992 | A |
| 5176745 | Moore et al. | Jan 1993 | A |
| 5181045 | Shields | Jan 1993 | A |
| 5183502 | Meichsner | Feb 1993 | A |
| 5184148 | Suga | Feb 1993 | A |
| 5190582 | Shinozuka et al. | Mar 1993 | A |
| 5196057 | Escano et al. | Mar 1993 | A |
| 5207824 | Moffatt | May 1993 | A |
| 5211747 | Breton et al. | May 1993 | A |
| 5212819 | Wada | May 1993 | A |
| 5215577 | Eida et al. | Jun 1993 | A |
| 5220346 | Carreira et al. | Jun 1993 | A |
| 5221148 | Suzuki et al. | Jun 1993 | A |
| 5221332 | Kohlmeier | Jun 1993 | A |
| 5221334 | Ma et al. | Jun 1993 | A |
| 5246518 | Hale | Sep 1993 | A |
| 5248363 | Hale | Sep 1993 | A |
| 5258066 | Kobayashi et al. | Nov 1993 | A |
| 5258505 | Eida et al. | Nov 1993 | A |
| 5262268 | Bertrand | Nov 1993 | A |
| 5272201 | Ma et al. | Dec 1993 | A |
| 5281261 | Lin | Jan 1994 | A |
| 5281569 | Amon et al. | Jan 1994 | A |
| 5296022 | Kobayashi et al. | Mar 1994 | A |
| 5300148 | Domingo et al. | Apr 1994 | A |
| 5302223 | Hale | Apr 1994 | A |
| 5310778 | Shor et al. | May 1994 | A |
| 5318617 | Nagasawa et al. | Jun 1994 | A |
| 5320668 | Shields | Jun 1994 | A |
| 5334435 | Rossi | Aug 1994 | A |
| 5342439 | Lauw | Aug 1994 | A |
| 5344483 | Hinton | Sep 1994 | A |
| 5352484 | Bernard et al. | Oct 1994 | A |
| 5364461 | Beach et al. | Nov 1994 | A |
| 5364462 | Crystal | Nov 1994 | A |
| 5364702 | Idei | Nov 1994 | A |
| 5372697 | Akutsu et al. | Dec 1994 | A |
| 5377024 | Dillinger | Dec 1994 | A |
| 5378269 | Rossi | Jan 1995 | A |
| 5389134 | Breton et al. | Feb 1995 | A |
| 5393461 | Fillipova | Feb 1995 | A |
| 5393821 | Shieh et al. | Feb 1995 | A |
| 5395435 | Mizobuchi | Mar 1995 | A |
| 5407725 | Ryoke et al. | Apr 1995 | A |
| 5421658 | Suzuki et al. | Jun 1995 | A |
| 5421871 | Onishi et al. | Jun 1995 | A |
| 5424780 | Cooper | Jun 1995 | A |
| 5428383 | Shields | Jun 1995 | A |
| 5431501 | Hale | Jul 1995 | A |
| 5437716 | Sano et al. | Aug 1995 | A |
| 5441564 | Vogt | Aug 1995 | A |
| 5484475 | Breton | Jan 1996 | A |
| 5484899 | Deitz et al. | Jan 1996 | A |
| 5485188 | Tochihara et al. | Jan 1996 | A |
| 5487614 | Hale | Jan 1996 | A |
| 5488401 | Mochizuki et al. | Jan 1996 | A |
| 5488402 | Shields et al. | Jan 1996 | A |
| 5488907 | Xu | Feb 1996 | A |
| 5503664 | Sano et al. | Apr 1996 | A |
| 5509140 | Koitabashi et al. | Apr 1996 | A |
| 5522317 | Hale | Jun 1996 | A |
| 5522922 | Furusawa | Jun 1996 | A |
| 5529616 | Prasad | Jun 1996 | A |
| 5529767 | Brox et al. | Jun 1996 | A |
| 5531816 | Wickramanayake | Jul 1996 | A |
| 5531818 | Lin | Jul 1996 | A |
| 5534051 | Lauw | Jul 1996 | A |
| 5536306 | Johnson et al. | Jul 1996 | A |
| 5538548 | Yamazaki et al. | Jul 1996 | A |
| 5550082 | Wolfe et al. | Aug 1996 | A |
| 5552182 | Scarpetti | Sep 1996 | A |
| 5554739 | Belmont | Sep 1996 | A |
| 5555813 | Hale | Sep 1996 | A |
| 5559169 | Belmont | Sep 1996 | A |
| 5560720 | Suzuki et al. | Oct 1996 | A |
| 5562762 | Mrvos et al. | Oct 1996 | A |
| 5570118 | Rezanka et al. | Oct 1996 | A |
| 5571311 | Belmont et al. | Nov 1996 | A |
| 5575845 | Belmont et al. | Nov 1996 | A |
| 5575877 | Hale | Nov 1996 | A |
| 5580372 | Gino et al. | Dec 1996 | A |
| 5585189 | Inoue et al. | Dec 1996 | A |
| 5589522 | Beach et al. | Dec 1996 | A |
| 5590600 | Hale | Jan 1997 | A |
| 5591455 | Signorino et al. | Jan 1997 | A |
| 5593459 | Gamblin | Jan 1997 | A |
| 5595592 | Signorino et al. | Jan 1997 | A |
| 5601023 | Hale | Feb 1997 | A |
| 5604276 | Suga | Feb 1997 | A |
| 5609671 | Nagasawa | Mar 1997 | A |
| 5611847 | Guistina et al. | Mar 1997 | A |
| 5615957 | Suzuki et al. | Apr 1997 | A |
| 5621027 | Roschger et al. | Apr 1997 | A |
| 5622439 | Suzuki et al. | Apr 1997 | A |
| 5622557 | Mahmud et al. | Apr 1997 | A |
| 5624485 | Calhoun | Apr 1997 | A |
| 5626655 | Pawlowski et al. | May 1997 | A |
| 5630868 | Belmont et al. | May 1997 | A |
| 5631309 | Yanagi et al. | May 1997 | A |
| 5640180 | Hale et al. | Jun 1997 | A |
| 5642141 | Hale | Jun 1997 | A |
| 5644988 | Xu | Jul 1997 | A |
| 5647896 | Nishimura et al. | Jul 1997 | A |
| 5647897 | Ouki et al. | Jul 1997 | A |
| 5648405 | Ma | Jul 1997 | A |
| 5656071 | Kappele | Aug 1997 | A |
| 5658376 | Noguchi et al. | Aug 1997 | A |
| 5665150 | Schwarz | Sep 1997 | A |
| 5667569 | Fujioka | Sep 1997 | A |
| 5667571 | Ono et al. | Sep 1997 | A |
| 5667572 | Taniguchi | Sep 1997 | A |
| 5672198 | Belmont | Sep 1997 | A |
| 5679143 | Looman | Oct 1997 | A |
| 5686508 | Shimomura | Nov 1997 | A |
| 5686633 | Vieira | Nov 1997 | A |
| 5688311 | Adamic | Nov 1997 | A |
| 5690721 | Itoh | Nov 1997 | A |
| 5690722 | Pawlowski | Nov 1997 | A |
| 5690723 | Sano | Nov 1997 | A |
| 5693126 | Ito | Dec 1997 | A |
| 5698016 | Adams et al. | Dec 1997 | A |
| 5700317 | Adamic | Dec 1997 | A |
| 5704969 | Kanaya | Jan 1998 | A |
| 5707432 | Adams et al. | Jan 1998 | A |
| 5709976 | Malhotra | Jan 1998 | A |
| 5713988 | Belmont | Feb 1998 | A |
| 5713989 | Wickramanayake | Feb 1998 | A |
| 5713992 | Satoh et al. | Feb 1998 | A |
| 5714538 | Beach et al. | Feb 1998 | A |
| 5718746 | Nagasawa et al. | Feb 1998 | A |
| 5719204 | Beach et al. | Feb 1998 | A |
| 5721344 | Baettig | Feb 1998 | A |
| 5725641 | MacLeod | Mar 1998 | A |
| 5725643 | Higashiyama | Mar 1998 | A |
| 5725644 | Sano et al. | Mar 1998 | A |
| 5730790 | Rehman | Mar 1998 | A |
| 5734396 | Hale | Mar 1998 | A |
| 5734403 | Suga et al. | Mar 1998 | A |
| 5735941 | Feeman et al. | Apr 1998 | A |
| 5745140 | Stoffel et al. | Apr 1998 | A |
| 5746816 | Xu | May 1998 | A |
| 5746817 | Katsen et al. | May 1998 | A |
| 5746818 | Yatake | May 1998 | A |
| 5747562 | Mahmud et al. | May 1998 | A |
| 5749950 | Mahmud et al. | May 1998 | A |
| 5749951 | Yoshiike et al. | May 1998 | A |
| 5749952 | Tsang et al. | May 1998 | A |
| 5750592 | Shinozuka et al. | May 1998 | A |
| 5751320 | Scheffelin et al. | May 1998 | A |
| 5766327 | Maze | Jun 1998 | A |
| 5769930 | Sano | Jun 1998 | A |
| 5772742 | Wang | Jun 1998 | A |
| 5777648 | Scheffelin et al. | Jul 1998 | A |
| 5785743 | Adamic et al. | Jul 1998 | A |
| 5786436 | Fischer et al. | Jul 1998 | A |
| 5788754 | Deardurff et al. | Aug 1998 | A |
| 5795375 | Yamazaki et al. | Aug 1998 | A |
| 5803958 | Katsen et al. | Sep 1998 | A |
| 5803959 | Johnson | Sep 1998 | A |
| 5814138 | Fague | Sep 1998 | A |
| 5814683 | Branham | Sep 1998 | A |
| 5814685 | Satake et al. | Sep 1998 | A |
| 5821283 | Hesler | Oct 1998 | A |
| 5825387 | Cowger et al. | Oct 1998 | A |
| 5830263 | Hale | Nov 1998 | A |
| 5830264 | Fujioka et al. | Nov 1998 | A |
| 5830265 | Tsang et al. | Nov 1998 | A |
| 5830930 | Mahmud et al. | Nov 1998 | A |
| 5837043 | Wong et al. | Nov 1998 | A |
| 5837045 | Johnson et al. | Nov 1998 | A |
| 5837374 | Hirayama et al. | Nov 1998 | A |
| 5846306 | Kubota | Dec 1998 | A |
| 5846307 | Nagasawa et al. | Dec 1998 | A |
| 5849067 | Tsuchiya et al. | Dec 1998 | A |
| 5851274 | Lin | Dec 1998 | A |
| 5851280 | Belmont et al. | Dec 1998 | A |
| 5853465 | Tsang | Dec 1998 | A |
| 5854307 | Kimura | Dec 1998 | A |
| 5854331 | Ma | Dec 1998 | A |
| 5858075 | Deardurff et al. | Jan 1999 | A |
| 5858078 | Andes et al. | Jan 1999 | A |
| 5861447 | Nagasawa et al. | Jan 1999 | A |
| 5863323 | Mahmud et al. | Jan 1999 | A |
| 5868823 | Yamazaki et al. | Feb 1999 | A |
| 5869550 | Mahmud | Feb 1999 | A |
| 5871572 | Marritt | Feb 1999 | A |
| 5874974 | Courian et al. | Feb 1999 | A |
| 5876491 | Gunn et al. | Mar 1999 | A |
| 5877100 | Smith et al. | Mar 1999 | A |
| 5877238 | Mahmud et al. | Mar 1999 | A |
| 5877253 | Matta et al. | Mar 1999 | A |
| 5885335 | Adams | Mar 1999 | A |
| 5885336 | Kitahara et al. | Mar 1999 | A |
| 5886065 | Tsang et al. | Mar 1999 | A |
| 5891232 | Moffatt | Apr 1999 | A |
| 5891934 | Moffatt et al. | Apr 1999 | A |
| 5895522 | Belmont et al. | Apr 1999 | A |
| 5897694 | Woolf | Apr 1999 | A |
| 5897961 | Malhotra | Apr 1999 | A |
| 5898445 | Becker et al. | Apr 1999 | A |
| 5900029 | Belmont et al. | May 1999 | A |
| 5904762 | Mahmud | May 1999 | A |
| 5911816 | Gore | Jun 1999 | A |
| 5916934 | Mahmud et al. | Jun 1999 | A |
| 5916956 | Wang et al. | Jun 1999 | A |
| 5919293 | Moffatt et al. | Jul 1999 | A |
| 5919841 | Mahmud et al. | Jul 1999 | A |
| 5919855 | Reed | Jul 1999 | A |
| 5922118 | Johnson | Jul 1999 | A |
| 5925176 | Rehman | Jul 1999 | A |
| 5928419 | Uemura et al. | Jul 1999 | A |
| 5932631 | Marritt | Aug 1999 | A |
| 5935309 | Moffatt et al. | Aug 1999 | A |
| 5938829 | Higashiyama et al. | Aug 1999 | A |
| 5946012 | Courian et al. | Aug 1999 | A |
| 5948150 | Lin | Sep 1999 | A |
| 5948835 | Mahmud et al. | Sep 1999 | A |
| 5951749 | Krepski et al. | Sep 1999 | A |
| 5952481 | Markham | Sep 1999 | A |
| 5955232 | Little | Sep 1999 | A |
| 5955515 | Kimura et al. | Sep 1999 | A |
| 5958999 | Bates et al. | Sep 1999 | A |
| 5961703 | Fraas | Oct 1999 | A |
| 5963238 | Scheffelin et al. | Oct 1999 | A |
| 5965196 | Sawada | Oct 1999 | A |
| 5966156 | Scheffelin et al. | Oct 1999 | A |
| 5968243 | Belmont | Oct 1999 | A |
| 5968244 | Ueda et al. | Oct 1999 | A |
| 5969003 | Foucher et al. | Oct 1999 | A |
| 5972083 | Iijima | Oct 1999 | A |
| 5976232 | Gore | Nov 1999 | A |
| 5976233 | Osumi et al. | Nov 1999 | A |
| 5977213 | Mahmud | Nov 1999 | A |
| 5981623 | McCain et al. | Nov 1999 | A |
| 5985015 | Kanaya | Nov 1999 | A |
| 5985016 | Tsang | Nov 1999 | A |
| 5990202 | Nguyen | Nov 1999 | A |
| 6004389 | Yatake | Dec 1999 | A |
| 6007611 | Mheidle et al. | Dec 1999 | A |
| 6008272 | Mahmud et al. | Dec 1999 | A |
| 6013123 | Scarpetti | Jan 2000 | A |
| 6015454 | Lacroix et al. | Jan 2000 | A |
| 6017980 | Wang | Jan 2000 | A |
| 6019828 | Rehman | Feb 2000 | A |
| 6020397 | Matzinger | Feb 2000 | A |
| 6022908 | Ma | Feb 2000 | A |
| 6024786 | Gore | Feb 2000 | A |
| 6028137 | Mahmud et al. | Feb 2000 | A |
| 6034153 | Tsang et al. | Mar 2000 | A |
| 6036759 | Wickramanayake | Mar 2000 | A |
| 6039796 | Kubota | Mar 2000 | A |
| 6042643 | Belmont et al. | Mar 2000 | A |
| 6050671 | Rotering | Apr 2000 | A |
| 6054238 | Little | Apr 2000 | A |
| 6056812 | Lin | May 2000 | A |
| 6057387 | Mahmud | May 2000 | A |
| 6068688 | Whitehouse et al. | May 2000 | A |
| 6069190 | Bates | May 2000 | A |
| 6074042 | Gasvoda et al. | Jun 2000 | A |
| 6083315 | Nakamura et al. | Jul 2000 | A |
| 6086197 | Kubota et al. | Jul 2000 | A |
| 6086198 | Shields | Jul 2000 | A |
| 6089687 | Helterline | Jul 2000 | A |
| 6099632 | Nagasawa et al. | Aug 2000 | A |
| 6100315 | Kitamura et al. | Aug 2000 | A |
| 6102996 | Parazak | Aug 2000 | A |
| 6103041 | Wagner et al. | Aug 2000 | A |
| 6103380 | Devonport | Aug 2000 | A |
| 6103782 | Mizobuchi | Aug 2000 | A |
| 6105502 | Wagner et al. | Aug 2000 | A |
| 6107350 | Boes et al. | Aug 2000 | A |
| 6110266 | Gonzalez-Blanco et al. | Aug 2000 | A |
| 6110994 | Cooke et al. | Aug 2000 | A |
| 6116409 | Yokajty | Sep 2000 | A |
| 6120594 | Curtis et al. | Sep 2000 | A |
| 6124376 | Nichols et al. | Sep 2000 | A |
| 6126731 | Kemeny | Oct 2000 | A |
| 6132021 | Smith | Oct 2000 | A |
| 6132502 | Yatake | Oct 2000 | A |
| 6136286 | Okuyama et al. | Oct 2000 | A |
| 6137502 | Anderson et al. | Oct 2000 | A |
| 6139139 | Stoffel et al. | Oct 2000 | A |
| 6142621 | Romano | Nov 2000 | A |
| 6149327 | Ward et al. | Nov 2000 | A |
| 6150433 | Tsang et al. | Nov 2000 | A |
| 6150453 | Mahmud et al. | Nov 2000 | A |
| 6152038 | Wagner et al. | Nov 2000 | A |
| 6169129 | Mahmud et al. | Jan 2001 | B1 |
| 6172154 | Brown | Jan 2001 | B1 |
| 6174354 | Takizawa et al. | Jan 2001 | B1 |
| 6176629 | Suzuki et al. | Jan 2001 | B1 |
| 6177498 | Rehman | Jan 2001 | B1 |
| 6180691 | Cheng et al. | Jan 2001 | B1 |
| 6184268 | Nichols et al. | Feb 2001 | B1 |
| 6187086 | Rehman | Feb 2001 | B1 |
| 6193364 | Iida | Feb 2001 | B1 |
| 6197274 | Mahmud et al. | Mar 2001 | B1 |
| 6206517 | Kovacs et al. | Mar 2001 | B1 |
| 6207719 | Pardikes | Mar 2001 | B1 |
| 6209998 | Yue | Apr 2001 | B1 |
| 6211279 | Mahmud | Apr 2001 | B1 |
| 6214100 | Parazak et al. | Apr 2001 | B1 |
| 6218067 | Belmont | Apr 2001 | B1 |
| 6221141 | Takada et al. | Apr 2001 | B1 |
| 6221142 | Wang et al. | Apr 2001 | B1 |
| 6221143 | Palumbo | Apr 2001 | B1 |
| 6221932 | Moffatt et al. | Apr 2001 | B1 |
| 6224202 | Romano, Jr. | May 2001 | B1 |
| 6231655 | Marritt | May 2001 | B1 |
| 6239193 | Cheng | May 2001 | B1 |
| H1967 | Woolf | Jun 2001 | H |
| 6241811 | Sano | Jun 2001 | B1 |
| 6242529 | Marritt | Jun 2001 | B1 |
| 6244687 | Gast et al. | Jun 2001 | B1 |
| 6247808 | Ma | Jun 2001 | B1 |
| 6258864 | Dalton et al. | Jul 2001 | B1 |
| 6264301 | Helterline | Jul 2001 | B1 |
| 6271285 | Miyabayashi et al. | Aug 2001 | B1 |
| 6276791 | Kovacs et al. | Aug 2001 | B1 |
| 6277183 | Johnson et al. | Aug 2001 | B1 |
| 6277184 | Kato | Aug 2001 | B1 |
| 6280512 | Botros | Aug 2001 | B1 |
| 6280513 | Osumi et al. | Aug 2001 | B1 |
| 6280516 | Lucchi et al. | Aug 2001 | B1 |
| 6280871 | Tosco et al. | Aug 2001 | B1 |
| 6281267 | Parazak | Aug 2001 | B2 |
| 6281917 | Katsuragi et al. | Aug 2001 | B1 |
| 6284029 | Sano et al. | Sep 2001 | B1 |
| 6291572 | Brown et al. | Sep 2001 | B1 |
| 6299675 | Ono et al. | Oct 2001 | B1 |
| 6300391 | Parazak et al. | Oct 2001 | B2 |
| 6306204 | Lin | Oct 2001 | B1 |
| 6312103 | Haluzak | Nov 2001 | B1 |
| 6314574 | Chan | Nov 2001 | B1 |
| 6323257 | Moffatt et al. | Nov 2001 | B1 |
| 6323258 | Lin | Nov 2001 | B1 |
| 6323273 | Mahmud et al. | Nov 2001 | B1 |
| 6328894 | Chan et al. | Dec 2001 | B1 |
| 6332919 | Osumi et al. | Dec 2001 | B2 |
| 6336965 | Johnson et al. | Jan 2002 | B1 |
| 6337358 | Whitehouse et al. | Jan 2002 | B1 |
| 6341856 | Thompson et al. | Jan 2002 | B1 |
| 6342094 | Kabalnov | Jan 2002 | B1 |
| 6342095 | Takizawa et al. | Jan 2002 | B1 |
| 6348939 | Xu | Feb 2002 | B1 |
| 6350519 | Devonport | Feb 2002 | B1 |
| 6352341 | Kovacs et al. | Mar 2002 | B2 |
| 6354693 | Looman et al. | Mar 2002 | B1 |
| 6361156 | Romano, Jr. et al. | Mar 2002 | B1 |
| 6364472 | Barinaga et al. | Apr 2002 | B1 |
| 6364944 | Mahmud et al. | Apr 2002 | B1 |
| 6367922 | Romano, Jr. | Apr 2002 | B2 |
| 6368239 | Devonport et al. | Apr 2002 | B1 |
| 6372329 | Graczyk et al. | Apr 2002 | B1 |
| 6372818 | Kimura et al. | Apr 2002 | B1 |
| 6372820 | Devonport | Apr 2002 | B1 |
| 6375317 | Osumi et al. | Apr 2002 | B1 |
| 6379443 | Komatsu et al. | Apr 2002 | B1 |
| 6383274 | Lin | May 2002 | B1 |
| 6383275 | Lin | May 2002 | B1 |
| 6386695 | Kowalski | May 2002 | B1 |
| 6387168 | Koitabashi et al. | May 2002 | B1 |
| 6387500 | Behl | May 2002 | B1 |
| 6391947 | Noguchi et al. | May 2002 | B1 |
| 6398858 | Yu et al. | Jun 2002 | B1 |
| 6399029 | Porteous | Jun 2002 | B1 |
| 6399202 | Yu | Jun 2002 | B1 |
| 6399674 | Kashiwazaki et al. | Jun 2002 | B1 |
| 6402313 | Xu et al. | Jun 2002 | B1 |
| 6402825 | Sun | Jun 2002 | B1 |
| 6406143 | Chen et al. | Jun 2002 | B1 |
| 6406528 | Macholdt et al. | Jun 2002 | B1 |
| 6412935 | Doumaux | Jul 2002 | B1 |
| 6417249 | Nguyen | Jul 2002 | B1 |
| 6419733 | Sano et al. | Jul 2002 | B1 |
| 6423375 | Bi et al. | Jul 2002 | B1 |
| 6425331 | Xu | Jul 2002 | B1 |
| 6425662 | Teraoka et al. | Jul 2002 | B1 |
| 6431677 | Anderson et al. | Aug 2002 | B1 |
| 6432194 | Johnson et al. | Aug 2002 | B2 |
| 6432523 | Ma et al. | Aug 2002 | B1 |
| 6435240 | Fagebaume et al. | Aug 2002 | B1 |
| 6435659 | Bruinsma | Aug 2002 | B1 |
| 6436178 | Hosmer | Aug 2002 | B1 |
| 6439710 | Hale | Aug 2002 | B1 |
| 6444017 | Yue | Sep 2002 | B1 |
| 6444294 | Malhotra et al. | Sep 2002 | B1 |
| 6447629 | Thompson et al. | Sep 2002 | B1 |
| 6448309 | Mahmud et al. | Sep 2002 | B2 |
| 6450098 | Hale | Sep 2002 | B1 |
| 6450632 | Tsang | Sep 2002 | B1 |
| 6451098 | Lye et al. | Sep 2002 | B1 |
| 6451103 | Uemura et al. | Sep 2002 | B1 |
| 6451379 | Tsao | Sep 2002 | B1 |
| 6454403 | Takada et al. | Sep 2002 | B1 |
| 6454846 | Yatake | Sep 2002 | B2 |
| 6458195 | Stoffel et al. | Oct 2002 | B1 |
| 6458458 | Cooke et al. | Oct 2002 | B1 |
| 6460987 | Katsuragi et al. | Oct 2002 | B1 |
| 6460989 | Yano et al. | Oct 2002 | B1 |
| 6461418 | Yue et al. | Oct 2002 | B1 |
| 6464334 | Lopez et al. | Oct 2002 | B2 |
| 6467896 | Meyer | Oct 2002 | B2 |
| 6468340 | Moffatt | Oct 2002 | B1 |
| 6468342 | Itoh et al. | Oct 2002 | B1 |
| 6471757 | Koitabashi et al. | Oct 2002 | B1 |
| 6471763 | Karl | Oct 2002 | B1 |
| 6472471 | Cooke et al. | Oct 2002 | B2 |
| 6475271 | Lin | Nov 2002 | B2 |
| 6475612 | Knight et al. | Nov 2002 | B1 |
| 6478863 | Johnson et al. | Nov 2002 | B2 |
| 6478963 | Rossmanith | Nov 2002 | B1 |
| 6479571 | Cooke et al. | Nov 2002 | B1 |
| 6485138 | Kubota et al. | Nov 2002 | B1 |
| 6486903 | Wagner et al. | Nov 2002 | B1 |
| 6488370 | Hale | Dec 2002 | B2 |
| 6488753 | Ito et al. | Dec 2002 | B1 |
| 6491976 | Horiuchi et al. | Dec 2002 | B2 |
| 6494943 | Yu et al. | Dec 2002 | B1 |
| 6494946 | Belmont et al. | Dec 2002 | B1 |
| 6497479 | Stoffel et al. | Dec 2002 | B1 |
| 6498222 | Kitamura et al. | Dec 2002 | B1 |
| 6500248 | Hayashi | Dec 2002 | B1 |
| 6500880 | Parazak | Dec 2002 | B1 |
| 6502917 | Shinada et al. | Jan 2003 | B1 |
| 6502920 | Anderson et al. | Jan 2003 | B1 |
| 6503307 | Noguchi | Jan 2003 | B1 |
| 6503308 | Stramel | Jan 2003 | B2 |
| 6503311 | Karl et al. | Jan 2003 | B1 |
| 6503317 | Ortalano | Jan 2003 | B1 |
| 6503978 | Tsao | Jan 2003 | B1 |
| 6505910 | Doval | Jan 2003 | B1 |
| 6505929 | Chow | Jan 2003 | B1 |
| 6506239 | Osumi | Jan 2003 | B1 |
| 6506240 | Takemoto | Jan 2003 | B2 |
| 6506245 | Kinney et al. | Jan 2003 | B1 |
| 6508871 | Kato | Jan 2003 | B1 |
| 6508872 | Nguyen | Jan 2003 | B2 |
| 6511534 | Mishina et al. | Jan 2003 | B1 |
| 6514330 | Kanaya et al. | Feb 2003 | B1 |
| 6514920 | Katsuragi et al. | Feb 2003 | B1 |
| 6517199 | Tomioka et al. | Feb 2003 | B1 |
| 6521034 | Osumi et al. | Feb 2003 | B1 |
| 6522522 | Yu | Feb 2003 | B2 |
| 6524383 | Komatsu et al. | Feb 2003 | B2 |
| 6528148 | Niu | Mar 2003 | B2 |
| 6530656 | Teraoka et al. | Mar 2003 | B1 |
| 6533406 | Katsuragi | Mar 2003 | B2 |
| 6533407 | Mouri et al. | Mar 2003 | B2 |
| 6533853 | Mishina | Mar 2003 | B1 |
| 6534569 | Mahmud et al. | Mar 2003 | B2 |
| 6536878 | Kasperchik et al. | Mar 2003 | B2 |
| 6536890 | Kato et al. | Mar 2003 | B1 |
| 6537364 | Dietz et al. | Mar 2003 | B2 |
| 6538047 | Miyabayashi | Mar 2003 | B1 |
| 6538049 | Kappele | Mar 2003 | B1 |
| 6540329 | Kaneko et al. | Apr 2003 | B1 |
| 6540334 | Mrvos et al. | Apr 2003 | B1 |
| 6540345 | Wagner et al. | Apr 2003 | B1 |
| 6541538 | Matzinger | Apr 2003 | B1 |
| 6543889 | Murcia et al. | Apr 2003 | B2 |
| 6547381 | Watanabe et al. | Apr 2003 | B2 |
| 6548572 | Breck | Apr 2003 | B1 |
| 6550901 | Iida | Apr 2003 | B2 |
| 6550902 | Shinada et al. | Apr 2003 | B2 |
| 6550903 | Katsuragi | Apr 2003 | B2 |
| 6551393 | Devonport et al. | Apr 2003 | B2 |
| 6554891 | Momose | Apr 2003 | B1 |
| 6562121 | Nickel et al. | May 2003 | B2 |
| 6565202 | Rose et al. | May 2003 | B2 |
| 6572226 | Tyvoll | Jun 2003 | B2 |
| 6572690 | Rehman et al. | Jun 2003 | B2 |
| 6572692 | Osumi | Jun 2003 | B1 |
| 6578943 | Arquilevich et al. | Jun 2003 | B2 |
| 6582508 | Dietz et al. | Jun 2003 | B2 |
| 6585815 | Koitabashi et al. | Jul 2003 | B2 |
| 6585817 | Lee | Jul 2003 | B2 |
| 6585818 | Thakkar et al. | Jul 2003 | B2 |
| 6586501 | Dalton et al. | Jul 2003 | B1 |
| 6588880 | Gasvoda et al. | Jul 2003 | B1 |
| 6592657 | Lee et al. | Jul 2003 | B2 |
| 6596065 | Ito | Jul 2003 | B2 |
| 6596068 | Ito et al. | Jul 2003 | B1 |
| 6596378 | Hanmura et al. | Jul 2003 | B2 |
| 6602333 | Miyabayashi | Aug 2003 | B2 |
| 6602335 | Moffatt et al. | Aug 2003 | B2 |
| 6604809 | Katsuragi | Aug 2003 | B2 |
| 6605420 | Nakai et al. | Aug 2003 | B2 |
| 6607266 | Katsuragi et al. | Aug 2003 | B2 |
| 6607268 | Bruinsma | Aug 2003 | B2 |
| 6607565 | Herrmann et al. | Aug 2003 | B1 |
| 6607589 | Adamic et al. | Aug 2003 | B2 |
| 6610129 | Sader et al. | Aug 2003 | B1 |
| 6616273 | Bruinsma | Sep 2003 | B1 |
| 6618066 | Hale | Sep 2003 | B2 |
| 6620229 | Doi et al. | Sep 2003 | B2 |
| 6630268 | Tosco et al. | Oct 2003 | B2 |
| 6631984 | Thompson et al. | Oct 2003 | B2 |
| 6632275 | Schoen et al. | Oct 2003 | B1 |
| 6632485 | Tang et al. | Oct 2003 | B1 |
| 6632594 | Nakai et al. | Oct 2003 | B2 |
| 6637876 | Hori | Oct 2003 | B2 |
| 6638350 | Butler et al. | Oct 2003 | B2 |
| 6641259 | Kopolow et al. | Nov 2003 | B1 |
| 6641651 | Suzuki | Nov 2003 | B2 |
| 6641653 | Yu | Nov 2003 | B2 |
| 6641656 | Yu | Nov 2003 | B2 |
| 6643220 | Anderson | Nov 2003 | B2 |
| 6644778 | Rotering | Nov 2003 | B2 |
| 6648950 | Lee | Nov 2003 | B2 |
| 6648953 | Yamazaki et al. | Nov 2003 | B2 |
| 6648954 | Uemura et al. | Nov 2003 | B2 |
| 6649317 | Wagner et al. | Nov 2003 | B2 |
| 6652084 | Teraoka | Nov 2003 | B1 |
| 6659582 | Underwood | Dec 2003 | B2 |
| 6660075 | Bergemann et al. | Dec 2003 | B2 |
| 6664312 | Devonport | Dec 2003 | B2 |
| 6673503 | Wagner et al. | Jan 2004 | B2 |
| 6679576 | Crivelli | Jan 2004 | B2 |
| 6679598 | Kato et al. | Jan 2004 | B2 |
| 6685769 | Karl et al. | Feb 2004 | B1 |
| 6686314 | Xu et al. | Feb 2004 | B2 |
| 6686409 | Mahmud et al. | Feb 2004 | B2 |
| 6688737 | Nagai et al. | Feb 2004 | B2 |
| 6689433 | Niu et al. | Feb 2004 | B2 |
| 6699319 | Adams | Mar 2004 | B2 |
| 6706104 | Takuhara et al. | Mar 2004 | B2 |
| 6706105 | Takada et al. | Mar 2004 | B2 |
| 6709506 | Mahmud et al. | Mar 2004 | B2 |
| 6715866 | Kasperchik | Apr 2004 | B2 |
| 6716278 | Prasad et al. | Apr 2004 | B2 |
| 6719420 | Tomioka et al. | Apr 2004 | B2 |
| 6720367 | Taniguchi et al. | Apr 2004 | B2 |
| 6722765 | Rolly et al. | Apr 2004 | B2 |
| 6723161 | Langenmayr et al. | Apr 2004 | B2 |
| 6723783 | Palumbo et al. | Apr 2004 | B2 |
| 6730152 | Rehman | May 2004 | B2 |
| 6733120 | Ogasawara et al. | May 2004 | B2 |
| 6737449 | Yatake | May 2004 | B1 |
| 6740151 | Belmont et al. | May 2004 | B2 |
| 6740689 | Lee et al. | May 2004 | B1 |
| 6749773 | Emanuel | Jun 2004 | B2 |
| 6753425 | Nakai et al. | Jun 2004 | B2 |
| 6759459 | Lin | Jul 2004 | B2 |
| 6761759 | Oki et al. | Jul 2004 | B2 |
| 6767640 | Moffatt | Jul 2004 | B2 |
| 6776830 | Marritt | Aug 2004 | B2 |
| 6777462 | Smith et al. | Aug 2004 | B2 |
| 6779864 | Underwood | Aug 2004 | B2 |
| 6779884 | Ma | Aug 2004 | B1 |
| 6780389 | Karl et al. | Aug 2004 | B2 |
| 6780901 | Endo et al. | Aug 2004 | B1 |
| 6786957 | Choy et al. | Sep 2004 | B2 |
| 6790268 | Lee et al. | Sep 2004 | B2 |
| 6790878 | Kurabayashi | Sep 2004 | B2 |
| 6793308 | Sugimoto et al. | Sep 2004 | B2 |
| 6793329 | Batley et al. | Sep 2004 | B2 |
| 6793722 | Chien et al. | Sep 2004 | B2 |
| 6793723 | Auslander et al. | Sep 2004 | B2 |
| 6794427 | Kurabayashi et al. | Sep 2004 | B2 |
| 6797347 | Chow | Sep 2004 | B2 |
| 6805736 | Wickramanayake | Oct 2004 | B2 |
| 6806300 | Waki et al. | Oct 2004 | B2 |
| 6806925 | Ishii et al. | Oct 2004 | B2 |
| 6808555 | Wang | Oct 2004 | B2 |
| 6808583 | Kwasny et al. | Oct 2004 | B2 |
| 6811597 | Oki et al. | Nov 2004 | B2 |
| 6814790 | Sir et al. | Nov 2004 | B2 |
| 6814791 | Moore | Nov 2004 | B2 |
| 6814792 | Taniguchi | Nov 2004 | B2 |
| 6814793 | Akers et al. | Nov 2004 | B2 |
| 6818048 | Prasad et al. | Nov 2004 | B2 |
| 6820972 | Kinalski | Nov 2004 | B2 |
| 6821328 | Tomioka et al. | Nov 2004 | B2 |
| 6821330 | Sano | Nov 2004 | B1 |
| 6822781 | Amici et al. | Nov 2004 | B1 |
| 6824263 | Taniguchi et al. | Nov 2004 | B2 |
| 6827403 | Paasche et al. | Dec 2004 | B2 |
| 6827434 | Katsuragi et al. | Dec 2004 | B1 |
| 6827768 | Andrievsky et al. | Dec 2004 | B2 |
| 6830326 | Tsao | Dec 2004 | B2 |
| 6830327 | Asakawa | Dec 2004 | B2 |
| 6830927 | Rao | Dec 2004 | B2 |
| 6832830 | Seino | Dec 2004 | B2 |
| 6833026 | Palumbo | Dec 2004 | B2 |
| 6834945 | Ishizawa et al. | Dec 2004 | B2 |
| H2113 | Nichols et al. | Jan 2005 | H |
| 6840614 | Wagner et al. | Jan 2005 | B2 |
| 6843838 | Zimmer et al. | Jan 2005 | B2 |
| 6844035 | Niu et al. | Jan 2005 | B2 |
| 6848779 | Lo et al. | Feb 2005 | B2 |
| 6848781 | Ogino et al. | Feb 2005 | B2 |
| 6849111 | Suzuki | Feb 2005 | B2 |
| 6851787 | Johnson | Feb 2005 | B2 |
| 6852153 | Uhlir-Tsang | Feb 2005 | B2 |
| 6852156 | Yeh et al. | Feb 2005 | B2 |
| 6855193 | Andrievsky et al. | Feb 2005 | B2 |
| 6858301 | Ganapathiappan | Feb 2005 | B2 |
| 6860593 | Kashiwazaki et al. | Mar 2005 | B2 |
| 6863719 | Butler et al. | Mar 2005 | B2 |
| 6866378 | Wotton et al. | Mar 2005 | B2 |
| 6866381 | Kelly-Rowley et al. | Mar 2005 | B2 |
| 6866707 | Kato | Mar 2005 | B2 |
| 6867286 | Holloway | Mar 2005 | B1 |
| 6869470 | Kato | Mar 2005 | B2 |
| 6869647 | Page | Mar 2005 | B2 |
| 6871929 | Crivelli et al. | Mar 2005 | B2 |
| 6872430 | Burch et al. | Mar 2005 | B2 |
| 6887640 | Zhang et al. | May 2005 | B2 |
| 6896647 | Karger | May 2005 | B1 |
| 6899754 | Yeh | May 2005 | B2 |
| 6908185 | Chen | Jun 2005 | B2 |
| 6911073 | Adams et al. | Jun 2005 | B2 |
| 6916088 | Smith et al. | Jul 2005 | B2 |
| 6916089 | Iida | Jul 2005 | B2 |
| 6921429 | Sago et al. | Jul 2005 | B2 |
| 6921433 | Kuribayashi et al. | Jul 2005 | B2 |
| 6935717 | Su et al. | Aug 2005 | B2 |
| 6945644 | Kabalnov | Sep 2005 | B2 |
| 6948021 | Derrico | Sep 2005 | B2 |
| 6948804 | Iida | Sep 2005 | B2 |
| 6953239 | Gondek et al. | Oct 2005 | B2 |
| 6955422 | Miyazawa et al. | Oct 2005 | B2 |
| 6961076 | Wagner | Nov 2005 | B2 |
| 6964702 | Shen et al. | Nov 2005 | B2 |
| 6966643 | Hale | Nov 2005 | B2 |
| 6969159 | Su et al. | Nov 2005 | B2 |
| RE38952 | Hale et al. | Jan 2006 | E |
| 6988796 | Rolly et al. | Jan 2006 | B2 |
| 6991329 | Gore | Jan 2006 | B2 |
| 6991676 | Kabalnov et al. | Jan 2006 | B2 |
| 6997979 | Bauer | Feb 2006 | B2 |
| 7001649 | Wagner et al. | Feb 2006 | B2 |
| 7001660 | Garitano | Feb 2006 | B2 |
| 7001936 | Akers, Jr. et al. | Feb 2006 | B2 |
| 7005003 | Mott | Feb 2006 | B2 |
| 7005461 | Sanada et al. | Feb 2006 | B2 |
| 7008053 | Hashii et al. | Mar 2006 | B2 |
| 7008977 | Sakai et al. | Mar 2006 | B2 |
| 7011397 | Miyazawa et al. | Mar 2006 | B2 |
| 7018030 | Seino et al. | Mar 2006 | B2 |
| 7018953 | Gore et al. | Mar 2006 | B2 |
| 7025813 | Vanmaele et al. | Apr 2006 | B2 |
| 7025820 | Champlin et al. | Apr 2006 | B2 |
| 7027185 | Subirada et al. | Apr 2006 | B2 |
| 7030174 | Yatake | Apr 2006 | B2 |
| 7030175 | Vincent | Apr 2006 | B2 |
| 7033423 | Rolly | Apr 2006 | B2 |
| 7034149 | Hirokazu | Apr 2006 | B2 |
| 7034273 | O | Apr 2006 | B1 |
| 7037398 | Kwasny et al. | May 2006 | B2 |
| 7041424 | Xu | May 2006 | B2 |
| 7045002 | Bauer et al. | May 2006 | B2 |
| 7046389 | Lopez et al. | May 2006 | B2 |
| 7049039 | Tazawa et al. | May 2006 | B2 |
| 7052535 | Uhlir-Tsang et al. | May 2006 | B2 |
| 7056962 | Johnson et al. | Jun 2006 | B2 |
| 7058339 | Wilcox | Jun 2006 | B2 |
| 7066590 | Lee et al. | Jun 2006 | B2 |
| 7074843 | Nakamura et al. | Jul 2006 | B2 |
| 7086732 | Kasperchik | Aug 2006 | B2 |
| 7090719 | Ishikawa et al. | Aug 2006 | B2 |
| 7097275 | Murcia | Aug 2006 | B2 |
| 7112629 | Niu et al. | Sep 2006 | B2 |
| 7115675 | Schut | Oct 2006 | B2 |
| 7119133 | Vincent | Oct 2006 | B2 |
| 7125100 | Ishizawa et al. | Oct 2006 | B2 |
| 7129284 | Ma | Oct 2006 | B2 |
| 7148182 | Field et al. | Dec 2006 | B2 |
| 7150522 | Sen | Dec 2006 | B2 |
| 7152965 | Ishizawa et al. | Dec 2006 | B2 |
| 7157504 | Ma et al. | Jan 2007 | B2 |
| 7159975 | Yue et al. | Jan 2007 | B2 |
| 7163577 | Tyrell | Jan 2007 | B2 |
| 7165836 | Ahlvin et al. | Jan 2007 | B2 |
| 7173078 | Lamprey et al. | Feb 2007 | B2 |
| 7204872 | Uhlir-Tsang | Apr 2007 | B2 |
| 7204873 | Bauer | Apr 2007 | B2 |
| 7214260 | Doi et al. | May 2007 | B2 |
| 7217315 | Bauer | May 2007 | B2 |
| 7220303 | Tyvoll | May 2007 | B2 |
| 7220304 | Momose | May 2007 | B2 |
| 7220528 | Ganapathiappan | May 2007 | B2 |
| 7221878 | Chen | May 2007 | B2 |
| 7241334 | Srinivas | Jul 2007 | B2 |
| 7247195 | Dodge et al. | Jul 2007 | B2 |
| 7253216 | Miyabayashi | Aug 2007 | B2 |
| 7264662 | Dodge et al. | Sep 2007 | B2 |
| 7294183 | Tyvoll | Nov 2007 | B2 |
| 7294185 | Belmont et al. | Nov 2007 | B2 |
| 7297202 | Ichinose et al. | Nov 2007 | B2 |
| 7314273 | Robertson et al. | Jan 2008 | B2 |
| 7355044 | Vanmaele et al. | Apr 2008 | B2 |
| 7390441 | Bollepalli | Jun 2008 | B2 |
| 7393403 | Lee et al. | Jul 2008 | B2 |
| 7413683 | Bollepalli | Aug 2008 | B2 |
| 7416587 | Kondo | Aug 2008 | B2 |
| 7416594 | Moffatt | Aug 2008 | B2 |
| 7416597 | Rehman | Aug 2008 | B2 |
| 7497563 | Rehman | Mar 2009 | B2 |
| 7927416 | Sujeeth et al. | Apr 2011 | B2 |
| 7964033 | Sujeeth et al. | Jun 2011 | B2 |
| 20010018472 | Parazak et al. | Aug 2001 | A1 |
| 20010031422 | Iwasaki | Oct 2001 | A1 |
| 20020005146 | Palumbo et al. | Jan 2002 | A1 |
| 20020088375 | Komatsu et al. | Jul 2002 | A1 |
| 20020130938 | Kowalski | Sep 2002 | A1 |
| 20020144626 | Schut | Oct 2002 | A1 |
| 20020158952 | Adachi et al. | Oct 2002 | A1 |
| 20020195022 | Moffatt et al. | Dec 2002 | A1 |
| 20030019398 | Komatsu et al. | Jan 2003 | A1 |
| 20030019529 | Reinelt | Jan 2003 | A1 |
| 20030024434 | Butler et al. | Feb 2003 | A1 |
| 20030038869 | Kaneko et al. | Feb 2003 | A1 |
| 20030164114 | Kitayama et al. | Sep 2003 | A1 |
| 20030205171 | Adams et al. | Nov 2003 | A1 |
| 20030209166 | Vanmaele et al. | Nov 2003 | A1 |
| 20040006157 | Gloster et al. | Jan 2004 | A1 |
| 20040020407 | Kato et al. | Feb 2004 | A1 |
| 20040035323 | Suzuki et al. | Feb 2004 | A1 |
| 20040074018 | Wuzik et al. | Apr 2004 | A1 |
| 20040092647 | Chauvin | May 2004 | A1 |
| 20040103822 | Champlin | Jun 2004 | A1 |
| 20040169165 | Srinivas | Sep 2004 | A1 |
| 20040201658 | Jackson et al. | Oct 2004 | A1 |
| 20040229974 | Miyabayashi | Nov 2004 | A1 |
| 20040252162 | Gondek et al. | Dec 2004 | A1 |
| 20050020728 | Nagaswa et al. | Jan 2005 | A1 |
| 20050129015 | Jamieson et al. | Jun 2005 | A1 |
| 20050171238 | Bauer et al. | Aug 2005 | A1 |
| 20050171239 | Bauer et al. | Aug 2005 | A1 |
| 20050171240 | Bauer et al. | Aug 2005 | A1 |
| 20050183629 | McCain | Aug 2005 | A1 |
| 20050187312 | Akers, Jr. et al. | Aug 2005 | A1 |
| 20050190244 | Tyrell | Sep 2005 | A1 |
| 20050199152 | Hale et al. | Sep 2005 | A1 |
| 20050199155 | Lauw et al. | Sep 2005 | A1 |
| 20050204957 | Momose et al. | Sep 2005 | A1 |
| 20050223938 | Tyvoll | Oct 2005 | A1 |
| 20060004790 | Brown et al. | Jan 2006 | A1 |
| 20060070549 | Jung et al. | Apr 2006 | A1 |
| 20060071992 | Sarkisian et al. | Apr 2006 | A1 |
| 20060135361 | Markel et al. | Jun 2006 | A1 |
| 20060150345 | Mazza | Jul 2006 | A1 |
| 20060162612 | Kabalnov et al. | Jul 2006 | A1 |
| 20060176349 | Nagai et al. | Aug 2006 | A1 |
| 20060189717 | Johnson et al. | Aug 2006 | A1 |
| 20060201380 | Kowalski | Sep 2006 | A1 |
| 20060211791 | Burns et al. | Sep 2006 | A1 |
| 20070154821 | Galloway et al. | Jul 2007 | A1 |
| 20070277699 | Bauer | Dec 2007 | A1 |
| 20070289072 | Mazza | Dec 2007 | A1 |
| 20080047462 | Klein et al. | Feb 2008 | A1 |
| 20080119613 | Klein et al. | May 2008 | A1 |
| 20080121138 | Kennedy et al. | May 2008 | A1 |
| 20080152808 | Kabalnov et al. | Jun 2008 | A1 |
| 20080308002 | Moffatt | Dec 2008 | A1 |
| 20090111917 | Bonora | Apr 2009 | A1 |
| 20090192248 | Palumbo et al. | Jul 2009 | A1 |
| 20100061951 | Sujeeth et al. | Mar 2010 | A1 |
| 20100251932 | Sujeeth et al. | Oct 2010 | A1 |
| Number | Date | Country |
|---|---|---|
| 768805 | Jan 2004 | AU |
| 2198750 | Mar 1996 | CA |
| 2207414 | Jun 1996 | CA |
| 2258188 | Dec 1997 | CA |
| 4215367 | Nov 1993 | DE |
| 19618564 | Nov 1997 | DE |
| 19823866 | Feb 1999 | DE |
| 19831869 | Jan 2000 | DE |
| 102005010468 | Sep 2006 | DE |
| 0475075 | Mar 1992 | EP |
| 0688836 | Dec 1995 | EP |
| 0761783 | Mar 1997 | EP |
| 0778798 | Jun 1997 | EP |
| 0834537 | Apr 1998 | EP |
| 0894835 | Mar 1999 | EP |
| 0960911 | Dec 1999 | EP |
| 1045014 | Oct 2000 | EP |
| 1061107 | Dec 2000 | EP |
| 1132439 | Sep 2001 | EP |
| 1243625 | Sep 2002 | EP |
| 1418209 | May 2004 | EP |
| 1469042 | Oct 2004 | EP |
| 1533347 | May 2005 | EP |
| 1616913 | Jan 2006 | EP |
| 1616915 | Jan 2006 | EP |
| 1681320 | Jul 2006 | EP |
| 2672307 | Aug 1992 | FR |
| 668724 | Mar 1948 | GB |
| 688776 | Mar 1953 | GB |
| 788195 | Dec 1957 | GB |
| 916132 | Jan 1963 | GB |
| 1348850 | Mar 1974 | GB |
| 1386543 | Mar 1975 | GB |
| 1527396 | Oct 1978 | GB |
| 1537379 | Dec 1978 | GB |
| 59122555 | Jul 1984 | JP |
| 59184161 | Oct 1984 | JP |
| 60115665 | Jun 1985 | JP |
| 3279369 | Dec 1991 | JP |
| 5255607 | Oct 1993 | JP |
| 6128517 | May 1994 | JP |
| 7258578 | Oct 1995 | JP |
| 8003498 | Jan 1996 | JP |
| 8283596 | Oct 1996 | JP |
| 10036726 | Feb 1998 | JP |
| 10036727 | Feb 1998 | JP |
| 10067957 | Mar 1998 | JP |
| 10110110 | Apr 1998 | JP |
| 10110111 | Apr 1998 | JP |
| 10110112 | Apr 1998 | JP |
| 10110114 | Apr 1998 | JP |
| 10120958 | May 1998 | JP |
| 10195331 | Jul 1998 | JP |
| 10195360 | Jul 1998 | JP |
| 10237349 | Sep 1998 | JP |
| 10330665 | Dec 1998 | JP |
| 11246806 | Sep 1999 | JP |
| 11323175 | Nov 1999 | JP |
| 11349312 | Dec 1999 | JP |
| 2000053902 | Feb 2000 | JP |
| 2000345085 | Dec 2000 | JP |
| 2000345086 | Dec 2000 | JP |
| 2000345094 | Dec 2000 | JP |
| 2000345095 | Dec 2000 | JP |
| 2002097236 | Apr 2002 | JP |
| 2002220557 | Aug 2002 | JP |
| 2003105235 | Apr 2003 | JP |
| 2003117995 | Apr 2003 | JP |
| 2004010632 | Jan 2004 | JP |
| 2005048114 | Feb 2005 | JP |
| 2005097491 | Apr 2005 | JP |
| 2005132985 | May 2005 | JP |
| 2005349827 | Dec 2005 | JP |
| 2006265379 | Oct 2006 | JP |
| WO 9213983 | Aug 1992 | WO |
| WO 9308237 | Apr 1993 | WO |
| WO 9312939 | Jul 1993 | WO |
| WO 9405732 | Mar 1994 | WO |
| WO 9606729 | Mar 1996 | WO |
| WO 9618688 | Jun 1996 | WO |
| WO 9624636 | Aug 1996 | WO |
| WO 9961529 | Dec 1999 | WO |
| WO 9963007 | Dec 1999 | WO |
| WO 0003609 | Jan 2000 | WO |
| WO 0075246 | Dec 2000 | WO |
| WO 0151566 | Jul 2001 | WO |
| WO 0162862 | Aug 2001 | WO |
| WO 02090448 | Nov 2002 | WO |
| WO 02092680 | Nov 2002 | WO |
| WO 03100884 | Dec 2003 | WO |
| WO 2004011558 | Feb 2004 | WO |
| WO 2004012515 | Feb 2004 | WO |
| WO 2004094537 | Nov 2004 | WO |
| WO 2005028576 | Mar 2005 | WO |
| WO 2005113677 | Dec 2005 | WO |
| WO 2006039034 | Apr 2006 | WO |
| WO 2006066132 | Jun 2006 | WO |
| WO 2006069165 | Jun 2006 | WO |
| WO 2006081299 | Aug 2006 | WO |
| WO 2006086660 | Aug 2006 | WO |
| WO 2007021731 | Feb 2007 | WO |
| WO 2007057111 | May 2007 | WO |
| WO 2007136540 | Nov 2007 | WO |
| WO 2008018873 | Feb 2008 | WO |
| WO 2008049735 | May 2008 | WO |
| WO 2008055244 | May 2008 | WO |
| WO 2008055245 | May 2008 | WO |
| WO 2009026552 | Feb 2009 | WO |
| WO 2009075802 | Jun 2009 | WO |
| WO 2010022377 | Feb 2010 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20110239903 A1 | Oct 2011 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60855573 | Oct 2006 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11933116 | Oct 2007 | US |
| Child | 13042803 | US |
