Surfactants for inks, coatings, and adhesives

Abstract

To provide a surfactant containing an amino acid derivative having a specific structure, and to provide a formulation.SOLUTION: The present disclosure provides surfactants for paints, inks, adhesives, and paint strippers that are in the form of derivatives of amino acids having surface active properties. The amino acids may be naturally occurring or synthetic amino acids, or they may be obtained via a ring-opening reaction of a molecule such as a lactam, for example caprolactam. The amino acid may be for forming a compound having surface active properties. Characteristically, these compounds may have a low critical micelle concentration (CMC) and / or the ability to reduce the surface tension of liquids.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Provisional Patent Application No. 62 / 988,191, filed March 11, 2020, which is incorporated herein by reference in its entirety.

[0002] Field The present disclosure relates to surfactants for use in adhesives and coatings. Such surfactants may comprise derivatives of amino acids, which derivatives have surface-active properties. [Background technology]

[0003] Surfactants (molecules with surface-active properties) are widely used in commercial formulations of inks, paints, adhesives, and paint strippers. Surfactants may be included as emulsifiers, wetting agents, foaming agents, dispersing agents, and / or agents to improve spreading.

[0004] The surfactants may be uncharged, zwitterionic, cationic, or anionic. In principle, any surfactant class (e.g., cationic, anionic, nonionic, amphoteric) is suitable, although it is contemplated that formulations may include combinations of two or more surfactants from two or more surfactant classes.

[0005] Surfactants are often amphiphilic molecules with a relatively water-insoluble hydrophobic "tail" group and a relatively water-soluble hydrophilic "head" group. These compounds can be adsorbed at interfaces, such as those between two liquids, between a liquid and a gas, or between a liquid and a solid. In systems containing relatively polar and relatively non-polar components, the hydrophobic tail preferentially interacts with the relatively non-polar component(s), and the hydrophilic head preferentially interacts with the relatively polar component(s). In the case of a water-oil interface, the hydrophilic head group preferentially extends into the water, and the hydrophobic tail preferentially extends into the oil. When added to a water-gas interface, the hydrophilic head group preferentially extends into the water, and the hydrophobic tail preferentially extends into the gas. The presence of a surfactant disrupts at least some of the intermolecular interactions between water molecules, replacing them with generally weaker interactions between at least some of the water molecules and the surface active agent. This results in a reduced surface tension and can help stabilize the interface.

[0006] At sufficiently high concentrations, surfactants can form aggregates that help limit the exposure of their hydrophobic tails to polar solvents. One such aggregate is a micelle. In a typical micelle, the molecules are arranged in a sphere, with the hydrophobic tails of the surfactant(s) preferentially located inside the sphere and the hydrophilic heads of the surfactant(s) preferentially located on the outside of the micelle, where they preferentially interact with more polar solvents. The effect of a given compound on surface tension and the concentration at which it forms micelles can serve as defining characteristics of a surfactant. Summary of the Invention

[0007] The present disclosure provides ink, paint, adhesive, and paint stripper formulations. These products may be formulated to include one or more surfactants from one or more of the surfactant classes disclosed herein. The surfactants may be used as emulsifiers, wetting agents, foaming agents, dispersants, and / or agents to improve spreading.

[0008] The present disclosure provides paints, inks, adhesives in the form of derivatives of amino acids that have surface active properties. The present invention provides surfactants for paint strippers and other liquids. The amino acids may be naturally occurring or synthetic, or may be obtained via a ring-opening reaction of a molecule such as a lactam, e.g., caprolactam. The amino acids may be used to form compounds with surface-active properties. These compounds may be characterized by a low critical micelle concentration (CMC) and / or the ability to reduce the surface tension of a liquid.

[0009] The present disclosure provides a compound of formula I

[0010] [ka]

[0011] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, where C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; an optional counterion associated with the compound, if present, selected from the group consisting of chloride, bromide, iodide, and hydroxide; one or more humectants; a metal carboxylate as a fixing agent; and an acid. The formulation may also include an aqueous vehicle and one or more colorants dispersed in the ink vehicle.

[0012] The present disclosure further provides a compound of formula I

[0013] [ka]

[0014] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl is optionally selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, and water; at least one surfactant of the formula (which may be substituted with one or more substituents selected from the group consisting of alkyl, carboxyl, and carboxylate); optionally present counterions associated with said compound, which, if present, are selected from the group consisting of chloride, bromide, iodide, and hydroxide; a latex; a binder; one or more driers; one or more pigments; one or more solvents; and water.

[0015] The present disclosure also provides a compound of formula I

[0016] [ka]

[0017] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; optionally present counter ions associated with the compound, when present, selected from the group consisting of chloride ions, bromide ions, iodide ions, and hydroxide ions; a resin; one or more fillers; and a solvent.

[0018] The present disclosure further provides a compound of formula I

[0019] [ka]

[0020] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl optionally has one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate. and optionally a counterion associated with the compound, the counterion being selected from the group consisting of chloride, bromide, iodide, and hydroxide; dichloroethylene; one or more co-solvents; one or more corrosion inhibitors; a wax; an optional thickener; and water.

[0021] The above and other features of the present disclosure, and the manner in which they are achieved, will become more apparent and better understood by reference to the following description of the embodiments taken in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0022] [Figure 1]FIG. 1 shows a plot of surface tension versus concentration for Surfactant 1 measured at pH=7 as described in Example 1b, where the Y-axis represents surface tension (γ) in millinewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 2] FIG. 2 shows a plot of dynamic surface tension versus time as a change in surface tension for surfactant 1 described in Example 1c, where the Y-axis represents surface tension in millinewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). [Figure 3] FIG. 3 shows a plot of surface tension versus concentration for Surfactant 2 measured at pH=7 as described in Example 2b, where the Y-axis represents surface tension (γ) in millinewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 4] FIG. 4 shows a plot of dynamic surface tension versus time as a change in surface tension for surfactant 2 described in Example 2c, where the Y-axis represents surface tension in millinewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). [Figure 5] FIG. 5 shows a plot of surface tension versus concentration for Surfactant 3 measured at pH=7 as described in Example 3b, where the Y-axis represents surface tension (γ) in millinewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 6] FIG. 6 shows a plot of dynamic surface tension versus time as a change in surface tension for surfactant 3 described in Example 3c, where the Y-axis represents surface tension in millinewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). [Figure 7] FIG. 7 shows a plot of surface tension versus concentration for surfactant 4 measured at pH=7 as described in Example 4b, where the Y-axis represents surface tension (γ) in millinewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 8]FIG. 8 shows a plot of dynamic surface tension versus time as a change in surface tension for surfactant 4 described in Example 4c, where the Y-axis represents surface tension in milliNewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). [Figure 9] FIG. 9 shows a plot of surface tension versus concentration for Surfactant 5 measured at pH=7 as described in Example 5b, where the Y-axis represents surface tension (γ) in millinewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 10] FIG. 10 shows a plot of dynamic surface tension versus time as a change in surface tension for surfactant 5 described in Example 5c, where the Y-axis represents surface tension in millinewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). DETAILED DESCRIPTION OF THE INVENTION

[0023] As used herein, the phrase "within any range utilizing these endpoints" refers to any range, regardless of whether the value is in the lower part of the list or in the higher part of the list. A range literally means that a range may be selected from any two of the values ​​listed before such phrase. For example, a pair of values ​​may be selected from two lower values, two higher values, or a lower value and an upper value.

[0024] As used herein, the term "alkyl" means any saturated carbon chain which may be straight or branched.

[0025] As used herein, the phrase "surface active" means that the associated compound is capable of lowering the surface tension of the medium in which it is at least partially dissolved and / or the interfacial tension with other phases, and thus may be at least partially adsorbed at liquid / vapor and / or other interfaces. The term "surfactant" may also be applied to such compounds.

[0026] With respect to imprecision terminology, the terms "about" and "approximately" may be used interchangeably to refer to a measurement that is inclusive of the stated measurement and also encompasses any measurement that is reasonably close to the stated measurement. A measurement that is reasonably close to the stated measurement deviates from the stated measurement by a reasonably small amount, as understood and readily ascertained by one of ordinary skill in the relevant art. Such deviations may be due, for example, to measurement error or minor adjustments made to optimize performance. In cases where it is determined that one of ordinary skill in the relevant art would not readily ascertain values ​​for such reasonably small differences, the terms "about" and "approximately" may be understood to mean plus or minus 10% of the stated value.

[0027] The present disclosure provides ink, paint, adhesive, and paint stripper formulations.

[0028] I. Ink There are several reasons why inkjet printing has become a popular method of recording images on various media surfaces, especially paper. Some of these reasons include low printer noise, high speed recording, high quality, and the ability to record multiple colors. Additionally, these advantages are available at a relatively low price to the consumer. However, while many improvements have been made in inkjet printing, these improvements have also been accompanied by increased consumer demands in this area, such as higher speeds, higher resolution, full color imaging, increased stability, and more durable images.

[0029] Ink jet sets are used in color ink jet printing systems. The ink sets often include multiple different color inks, typically in groups of four, six, or eight (e.g., one or more shades of cyan, magenta, yellow, and / or black), and may further include an image fixing / fixing fluid. The fixing fluid is often applied before or after the inks are fixed to the print media surface. The fixing fluid is a substantially colorless liquid that interacts with the colorants and / or polymer components of the ink(s), thereby causing the ink(s) to precipitate or otherwise fix to the print media surface.

[0030] The precipitated colorant deposits on the media surface, resulting in enhanced image quality attributes, such as optical density and saturation. Durability attributes such as waterfastness and highlighter smear also benefit from such reactive ink chemistry. While several suitable ink sets, including fixers, are currently available, improvements to the ink set are desirable to formulate more durable and reliable inks that produce high-quality printed images on the print media surface without damaging the printhead containing them. Without being bound by any theory, after the fixer composition is overcoated with the inkjet ink composition on the substrate surface, i.e., when the ink and fixer meet at the media surface, highly effective collision of the ink colorants is achieved, with nearly all of the colorant depositing on the media surface rather than penetrating the media and depositing below the surface. At the same time, upon mixing with the ink vehicle, the fixer vehicle becomes more highly wetted, and the combined vehicle rapidly penetrates the media, leaving the colorant behind.

[0031] In such inkjet printing processes, the combination of a fixer fluid and an inkjet ink composition results in a system and method that provides high-quality and durable inkjet image printing. The use of the fixer fluid of the present disclosure results in enhanced image quality attributes, such as optical density, saturation, and durability. Furthermore, the fixer fluid composition provides good image quality and does not adversely affect the reliability of the inkjet infrastructure when used in inkjet printing systems. In fact, it has been found that the fixer fluid does not cause damage to printheads containing it and is low in corrosiveness to inkjet systems and inkjet pens.

[0032] The ink formulation of the present disclosure includes an inkjet fixer composition comprising one or more surfactants selected from one or more surfactant classes, one or more humectants, a metal carboxylate salt as a fixer, and an acid for adjusting the pH of the composition to a pH between about 5.0 and about 7.0. The formulation may also include an aqueous vehicle and one or more colorants dispersed in the ink vehicle.

[0033] 1. Surfactants The ink formulation of the present disclosure includes one or more surfactants, also referred to as a surfactant system. Surfactants have excellent ability to maintain the surface tension and interfacial tension at the proper level. Surfactants may also be used as wetting agents and dispersants. Suitable surfactants for use in the ink formulation of the present disclosure are those represented by Formula I:

[0034] [ka]

[0035] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; and optionally present counter ions associated with said compounds, when present, selected from the group consisting of chloride, bromide, iodide, and hydroxide.

[0036] In particular, suitable surfactants or co-surfactants may include any one or more of Surfactants 1-5 described herein.

[0037] The amount of surfactant system in the ink formulation may be about 0 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, about 0.4 wt% or more, about 0.6 wt% or more, about 0.8 wt% or more, or about 1.0 wt% or less, about 1.2 wt% or less, about 1.4 wt% or less, about 1.6 wt% or less, about 1.8 wt% or less, about 2.0 wt% or less, or any combination thereof, by weight of the composition. It may range within any of the ranges used.

[0038] 2. Moisturizer The ink formulations of the present disclosure include a humectant. "Humectant," as used herein, means any substance used as a humectant or moisturizing agent. Without being bound to any theory, humectants are added to maintain a narrow range of fixer moisture content despite humidity fluctuations, and therefore often to prevent clogging of narrow inkjet pen nozzles.

[0039] The humectant is a high-boiling, water-miscible organic compound, such as polyol, amide, or polyether.The humectant may be water-soluble.Suitable water-soluble humectants for this purpose include, but are not limited to, heterocyclic ketones (e.g., 2-pyrrolidone, N-methyl-pyrrolidone-2-one, 1,3-dimethyl-imidazolidone-2-one, octyl-pyrrolidone, etc.); glycols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, etc.); glycerol; and diols (e.g., butanediol, pentanediol, hexanediol, etc.).

[0040] The humectant may be present in the ink formulation in an amount of about 1 wt% or more, 2 wt% or more, 5 wt% or more, 8 wt% or more, or 10 wt% or less, 12 wt% or less, 15 wt% or less, 18 wt% or less, 20 wt% or less, or any range using these endpoints. 3. Fixing agent A "fixer" or "fixing solution" contains an aqueous vehicle and an effective amount of one or more fixing agents. The fixing agent is an ingredient that initiates a change in the solubility or stability of the colorant, fixing the colorant in place in the printed image. An "effective amount" of fixing agent is an amount effective to achieve improved print quality, such as reduced strike-through and bleed, increased optical density (OD), color saturation, edge acuity, and improved drip and smear fastness, compared to an unfixed print. The fixer can be formulated for high speed and rapid penetration and drying. The surface tension can be less than about 45 mN / m.

[0041] The adhesion promoter may be a metal carboxylate, such as a metal salt composed of a polyvalent metal ion and a carboxylate ion.

[0042] Suitable metal carboxylates include Ca 2+ , Mg 2+ , Cu 2+ Divalent metal ions such as Al 3+ , La 3+ or Fe 3+ The present invention may also include polyvalent metal carboxylates, including trivalent metal ions such as:

[0043] The carboxylate ion may be an aliphatic monocarboxylic acid having 1 to 6 carbon atoms. Suitable carboxylate ions include acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate, and hexanoate.

[0044] The fixing agent is present in the fixer composition in an amount of about 3 wt% or more, about 4 wt% or more, about 5 wt% or more, about 6 wt% or more, about 7 wt% or more, about 8 wt% or more, about 9 wt% or more, or about 10 wt% or less, about 11 wt% or less, about 12 wt% or less, about 13 wt% or less, about 14 wt% or less, about 15 wt% or less, about 16 wt% or less, or any range using these endpoints.

[0045] 4. Acid The fixer may contain an acid. Any suitable acid may be selected. For example, a strong acid (i.e., an acid that is completely ionized in water) may be added to the fixer composition. Non-limiting examples of such acids include methanesulfonic acid, hydrochloric acid, nitric acid, hydrobromic acid, sulfuric acid, and perchloric acid. Examples of suitable anti-inflammatory agents include benzotriazole, benzotriazole, benzophenone, benzotriazole ...

[0046] The acid assists in adjusting the pH of the fixer composition, which may be about 5.0 or greater, about 5.5 or greater, about 6.0 or greater, or about 6.5 or less, about 7.0 or less, or any range using these endpoints.

[0047] In some embodiments, the fixer formulation will not form acid vapors or will form less than 0.5% acid vapors (volatile organic acids) upon formation, hi some other embodiments, the pH of the fixer will be adjusted within an appropriate range to avoid fixer compositions containing more than 0.5 wt% volatile organic acids.

[0048] 5. Water-based medicine The fixing solution of the present disclosure may contain an aqueous vehicle. As defined herein, the term "aqueous vehicle" refers to the aqueous mixture into which the fixing agent is placed to form the fixing solution. Suitable aqueous vehicle components may include, but are not limited to, water, cosolvents, surfactants, additives (such as corrosion inhibitors, salts, etc.), and / or combinations thereof.

[0049] The aqueous vehicle can include a water-soluble organic co-solvent, an additional surfactant, and water. Non-limiting examples of water-soluble organic co-solvents include 2-ethyl-2-hydroxymethyl-1,3-propanediol, glycerol propoxylate, tripropylene glycol, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2-imidazolidinone, and / or combinations thereof.

[0050] 6. Coloring Agents The inkjet ink set of the present disclosure may include some form of the fixer composition described above and an ink having a colorant dispersed or dissolved in an ink vehicle. The inkjet ink set may include at least an inkjet ink composition including a colorant dispersed in an ink vehicle, and a fixer including one or more surfactants selected from one or more surfactant classes, one or more humectants, a metal carboxylate as a fixer, and an acid.

[0051] It should be understood that any number of color ink compositions can be included in the ink set along with the fixer. Furthermore, any desired combination of color inks can be used. For example, each of the color ink compositions can be a different color, or two or more of the inks can be different shades of the same color (i.e., light magenta and dark magenta). In some embodiments, the inkjet ink set includes four different color inks: a black ink, a yellow ink, a cyan ink, and a magenta ink. In other embodiments, the inkjet ink set includes any desired number of inks selected from a black ink, a yellow ink, a cyan ink, a magenta ink, an orange ink, a red ink, a green ink, and / or combinations thereof. In some embodiments, the inkjet ink set includes a fixer as described herein and an inkjet ink composition selected from a black ink, a yellow ink, a cyan ink, a magenta ink, an orange ink, a red ink, and a green ink, and the ink set further includes at least one other ink selected from a black ink, a yellow ink, a cyan ink, a magenta ink, an orange ink, a red ink, and a green ink.

[0052] The colorant for each ink is selected from a pigment, a dye, or a combination thereof. In some embodiments, the ink contains a pigment as the colorant. As used herein, "pigment" refers to colorant particles that are substantially insoluble in the liquid vehicle used. Pigments may also be used in combination with other inks. The pigment may be dispersed using a dispersant, or may be self-dispersed by attaching a dispersant to the pigment's surface. As used herein, "self-dispersed" generally refers to a pigment functionalized with a dispersant, such as by chemically attaching the dispersant to the pigment's surface. The dispersant may be a small molecule or a polymer or oligomer. The pigment includes both self-dispersed pigments and dispersed pigments, for example, pigments dispersed with a separate dispersant that is not covalently attached to the surface. In one example, the pigment is not self-dispersed, and a dispersing aid may be added to the vehicle. In another example, the pigment is self-dispersed and modified to include at least one chemically attached polymer.

[0053] The colorants for the cyan and / or magenta inks may be a combination of pigments and dyes. The pigments and / or dyes for the cyan and magenta colorants may be selected from several commercially available pigments and / or dyes. Non-limiting examples of suitable pigments for the cyan colorant include Pigment Blue 1, Pigment Blue 2, Pigment Blue 3, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 16, Pigment Blue 22, VAT Blue 4, VAT Blue 6, and / or the like, and / or combinations thereof. Examples of suitable dyes for the cyan colorant include, but are not limited to, triphenylmethane dyes such as Acid Blue 9 and Acid Blue 7, and phthalocyanine dyes such as Direct Blue 199. Non-limiting examples of suitable pigments for the magenta colorant include Pigment Red 5, Pigment Red 7, Pigment Red 12, Pigment Red 48, Pigment Red 57, Pigment Red 112, Pigment Red 122, and / or the like, and / or combinations thereof. Examples of suitable dyes for the magenta colorant include, but are not limited to, xanthene dyes such as, for example, Acid Red 52, Acid Red 289, gamma acid dyes, H acid dyes, and / or combinations thereof.

[0054] Colorants for the black and / or yellow inks may be dyes or pigments. Examples of suitable dyes for black colorants include, but are not limited to, water-soluble metal complex azo dyes such as Reactive Black 31 and Reactive Black 8, water-soluble polyazo dyes such as Direct Black 19, Direct Black 195, and Direct Black 168, and water-soluble sulfur dyes such as solubilized Sulfur Black 1. Materials such as carbon black or derivatives of carbon black are non-limiting examples of suitable pigments for black inks.

[0055] Examples of suitable dyes for the yellow colorant include, but are not limited to, AY-17, AY-23, DY-132, Y-104, and / or combinations thereof. PY-74 is a non-limiting example of a suitable pigment for the yellow ink.

[0056] It should be understood that one or more of the inks in an ink set may contain substantially the same colorants and / or substantially the same ink vehicle formulation. In one example, an ink set includes a yellow ink, a cyan ink, and a magenta ink, each of which has substantially the same ink vehicle formulation.

[0057] The amount of colorant present in each ink composition ranges from about 2.7 wt% or more, about 2.9 wt% or more, about 3.0 wt% or more, about 3.2 wt% or more, about 3.4 wt% or more, or about 3.6 wt% or less, about 3.8 wt% or less, about 4.0 wt% or less, about 4.2 wt% or less, about 4.4 wt% or less, about 4.5 wt% or less, or any range using these endpoints, although it should be understood that the colorant loading can be higher or lower as desired.

[0058] 7. Other additives One or more additives may also be incorporated into the fixer composition. As used herein, the term "additive" refers to a component of the fluid that acts to enhance the fluid's performance, environmental benefits, aesthetic benefits, or other similar properties. Suitable additives include biocides, sequestering agents, chelating agents, corrosion inhibitors, marker dyes (e.g., visible, ultraviolet, infrared, fluorescent, etc.), and / or the like, and / or combinations thereof. Fixers can include corrosion inhibitors, such as Cobratec® CBT, a carboxybenzotriazole available from PMC Specialties Group Inc.

[0059] The additive is present in the fixer composition in an amount ranging from about 0 wt% or more, about 0.01 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, about 0.3 wt% or more, about 0.4 wt% or more, or about 0.5 wt% or less, about 0.6 wt% or less, about 0.7 wt% or less, about 0.8 wt% or less, about 0.9 wt% or less, about 1 wt% or less, or any range using these endpoints. It should be understood that the upper limit of the amount of additive present will depend, at least in part, on the additive used, its impact on the image, its solubility, its impact on pen function, and / or a combination thereof.

[0060] 8. Ink vehicle Each colorant or combination of colorants is combined with a respective ink vehicle to form one or more inks of the ink set. As defined herein, "ink vehicle" refers to the vehicle in which the colorants are placed to form the ink. A wide variety of ink vehicles may be used in the inks, ink sets, and methods according to embodiments disclosed herein. Non-limiting examples of suitable components for ink vehicles include water-soluble polymers, anionic polymers, surfactants, solvents, co-solvents, buffers, biocides, sequestering agents, viscosity modifiers, surface-active agents, chelating agents, resins, and / or water, and / or combinations thereof.

[0061] Suitable solvents for the ink vehicle include, but are not limited to, glycerol polyoxyethyl ether, tripropylene glycol, tetraethylene glycol, 1-(2-hydroxyethyl)-2-imidazolidinone, 1-(2-hydroxyethyl)-2-pyrrolidone, 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolpropane, dipropylene glycol, Dantocol® DHE (Lonza Inc., Fair Lawn, NJ), and / or combinations thereof. The ink used in combination with the fixative may contain one or more of the following solvents: ethylene glycol, diethylene glycol, triethylene glycol, or 1-propoxy-2-propanol.

[0062] The solvent may be present in the ink vehicle in an amount of about 1 wt% or more, about 5 wt% or more, about 10 wt% or more, or about 15 wt% or less, about 20 wt% or less, about 25 wt% or less, or any range using these endpoints.

[0063] The amount and type of solvent used will depend, at least in part, on the desired properties of the ink. Therefore, the amount may vary as desired. In some embodiments, a single solvent is used in the ink vehicle of one or more color inks. Suitable solvents include, but are not limited to, tripropylene glycol, tetraethylene glycol, or 1-(2-hydroxyethyl)-2-pyrrolidone. In other embodiments, the ink comprises a mixture of two or more of the solvents listed above.

[0064] As a non-limiting example, cyan, magenta, yellow, and black inks may be used. The solvent mixture may comprise a mixture of 1-(2-hydroxyethyl)-2-pyrrolidone and 1-(2-hydroxyethyl)-2-pyrrolidone. The total weight percent of the solvent mixture may be about 7 wt% or more, about 9 wt% or more, about 11 wt% or more, about 13 wt% or more, about 15 wt% or more, or about 17 wt% or less, about 19 wt% or less, about 21 wt% or less, about 22 wt% or less, or any range using these endpoints.

[0065] Suitable surfactants include surfactants of the present disclosure and / or ethoxylated alcohols, fluorinated surfactants, 2-diglycol surfactants, phosphate ester surfactants, diphosphate ester surfactants, alkyl sulfates, alkyl ether sulfates, and / or combinations thereof.

[0066] The one or more surfactants may be present in the ink vehicle in an amount of about 8 wt% or less, about 6 wt% or less, about 4 wt% or less, about 2 wt% or less, about 1 wt% or less, or about 0.1 wt% or less.

[0067] The ink vehicle may include at least one polymer. Polymers for the ink vehicle are generally water-soluble and may be selected from salts of styrene-(meth)acrylic acid copolymers, polystyrene-acrylic acid polymers, polyurethanes, and / or other water-soluble polymer binders, and / or combinations thereof. Non-limiting examples of suitable polyurethanes include those available from Dainippon Ink & Coatings, Inc., Osaka, Japan. Chem., Inc. (DIC).

[0068] The polymer may be present in the ink vehicle in an amount of about 0.01 wt% or more, about 0.1 wt% or more, about 0.5 wt% or more, about 1 wt% or more, or about 2 wt% or less, about 3 wt% or less, about 4 wt% or less, or any range using these endpoints.

[0069] Additives may be incorporated into aspects of the ink vehicle for the ink. As a non-limiting example, a bactericide such as Proxel® GXL may be added to the ink to prevent bacterial growth in the ink. Other suitable additives include, but are not limited to, buffers, biocides, sequestering agents, chelating agents, or the like, or combinations thereof.

[0070] The ink vehicle includes one or more additives present in an amount ranging from about 0 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, or about 0.3 wt% or less, about 0.4 wt% or less, about 0.5 wt% or less, or any range using these endpoints.

[0071] 9. Preparation method The ink formulation may be prepared by combining a solvent, a surfactant, optional additive(s), and water and adjusting the pH to a basic pH. In some embodiments, the pH of the color ink ranges from about 8 to about 11. In other embodiments, the pH of the color ink ranges from about 8.5 to about 9.5. A colorant and a polymer are then added to form the ink composition.

[0072] II.Paint The present disclosure provides latex compositions or paint vehicles for paint formulations, particularly semi-gloss and matte interior paint compositions. Latex paint compositions have captured a significant portion of the interior and exterior paint market due to their multiple advantages over organic solvent-based types.

[0073] The coating formulations of the present disclosure comprise a film former, a binder, and one or more surfactant classes. It may include a selected one or more surfactants, one or more drying agents, one or more pigments, one or more solvents, and water.

[0074] 1. Film former Film formers are a group of chemicals that leave a soft, adherent, and continuous coating on a surface. This coating has strong hydrophilic properties. Film formers comprise a large group of chemicals that can be broadly divided into two categories: natural and synthetic.

[0075] Natural film formers include oils, rosins, carbohydrates, and endosperms. Such natural film formers may include cyclic oligoterpenes, polyterpenes, shellac, starches, cellulose, and the like.

[0076] Synthetic film formers include polycondensation materials, polyaddition materials, and polymer resins, and may include cross-linked materials such as alkyd resins, polyesters, polyamide / imides, silicone resins, phenolic resins, melamine resins, urea resins, polyurethanes, epoxy resins, polyolefins, polyvinyl resins, and polyacrylic resins.

[0077] Latex paints often contain synthetic film formers such as polyacrylate resins and alkyd resins, as discussed further below.

[0078] a.Latex emulsion Two types of emulsions commonly used in formulating latex paints include all-acrylic systems, such as copolymerized methyl methacrylate, butyl acrylate, or 2-ethylhexyl acrylate, optionally with a small proportion of acrylic acid, and vinyl acetate formulations, usually combined with a small proportion of a lower alkyl acrylate, such as 2-ethylhexyl acrylate, methyl methacrylate, or butyl acrylate. Traditionally, all-acrylic systems have been used in premium paints because the emulsions have provided good water resistance, desirable leveling, film hardness, durability, scrubability, and the like. Vinyl acetate-acrylic copolymer systems have been used in formulating interior matte and semi-gloss paints and exterior house paints, with vinyl acetate-butyl acrylate latexes producing paint films with excellent toughness, scrub resistance, and durability, while vinyl acetate-dibutyl maleate emulsions have good abrasion resistance, flexibility, and durability.

[0079] Wet adhesion, i.e., the quality of adhesion to previously painted and aged surfaces under wet or wet conditions, has been imparted to both acrylic and vinyl acetate systems by polymerizing wet adhesion monomers into copolymers. Typically, these monomers have terminal olefinic unsaturation at one end and a terminal ureido or urea functionality at the other end of the monomer. While these monomers increase the emulsion's ability to adhere to previously applied coatings under wet conditions, they sometimes make it difficult to polymerize into systems, particularly acrylic systems, and to achieve other desired properties in the paint. Therefore, wet adhesion in paint vehicles is imparted by blending different types of acrylic polymer emulsions to achieve the overall desired properties in the paint vehicle, i.e., durability, wet adhesion, scrubability, flexibility, good leveling, abrasion resistance, toughness, etc.

[0080] Suitable emulsions include vinyl acetate latex. For interior and exterior applications, vinyl acetate is copolymerized with monomers copolymerizable therewith, namely, lower alkyl acrylates such as C1-C6 esters of acrylic and methacrylic acid, including methyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; olefins such as ethylene; alkyl esters of alpha-beta unsaturated dicarboxylic acids, such as dibutyl maleate; vinyl chloride, vinyl esters such as vinyl butyrate, vinyl propionate; vinyl ethers such as methyl vinyl ether, n-butyl vinyl ether; and unsaturated carboxylic acids and amides such as acrylic acid and methacrylic acid, acrylamide and methacrylamide.

[0081] To achieve the wet adhesion in emulsions required for most coating applications, wet adhesion monomers may be interpolymerized with vinyl acetate to form vinyl acetate terpolymers. They can also be copolymerized with blends of other monomers and vinyl acetate copolymers to provide wet adhesion. As used herein, "wet adhesion monomer" is understood to mean those monomers having allylic or acrylic unsaturation in one portion of the molecule and pendant urea or acrylic and cyclic ureido functionality on the other end.

[0082] The latex may be present in the formulation in an amount, as a percentage of the total formulation, of about 40 wt% or more, about 45 wt% or more, about 50 wt% or more, about 55 wt% or more, or about 60 wt% or less, about 65 wt% or less, about 70 wt% or less, or any range using these endpoints.

[0083] Vinyl acetate may be present in the copolymer in an amount, as a percentage of polymer weight, of about 25 wt% or more, about 35 wt% or more, about 45 wt% or more, about 55 wt% or more, about 65 wt% or more, about 75 wt% or more, or about 80 wt% or less, about 85 wt% or less, about 90 wt% or less, about 95 wt% or less, about 98 wt% or less, or any range using these endpoints.

[0084] Comonomers such as lower alkyl acrylates or olefins may be present in the copolymers in an amount, as a percentage of the polymer weight, of about 5 wt% or more, about 8 wt% or more, about 10 wt% or more, or about 12 wt% or less, about 15 wt% or less, about 17 wt% or less, about 20 wt% or less, or any range using these endpoints.

[0085] Wetting adhesion monomers, such as monomers having allylic or acrylic unsaturation on one side of the molecule and pendant urea or acrylic and cyclic ureido functional groups on the other end, may be included in the coating formulation. The wetting adhesion monomers may be present in the coating formulation in an amount, as a percentage of the polymer weight, of about 0.2 wt% or more, about 0.4 wt% or more, about 0.8 wt% or more, about 1.0 wt% or more, about 1.2 wt% or more, or about 1.4 wt% or less, about 1.6 wt% or less, about 1.8 wt% or less, about 2.0 wt% or less, about 2.2 wt% or less, about 2.4 wt% or less, about 2.6 wt% or less, or any range using these endpoints.

[0086] For tetrapolymers, a suitable composition may include vinyl chloride, vinyl acetate, ethylene, and a wettable adhesive monomer.

[0087] Vinyl chloride may be present in an amount, as a percentage of total polymer weight, of about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, about 40 wt% or more, about 45 wt% or more, or about 50 wt% or less, about 55 wt% or less, about 60 wt% or less, about 65 wt% or less, or any range using these endpoints.

[0088] Vinyl acetate, as a percentage of the total polymer weight, is about 30 wt% or more, about 35 wt% or more, about 40 wt% or more, about 45 wt% or more, or about 50 wt% or less, about 55 wt% It may be present in an amount of up to about 60 wt %, up to about 65 wt %, or any range using these endpoints.

[0089] Ethylene may be present in an amount, as a percentage of total polymer weight, of about 10 wt% or more, about 11 wt% or more, about 12 wt% or more, or about 13 wt% or less, about 14 wt% or less, about 15 wt% or less, or any range using these endpoints.

[0090] The wettable adhesive monomer may be present in an amount, as a percentage of the polymer weight, of about 0.2 wt% or more, about 0.4 wt% or more, about 0.8 wt% or more, about 1.0 wt% or more, about 1.2 wt% or more, or about 1.4 wt% or less, about 1.6 wt% or less, about 1.8 wt% or less, about 2.0 wt% or less, about 2.2 wt% or less, about 2.4 wt% or less, about 2.6 wt% or less, or any range using these endpoints.

[0091] b. Alkyd resin The coating formulation may include one or more binders. Suitable binders include various types of alkyd resins. Exemplary alkyd resins include alkyd resins with short, medium, long, and extra-long oil lengths. The term "alkyd resin" also encompasses alkyds modified with other resins, such as acrylic, epoxy, phenolic, urethane, polystyrene, silicone, rosin, and rosin ester alkyds, as well as bio-alkyds such as Setal 900 SM-90, in which the polyester segment is derived from renewable acids and esters.

[0092] The paint formulation may include an amount of binder, based on the total weight of the composition, of about 1 wt% or more, about 5 wt% or more, about 10 wt% or more, about 15 wt% or more, about 25 wt% or more, about 30 wt% or more, or about 35 wt% or less, about 40 wt% or less, about 50 wt% or less, about 60 wt% or less, or any range using these endpoints.

[0093] 2. Surfactants The paint formulations of the present invention include one or more surfactants, also referred to as a surfactant system. The surfactant system includes at least one surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, and optionally at least one other surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof. The surfactant system is present in the paint formulation to aid in emulsion stabilization.

[0094] Suitable surfactants for use in the paint formulations of the present disclosure are those represented by Formula I

[0095] [ka]

[0096] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; and optionally present counter ions associated with said compounds, when present, selected from the group consisting of chloride, bromide, iodide, and hydroxide.

[0097] In particular, suitable surfactants or co-surfactants may include any one or more of Surfactants 1-5 described herein.

[0098] The total amount of one or more surfactants in the paint formulation may be about 0.5 wt% or more, about 1 wt% or more, about 2 wt% or more, or about 3 wt% or less, about 4 wt% or less, about 5 wt% or less, or any range using these endpoints.

[0099] 3. Desiccants The paint formulation may include one or more drying agents. A drying agent is a catalyst used to accelerate the drying process. Suitable drying agents may include oxidation catalysts such as cobalt or manganese salts, polymerization catalysts such as zirconium salts, and / or co-catalysts such as calcium salts to control film formation. The drying agent completely dries the paint within a few hours, such as within three hours, two hours, or less, after application to the surface. Cobalt or manganese esters are oxidation catalysts responsible for initiating the oxidation process, and are used in the preparation of C6-C6O ... 19 Esters of branched fatty acids are included. Examples include cobalt 2-ethylhexanoate, propionate, neodecanoate, naphthenate, a cobalt-embedded polymer product called ECOS ND15 available from Umicore, manganese octoate, and a manganese-amine complex called Nuodex Drycoat available from Huntsman.

[0100] The desiccant composition may be at least about 0.1 wt%, at least about 0.3 wt%, at least about 0.6 wt%, or about 1.0 wt% or less, about 1.2 wt% or less, about 1.5 wt% or less, about 3.5 wt% It may be included in the paint formulation in amounts up to about 6.0 wt % or less, or up to about 6.0 wt %, or any range using these endpoints.

[0101] 4. Pigments Pigments used in aqueous coating compositions typically include opacifying pigments that impart opacity and hiding power to the coating. The coating formulations of the present disclosure may contain one or more pigments to color and / or provide opacity to the composition. Pigments as used herein include both inorganic metal oxides and organic color pigments. Suitable pigments include metal oxides such as titanium oxide and iron oxide, zinc chromate, chromium oxide, cadmium sulfide, azurite (made from kaolin, sodium carbonate, sulfur, and carbon), and lithopone (a blend of zinc sulfide and barium sulfate). Examples of organic color pigments are phthalocyanine blue (alpha and beta), dinitraniline orange (PO-5), perylene red, toluidine red (PR-3), diarylide yellow (PY-12, 13), and quinacridone red (PV-19).

[0102] The pigment may be included in the coating composition in an amount of about 0 wt% or more, about 1 wt% or more, about 5 wt% or more, about 10 wt% or more, or about 15 wt% or less, about 20 wt% or less, about 25 wt% or less, about 30 wt% or less, or any range using these endpoints.

[0103] 5. Solvent The paint formulation may contain one or more aqueous solvents or organic solvents such as mineral spirits and alcohol. Suitable solvents include hydrocarbon solvents or blends thereof. The hydrocarbon solvent may be an aliphatic or aromatic solvent. Examples of organic solvents are petroleum fractions such as pentane, hexane, petroleum naphtha, heptane, and 90 solvent (an aliphatic solvent with a flash point of 140°F). Aromatic solvents include xylene, toluene, Aromatic 100, and other suitable aromatic solvents. The term "mineral spirits," also known as "white spirits," refers to a mixture of C7-C8 12 In a more specific embodiment, the composition includes a mixture of aliphatic and alicyclic hydrocarbons, and in a more specific embodiment, the mixture comprises 15 wt. % to 20 wt. % or less than C7 to C8 based on the total weight of the composition. 12 Mineral spirits contain mixtures or blends of paraffins, cycloparaffins, and aromatic hydrocarbons. Typical mineral spirits, with boiling points ranging between about 150°C and 220°C, are generally clear water to white liquids, are chemically stable, non-corrosive, and have a slight odor. Exemplary mineral spirits include low-aromatic white spirits (LAWS) such as Shell Sol 15 (CAS 64742-88-7) and Shell Sol H (CAS 64742-82-1). The term "alcohol" refers to any alcohol containing C1 to C6 12 C1-C, including straight and branched chain alcohols 12 Alcohols are intended to be included. Exemplary alcohols include triethylene glycol (CAS 112-27-6) and diethylene glycol ethyl ether (CAS 111-90-0). In a more specific embodiment, the coating composition comprises a solvent selected from the group consisting of xylene, mineral spirits, alcohol, water, and combinations thereof.

[0104] The amount of solvent in the paint formulation may be about 5 wt% or more, about 10 wt% or more, about 15 wt% or more, about 17 wt% or more, about 20 wt% or more, about 25 wt% or more, or about 30 wt% or less, about 40 wt% or less, about 60 wt% or less, or any range using these endpoints.

[0105] 6. Other additives The paint formulation may further include one or more additives such as fillers, pigments, surfactants, stabilizers, thickeners, emulsifiers, texture additives, adhesion promoters, biocides, flow promoters, dispersants, and additives that modify the viscosity or appearance of the finish.

[0106] The additives may be included in the paint formulation in an amount of about 0.1 wt% or more, about 0.5 wt% or more, about 1.0 wt% or more, about 1.5 wt% or more, or about 2.0 wt% or less, about 5.0 wt% or less, about 10.0 wt% or less, about 20 wt% or less, about 25 wt% or less, about 30 wt% or less, or any range using these endpoints.

[0107] The paint formulation may contain one or more fillers to thicken and increase the volume of the composition. Suitable fillers include titanium dioxide, calcium carbonate, clay and talc.

[0108] The paint formulation may include one or more additives selected from the group consisting of surfactants, stabilizers, thickeners, emulsifiers, texture additives, adhesion promoters, biocides, and additives that modify the viscosity or appearance of the finish.

[0109] 7. Preparation method The paint formulation may be synthesized by starting with a standard premix of protective colloid, surfactant, and oxidizing agent, after which the monomer may be added, followed by additional surfactant and reducing agent.

[0110] Protective colloids can include hydroxyethyl cellulose, polyvinyl alcohol, casein, hydroxyethyl starch, and carboxymethyl cellulose.

[0111] The protective colloid may be added in an amount of about 0.05 wt% or more, about 0.1 wt% or more, about 0.5 wt% or more, about 1.0 wt% or more, about 1.5 wt% or more, about 2 wt% or more, or about 2.5 wt% or less, about 3.0 wt% or less, about 3.5 wt% or less, about 4.0 wt% or less, about 4.5 wt% or less, or any range using these endpoints, of the weight of the monomers used in the synthesis.

[0112] The free radical initiation catalyst used to carry out the polymerization is commonly referred to as a redox catalyst. As is known, a redox catalyst comprises an oxidizing agent and a reducing agent. The oxidizing and reducing components can be any of those conventionally used in vinyl acetate emulsion polymerization, such as hydrogen peroxide, potassium persulfate, t-butyl peroxypivalate, etc. The preferred reducing agents are ammonium iron(II) sulfate and sodium or zinc formaldehyde sulfoxylate.

[0113] A premix may be formed by charging a first vessel with water, a protective colloid, such as hydroxyethyl cellulose, and a free radical initiator oxidizing agent in conventional amounts. Approximately 0-70% of the total surfactants to be used may then be charged to the first vessel and mixed therein. The remainder of the surfactants may be mixed with the monomers in the second vessel or added separately. In either case, they may be added in a delayed manner. To induce polymerization, monomers and a reducing agent may be added to the first vessel for a period and at a rate such that the unreacted vinyl acetate in the first vessel remains at approximately 3-5% by weight of the emulsion or latex. After all of the monomers have been added to the first vessel, the remaining vinyl acetate is then reduced to less than 0.5% by the addition of additional oxidizing and reducing agents. At the end of the polymerization, the pH may be adjusted to approximately 5.5 by the addition of a base, such as ammonium hydroxide.

[0114] In regard to the polymerization procedure, protective colloids, especially cellulose esters, are used to maintain emulsion stability. Higher levels of colloids tend to increase stability and also tend to increase particle size. Surfactants also provide emulsion stability. However, in contrast to colloids, surfactants tend to reduce particle size when present in the initial polymerization, and tend to exhibit better particle size trends when added later. By using protective colloids and surfactants together, particle size optimization can be achieved.

[0115] Agitation is another variable that can affect the particle size of polymer emulsions. Agitation must be light so that adequate heat transfer can be achieved and product stability can be maintained. Vigorous agitation must be avoided. With regard to particle size control, if larger particles are desired, the agitation speed can be reduced, and if smaller particles are needed, the degree of agitation can be increased. If agitation cannot be improved, adaptation of surfactants or protective colloids may be made.

[0116] III. Adhesive Formulations The present disclosure further provides adhesive formulations that may be used in the manufacture of wood-based boards such as plywood, backboards, chalkboards, fiberboards, OBS boards, or the like.

[0117] The adhesive formulations of the present disclosure comprise a resin, a filler, a solvent, and one or more surfactant classes. The surfactant may contain one or more surfactants selected from the following.

[0118] 1. Resin The resin is present in the adhesive formulation to function as an adhesive itself. Suitable resins include phenol-formaldehyde resins, urea-formaldehyde resins, amino resins, or other corresponding resins. In one embodiment, the resin used is UF (urea-formaldehyde resin), MUF (melamine urea-formaldehyde), MUFP (modified urea-formaldehyde polymer), PF (phenol-formaldehyde), or a derivative or mixture of these or equivalents.

[0119] The resin may be present in the adhesive formulation in an amount of about 40 wt% or more, about 45 wt% or more, about 50 wt% or more, about 55 wt% or more, or about 60 wt% or less, about 65 wt% or less, about 70 wt% or less, about 75 wt% or less, about 80 wt% or less, or any range using these endpoints.

[0120] 2. Filler As used herein, "filler" refers to any known filler or hardener, or a mixture thereof. The hardener performs hardening of the glue during application, i.e., during the manufacture of wood-based boards, often using heat, preferably simultaneously, of compression. Suitable fillers include starch, wheat flour, chalk, sodium carbonate, potassium carbonate, calcium carbonate, ammonium sulfate, wood flour, quebracho, or derivatives thereof, or mixtures thereof, or equivalents. Quebracho refers to the hard woody material of certain South American hardwoods. As used herein, "chalk" refers to loosely structured, lightweight, and easily crumbly limestone.

[0121] The filler may be present in the adhesive composition in an amount of about 5 wt% or more, about 10 wt% or more, about 15 wt% or more, or about 20 wt% or less, about 25 wt% or less, about 30 wt% or less, or any range using these endpoints.

[0122] 3. Solvent The adhesive formulation may contain a solvent such as water. The water may be obtained from outside the process, or it may be recycled water from within the process, i.e., process wash water. Alternatively, the solvent may be an organic solvent.

[0123] The solvent may be present in the adhesive composition in an amount of about 0 wt% or more, about 5 wt% or more, about 10 wt% or more, about 15 wt% or more, about 20 wt% or more, or about 25 wt% or less, about 30 wt% or less, about 35 wt% or less, about 40 wt% or less, or any range using these endpoints.

[0124] 4. Surfactants One or more surfactants may be included in the adhesive composition as foaming agents for the express purpose of promoting foaming. Suitable surfactants for use in the adhesive formulations of the present disclosure are those represented by Formula I

[0125] [ka]

[0126] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; and optionally present counter ions associated with said compounds, when present, selected from the group consisting of chloride, bromide, iodide, and hydroxide.

[0127] In particular, suitable surfactants or co-surfactants may include any one or more of Surfactants 1-5 described herein.

[0128] The adhesive formulation may include one or more surfactants in an amount of about 0.1 wt% or more, about 0.5 wt% or more, about 1 wt% or more, about 2 wt% or more, about 3 wt% or more, about 4 wt% or more, or about 5 wt% or less, about 6 wt% or less, about 7 wt% or less, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, or any range using these endpoints.

[0129] 5. Other additives The adhesive formulation may also include one or more additional compatible ingredients. These additional ingredients may include one or more additional surfactants not intended purely for foaming purposes, such as surfactants of the present disclosure. These additional surfactants may be present in the adhesive formulation in an amount of about 0.1 wt% or more, about 0.5 wt% or more, or about 1.0 wt% or less, about 1.5 wt% or less, about 2.0 wt% or less, or any range using these endpoints.

[0130] The adhesive composition may include a catalyst.

[0131] 6. Preparation method The adhesive formulation may be prepared as an emulsion. To prepare the emulsion, the liquid components may be mixed together and the mixture may be heated at a relatively high temperature (above 40°C).

[0132] IV. Paint stripping formulations The present disclosure also provides a paint stripper formulation. The composition of the present invention can be used to remove adhesives, sealants, and other organic coatings, such as enamel, varnish, or lacquer, from a variety of substrates, including metal substrates such as aluminum and aluminum alloys. Generally, the composition is contacted with the surface for a period of time sufficient to produce blistering of the polymer coating, after which the blistered coating can be removed with an abrasive material. Alternatively, the coating can be removed by spraying water on the blistered coating, which lifts the blistered coating off the surface.

[0133] The paint stripper formulations of the present disclosure may include dichloroethylene, one or more surfactants selected from one or more surfactant systems, one or more co-solvents, a corrosion inhibitor, a wax, a thickener, an organic solvent, and water.

[0134] 1. Dichloroethylene The release formulation may include dichloroethylene (1,1-dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, or mixtures thereof).

[0135] Dichloroethylene may be present in the stripping formulation in an amount of about 55 wt% or more, about 57 wt% or more, about 59 wt% or more, or about 61 wt% or less, about 63 wt% or less, about 65 wt% or less, or any range using these endpoints.

[0136] 2. Surfactants Surfactants may be included in the stripping formulation to increase the solubility of certain ingredients.

[0137] Suitable surfactants for use in the stripping formulations of the present disclosure are those represented by Formula I

[0138] [ka]

[0139] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; and optionally present counter ions associated with said compounds, when present, selected from the group consisting of chloride, bromide, iodide, and hydroxide.

[0140] In particular, suitable surfactants or co-surfactants may include any one or more of Surfactants 1-5 described herein.

[0141] The surfactant may be present in the stripping formulation in an amount of about 1 wt% or more, about 2 wt% or more, about 3 wt% or more, about 4 wt% or more, about 5 wt% or more, or about 6 wt% or less, about 7 wt% or less, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, or any range using these endpoints.

[0142] 3. Co-solvent Co-solvents may be used to increase the expansion of the target coating. The release formulations of the present disclosure may include such co-solvents. Suitable solvents include diphenoxybenzene, propoxybenzene, methoxybenzene, ethoxybenzene, benzyl ether, diphenyl ether, cyclopentanol, naphthalenol, phenylcarbinal, tolyl alcohol, melityl alcohol, and aromatic ring-forming solvents. Included are aromatic alcohols and aromatic ethers, such as other aromatic alcohols containing a hydroxyl group in the side chain. Other suitable solvents include aliphatic alcohols, ethanol, propanol, butanol, pentanol, hexanol, and alcohols having up to 12 carbon atoms. Such co-solvents are generally considered environmentally friendly and non-toxic, and can be effective co-solvents that do not require additional activators for stripping formulations, such as 1,2-dichloroethylene.

[0143] The aromatic alcohols and aromatic ethers may be present in the stripping formulation in an amount of about 10 wt% or more, about 11 wt% or more, about 12 wt% or more, about 13 wt% or more, about 14 wt% or more, about 15 wt% or more, or about 16 wt% or less, about 17 wt% or less, about 18 wt% or less, about 19 wt% or less, about 20 wt% or less, or any range using these endpoints.

[0144] The fatty alcohol may be present in the stripping formulation in an amount of about 1 wt% or more, about 2 wt% or more, about 3 wt% or more, about 4 wt% or more, about 5 wt% or more, or about 6 wt% or less, about 7 wt% or less, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, or any range using these endpoints.

[0145] 4. Corrosion inhibitors The stripping formulations of the present disclosure may also include a corrosion inhibitor. Suitable corrosion inhibitors may include benzimidazoles, benzazoles, benzoxazoles, and mixtures of these corrosion inhibitors, as well as triazoles such as benzotriazole and tolytriazole.

[0146] The corrosion inhibitor may be included in the stripping formulation in an effective amount of about 0 wt% or more, about 1 wt% or more, about 2 wt% or more, about 3 wt% or more, about 4 wt% or more, about 5 wt% or more, or about 6 wt% or less, about 7 wt% or less, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, or any range using these endpoints.

[0147] 5. Wax The stripping formulation of the present disclosure may contain a wax. Suitable waxes include paraffin wax. To facilitate mixing with the other components of the stripping formulation, the wax may be dissolved in a solvent prior to mixing with the other components. Substantially non-polar or lipophilic solvents may be used for this purpose. Suitable solvents include aromatic and aliphatic hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, heptane, octane, and similar linear and branched hydrocarbons, and mixtures thereof. Included are fractions from the distillation of petroleum-based mineral spirits, and various mixtures of these solvents.

[0148] The wax may be present in the release formulation in an amount of about 1.0 wt% or more, 1.5 wt% or more, 2.0 wt% or more, 2.5 wt% or more, or 3.0 wt% or less, 3.5 wt% or less, 4.0 wt% or less, 4.5 wt% or less, or 5.0 wt% or less, or any range using these endpoints.

[0149] 6. Thickeners The release formulations of the present disclosure may also include a thickener. In applications where vertical surfaces are treated with the formulation, a thickener may be used to hold the formulation to the coating surface long enough to loosen the coating. Suitable thickeners may include celluloses such as ethyl cellulose, ethylhydroxyethyl cellulose, methyl cellulose, colloidal silica, clays such as bentonite, starch, colloidal alumina, or gum arabic. can.

[0150] The thickener may be present in the stripping formulation in an amount of 0 wt% or more, 1.0 wt% or more, 1.5 wt% or more, 2.0 wt% or more, 2.5 wt% or more, or 3.0 wt% or less, 3.5 wt% or less, 4.0 wt% or less, 4.5 wt% or less, or 5.0 wt% or less, or any range using these endpoints.

[0151] 7. Solvent The stripping formulations of the present disclosure may include additional solvents, such as organic solvents and water.

[0152] The organic solvent may be present in the stripping formulation in an amount of about 1.0 wt% or more, 1.5 wt% or more, 2.0 wt% or more, 2.5 wt% or more, or 3.0 wt% or less, 3.5 wt% or less, 4.0 wt% or less, 4.5 wt% or less, or 5.0 wt% or less, or any range using these endpoints.

[0153] Water may be present in the stripping formulation in an amount of about 1 wt% or more, about 5 wt% or more, about 8 wt% or more, about 10 wt% or more, or about 12 wt% or less, about 15 wt% or less, about 18 wt% or less, about 20 wt% or less, or any range using these endpoints.

[0154] 8.How to use The stripping formulations of the present disclosure are generally applied to the surface to be stripped in the usual manner, i.e., the composition is applied with a brush or other applicator and then spread on the surface to be stripped, or the formulation may be sprayed onto the surface using a spray system, which takes advantage of the tiotropic properties of the formulation on a vertical panel.

[0155] VI. Surfactants The present disclosure provides surfactants for use in inks, paints, adhesives, and paint strippers in the form of derivatives of amino acids. The amino acids may be naturally occurring or synthetic, or they may be obtained from the ring-opening reaction of lactams such as caprolactam. The compounds of the present disclosure have been shown to have surface-active properties and may be used, for example, as surfactants and wetting agents. In particular, the present disclosure provides compounds of formula I

[0156] [ka]

[0157] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; and optionally present, when present, an ion selected from the group consisting of chloride ion, bromide ion, iodide ion, and hydroxide ion. and a counter ion associated with the compound, which is selected.

[0158] One specific compound provided by the present disclosure is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide (Surfactant 1), which has the formula:

[0159] [ka]

[0160] A second specific compound provided by the present disclosure is dodecyl 6-(dimethylamino)hexanoate N-oxide (Surfactant 2), which has the following formula:

[0161] [ka]

[0162] In the above structures, the "N→O" notation is intended to mean a non-ionic bonding interaction between the nitrogen and oxygen.

[0163] A third specific compound provided by the present disclosure is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride (Surfactant 3), which has the formula:

[0164] [ka]

[0165] A fourth specific compound provided by the present disclosure is 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (Surfactant 4), which has the following formula:

[0166] [ka]

[0167] A fifth specific compound provided by the present disclosure is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride (Surfactant 5), which has the formula:

[0168] [ka]

[0169] These surfactants can be synthesized by various methods. One such method involves ring-opening a lactam to obtain an amino acid having an N-terminus and a C-terminus. The N-terminus can be reacted with one or more alkylating agents and / or acids to obtain a quaternary ammonium salt. Alternatively, the N-terminus can be reacted with an oxidizing agent to obtain an amine N-oxide. The C-terminus can be reacted with an alcohol in the presence of an acid to obtain an ester.

[0170] The amino acids may be natural or synthetic, or may be derived from the ring-opening reaction of a lactam such as caprolactam. The ring-opening reaction may be acid or alkali catalyzed, an example of an acid catalyzed reaction is shown in Scheme 1 below.

[0171] [ka]

[0172] The amino acid may have as few as one or as many as 12 carbons between the N-terminus and C-terminus. The alkyl chain may be branched or straight. The alkyl chain may be interrupted by nitrogen, oxygen, or sulfur. The alkyl chain may be further substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carboxyl, and carboxylate. The N-terminal nitrogen may be acylated or alkylated with one or more alkyl groups. For example, the amino acid may be 6-(dimethylamino)hexanoic acid.

[0173] Surfactant 1 can be synthesized as shown in Scheme 2 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid under reflux to give 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then treated with an alcohol such as dodecanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-(dimethylamino)hexanoate. The N-terminus is then alkylated with methyl iodide in the presence of sodium carbonate.

[0174] [ka]

[0175] Surfactant 2 can be synthesized as shown in Scheme 3 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid under reflux to give 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then treated with an alcohol such as dodecanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-(dimethylamino)hexanoate. The N-terminus is then oxidized with hydrogen peroxide to give the amine oxide.

[0176] [ka]

[0177] Surfactant 3 can be synthesized as shown in Scheme 4 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid under reflux to give 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then treated with an alcohol such as dodecanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-(dimethylamino)hexanoate. The N-terminus is then alkylated with methyl iodide in the presence of sodium carbonate.

[0178] [ka]

[0179] Surfactant 4 can be synthesized as shown in Scheme 5 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid at reflux to give 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then treated with an alcohol such as dodecanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-(dimethylamino)hexanoate. The N-terminus is then treated with 1,4-butanesultone in ethyl acetate at reflux to give the desired sulfonate.

[0180] [ka]

[0181] Surfactant 5 can be synthesized as shown below in Scheme 6. As shown, 6-aminohexanoic acid is treated with an alcohol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-aminohexanoate. The N-terminus is protonated with hydrochloric acid to give the desired hydrochloride salt.

[0182] [ka]

[0183] The compounds of the present disclosure exhibit surface active properties. These properties can be measured and expressed by various methods. One way to express surfactants is by the critical micelle concentration (CMC) of the molecule. CMC can be defined as the concentration of surfactant that forms micelles, and at a higher concentration, all additional surfactants are incorporated into the micelles.

[0184] As surfactant concentration increases, surface tension decreases. When the surface is completely covered with surfactant molecules, micelles begin to form. This point represents the CMC, or minimum surface tension. Adding more surfactant does not further affect the surface tension. The CMC can therefore be measured by observing the change in surface tension as a function of surfactant concentration. One such method for measuring this value is the Wilhelmy plate method. A Wilhelmy plate is typically a thin iridium-platinum plate attached to a balance by wires and positioned perpendicular to the air-liquid interface. The balance is used to measure the force exerted on the plate by wetting. This value is then used to calculate the surface tension (γ) according to Equation 1: Equation 1: γ = F / l cosθ where l is equal to the wetted perimeter (2w+2d, where w and d are the thickness and width of the plate, respectively), and for cosθ, the contact angle between the liquid and the plate is assumed to be 0 in the absence of an existing literature value.

[0185] Another parameter used to evaluate the performance of surfactants is dynamic surface tension. Dynamic surface tension is the value of the surface tension of a particular surface or interface over time. For liquids to which surfactants have been added, this may differ from the equilibrium value. Immediately after the surface is created, the surface tension is equal to that of the pure liquid. As mentioned above, surfactants reduce surface tension, so the surface tension decreases until it reaches an equilibrium value. The time required to reach equilibrium depends on the diffusion and adsorption rates of the surfactant.

[0186] One method for measuring dynamic surface tension is with a maximum bubble pressure tensiometer. This device measures the maximum internal pressure of a bubble formed in a liquid by a capillary. The measured value corresponds to the surface tension at a specific surface elapsed time, which is the time from the start of bubble formation to the maximum pressure. The dependence of surface tension on surface elapsed time can be measured by varying the rate at which the bubbles are generated.

[0187] Surface active compounds can also be evaluated by their wetting ability on solid substrates, measured by contact angles. When a liquid droplet contacts a solid surface in a third medium, such as air, a three-phase line is formed between the liquid, the gas, and the solid. The surface tension line, which plays a role in the three-phase line and is tangent to the droplet, The angle between the unit vector of force and the surface is expressed as the contact angle. The contact angle (also known as the wetting angle) is a measure of the wettability of a solid by a liquid. In the case of complete wetting, the liquid spreads completely on the solid, and the contact angle is 0°. Wetting properties are typically measured at concentrations between 1 and 100 x CMC for any compound, but as it is not a concentration-dependent property, measurements of wetting properties may be measured at higher or lower concentrations.

[0188] In one method, an optical contact angle goniometer can be used to measure contact angles. This instrument uses a digital camera and software to determine the contact angle by analyzing the contour shape of a sedentary drop of liquid on a surface.

[0189] Potential applications for the surface-active compounds of the present disclosure include formulations for use as shampoos, hair conditioners, detergents, spot-free rinse solutions, floor and carpet cleaners, cleaners for graffiti removal, wetting agents for crop protection, adjuvants for crop protection, and wetting agents for aerosol spray coatings.

[0190] Those skilled in the art will appreciate that small differences between compounds can lead to significantly different surfactant properties, and therefore different compounds may be used with different substrates in different applications.

[0191] The following non-limiting examples are provided to illustrate the different properties of different surfactants. Table 1 below associates surfactant abbreviations with their corresponding chemical structures.

[0192] [Table 1]

[0193] Each of the five compounds is effective as a surfactant and is useful as a wetting or foaming agent, dispersing agent, emulsifier, and detergent, among other uses.

[0194] Surfactant 1, Surfactant 3, and Surfactant 5 are cationic. These surfactants are useful in both the applications mentioned above and in some further specialty applications, such as surface treatments, personal hair care products, and can also be used to create water-repellent surfaces.

[0195] Surfactant 4 is non-ionic and can be used in shampoos, detergents, hard surface cleaners, and a variety of other surface cleaning formulations.

[0196] Surfactant 5 is zwitterionic. These surfactants are useful as co-surfactants in all of the applications mentioned above.

[0197] Example Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500 MHz spectrometer. The critical micelle concentration (CMC) was determined by the Wilhelmy plate method using a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate. The dynamic surface tension was determined at 23°C using a maximum bubble pressure tensiometer (Kruss BP100, Kruss GmbH). The contact angle was determined using an optical contact angle goniometer (OCA 15 Pro, DataPhysics GmbH) equipped with a digital camera.

[0198] Example 1a: Synthesis of 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide (surfactant 1) 6-(Dimethylamino)hexanoic acid (11.99 g, 75.36 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (12.68 g, 75.36 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (14.33 g, 75.36 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-(dimethylamino)hexanoate in 51% yield. 1H NMR(DMSO)δ 4.00(t,J=6.5Hz,2H),2.27(t,J=7.3Hz,2H),2.13-2.16(m,2H),2.01(s,6H),1.54-1.53(m,6H),1.27-1.18(m,20H),0.86(t,3H).

[0199] Dodecyl 6-(dimethylamino)hexanoate (1.0 g, 3.05 mmol) was dissolved in acetonitrile (10 mL). Sodium carbonate (0.388 g, 3.66 mmol) was then added, and the reaction was stirred at room temperature for 10 minutes. Methyl iodide (0.57 mL, 9.16 mmol) was added, and the reaction mixture was heated to 40° C. for 24 hours and then cooled to room temperature. The mixture was filtered and concentrated to give 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide as a yellow solid in 92% yield. 1H NMR (DMSO)δ 4.00(t,J=6.7Hz,2H),3.30-3.22(m,2H),3.04(s,9H),2.34(t,J=7.4Hz,2H),1 .70-1.63(m,2H),1.62-1.46(m,4H),1.31-1.20(m,20H),0.86(t,J=6.9Hz,3H).

[0200] Example 1b: Identification of the critical micelle concentration (CMC) of surfactant 1 The critical micelle concentration (CMC) was determined. From the change in surface tension with concentration in water, the CMC was determined to be approximately 1 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 33 mN / m, i.e., 33 mN / m ± 3.3 mN / m. Figure 1 is a plot of these results, showing surface tension versus concentration. The plot shows that the surface tension is approximately 34 mN / m at the CMC and approximately 33.8 mN / m at concentrations above 1.0 mmol.

[0201] Example 1c: Determining the dynamic surface tension of surfactant 1 Dynamic surface tension was determined with a maximum bubble pressure tensiometer, which measures the change in surface tension of a newly created air-water interface over time. Figure 2 presents a plot of the results as surface tension versus time, showing that over the time interval from 1 ms to 75 ms, the surface tension rapidly decreases from approximately 55.5 mN / m to approximately 39.9 mN / m. Over the time interval from 75 ms to 50,410 ms, the surface tension decreases more slowly from approximately 39.9 mN / m to approximately 34 mN / m, asymptotically approaching the saturated value of surface tension at the CMC.

[0202] Example 1d: Identification of the wetting properties of surfactant 1 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit surface wetting with a contact angle of 32°. On oleophobic and hydrophobic substrates such as Teflon®, the measured contact angle was 67.1°, much lower than that of water (Table 2).

[0203] [Table 2]

[0204] Example 2a: Synthesis of dodecyl 6-(dimethylamino)hexanoate N-oxide (surfactant 2) 6-(Dimethylamino)hexanoic acid (11.99 g, 75.36 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (12.68 g, 75.36 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (14.33 g, 75.36 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-(dimethylamino)hexanoate in 51% yield. 1 H NMR(DMSO)δ 4.00(t,J=6.5Hz,2H),2.27(t,J=7.3Hz,2H),2.13-2.16(m,2H),2.01(s,6H),1.54-1.53(m,6H),1.27-1.18(m,20H),0.86(t,3H).

[0205] Dodecyl 6-(dimethylamino)hexanoate (1.0 g, 3.05 mmol) was dissolved in distilled water (80 mL). Hydrogen peroxide (50% solution, 1.04 g, 30.5 mmol) was added. The reaction was heated to reflux for 12 hours, and then the solvent was removed in vacuo. The resulting solid was washed with acetone to give the desired N-oxide in 90% yield. 1 H NMR(500MHz,DMSO)δ 4.00(t,J=6.6Hz,2H),3.30-3.26(m,2H),3.18(s,6H),2.31(t,J=7.4Hz,2H),1 .76-1.73(m,2H),1.54-1.57(m,4H),1.30-1.24(m,22H),0.86(t,J=6.9Hz,3H).

[0206] Example 2b: Identification of the critical micelle concentration (CMC) of surfactant 2 The critical micelle concentration (CMC) was determined. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.08 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 28 mN / m, i.e., 28 mN / m ± 2.8 mN / m. Figure 3 is a plot of these results, showing surface tension versus concentration. The resulting plot indicates that the surface tension at the CMC is approximately 30 mN / m or less. The plot further indicates that at concentrations of 0.08 mmol or greater, the surface tension is 30 mN / m or less.

[0207] Example 2c: Determining the dynamic surface tension of surfactant 2 Dynamic surface tension was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension of a newly created air-water interface over time. Figure 4 shows a plot of surface tension versus time, showing that the compound fully saturated the surface in approximately 7.6 seconds. As can be seen from the plot, the dynamic surface tension is below 40 mN / m for surface dwell times of over 4900 ms.

[0208] Example 2d: Identification of the wetting properties of surfactant 2 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit surface wetting with a contact angle of 39.3°, which is significantly lower than that of water. On oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was 57.4°, significantly lower than that of water (Table 3).

[0209] [Table 3]

[0210] Example 3a: Synthesis of 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride (surfactant 3) 6-(Dimethylamino)hexanoic acid (11.99 g, 75.36 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (12.68 g, 75.36 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (14.33 g, 75.36 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-(dimethylamino)hexanoate in 51% yield. 1H NMR(DMSO)δ 4.00(t,J=6.5Hz,2H),2.27(t,J=7.3Hz,2H),2.13-2.16(m,2H),2.01(s,6H),1.54-1.53(m,6H),1.27-1.18(m,20H),0.86(t,3H).

[0211] Dodecyl 6-(dimethylamino)hexanoate (100 mg, 0.305 mmol) was dissolved in water (10 mL). Concentrated hydrochloric acid (11.14 mg, 0.305 mmol) was added.

[0212] Example 3b: Identification of the critical micelle concentration (CMC) of surfactant 3 The critical micelle concentration (CMC) was investigated. From the change in surface tension with concentration in water, the CMC was determined to be approximately 1.4 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 30 mN / m, i.e., 30 mN / m ± 3 mN / m. Figure 5 is a plot of these results, showing surface tension versus concentration. The resulting plot indicates that the surface tension at the CMC is approximately 30 mN / m or less. The plot further indicates that the CMC is approximately 2.7 mmol. It also shows that at these concentrations, the surface tension is 33 mN / m or less.

[0213] Example 3c: Determining the dynamic surface tension of surfactant 3 Dynamic surface tension was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension over time at a newly created air-water interface. Figure 6 shows a plot of surface tension versus time, showing that over the time interval of 1 to 100 ms, the surface tension rapidly decreases from approximately 50 mN / m to approximately 40 mN / m. Over the time interval of 100 to 50,000 ms, the surface tension decreases more slowly from 40 mN / m to approximately 34 mN / m, asymptotically approaching the saturated value of surface tension at the CMC.

[0214] Example 3d: Identification of the wetting properties of surfactant 3 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit a surface wetting contact angle of 42.5°. On oleophobic and hydrophobic substrates such as Teflon®, the measured contact angle was 66.6°, much lower than that of water (Table 4).

[0215] [Table 4]

[0216] Example 4a: Synthesis of 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (surfactant 4) 6-(Dimethylamino)hexanoic acid (11.99 g, 75.36 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (12.68 g, 75.36 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (14.33 g, 75.36 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-(dimethylamino)hexanoate in 51% yield. 1H NMR(DMSO)δ 4.00(t,J=6.5Hz,2H),2.27(t,J=7.3Hz,2H),2.13-2.16(m,2H),2.01(s,6H),1.54-1.53(m,6H),1.27-1.18(m,20H),0.86(t,3H).

[0217] Dodecyl 6-(dimethylamino)hexanoate (1.0 g, 3.05 mmol) was dissolved in ethyl acetate (30 mL). 1,4-butanesultone (0.62 g, 4.57 mmol) was then added, and the mixture was heated to reflux for 12 hours. The reaction was cooled to room temperature, and the solvent was removed in vacuo. 1H NMR (DMSO) δ 4.00 (t, J = 6.7 Hz, 2H), 3.29-3.15 (m, 4H), 2.97 (s, 6H), 2.47 (t, J = 7.4 Hz, 2H), 2.33 (t, J = 7.4 Hz, 2H), 1.81-1.7 0(m,2H),1.66-1.55(m,6H),1.32-1.23(m,20H),0.86(t,J=6.9Hz,3H).

[0218] Example 4b: Identification of the critical micelle concentration (CMC) of surfactant 4 The critical micelle concentration (CMC) was determined. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.1 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 38 mN / m, i.e., 38 mN / m ± 3.8 mN / m. Figure 7 is a plot of these results, showing surface tension versus concentration. The resulting plot shows that the surface tension is approximately 38 mN / m at the CMC, and at concentrations of 1 mmol or greater, the surface tension is 37 mN / m or less.

[0219] Example 4c: Determining the dynamic surface tension of surfactant 4 Dynamic surface tension was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension of a newly created air-water interface over time. Figure 8 shows a plot of surface tension versus time, indicating that the compound fully saturated the surface in approximately 1 second. From the plot, the dynamic surface tension is below 40.5 mN / m for surface dwell times of 4000 ms or more.

[0220] Example 4d: Identification of the wetting properties of surfactant 4 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit a surface wetting contact angle of 46.5°. On oleophobic and hydrophobic substrates such as Teflon®, the measured contact angle was 62.7°, much lower than that of water (Table 5).

[0221] [Table 5]

[0222] Example 5a: Synthesis of 6-(dodecyloxy)-6-oxohexane-1-aminium chloride (surfactant 5) 6-Aminohexanoic acid (5.0 g, 38.11 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (6.41 g, 38.11 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (7.24 g, 38.11 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-aminohexanoate in 40% yield.

[0223] Dodecyl 6-aminohexanoate (100 mg, 0.363 mmol) was dissolved in water (10 mL), and then concentrated hydrochloric acid (13.23 mg, 0.363 mmol) was added.

[0224] Example 5b: Identification of the critical micelle concentration (CMC) of surfactant 5 The critical micelle concentration (CMC) was determined. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.75 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 23 mN / m, i.e., 23 mN / m ± 2.3 mN / m. Figure 9 is a plot of these results, showing surface tension versus concentration. The resulting plot shows that the surface tension is approximately 23 mN / m at the CMC, and at concentrations of 0.7 mmol or greater, the surface tension is 23.2 mN / m or less.

[0225] Example 5c: Determination of the dynamic surface tension of surfactant 5 Dynamic surface tension was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension over time at a newly created air-water interface. Figure 10 shows a plot of surface tension versus time, indicating that the compound fully saturated the surface in approximately 1.5 seconds. From the plot, the dynamic surface tension is below 28.5 mN / m for a surface dwell time of 3185 ms or more.

[0226] Example 5d: Identification of the wetting properties of surfactant 5 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit very low surface wetting with a contact angle of 16.6°. On oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was 39.3°, much lower than that of water (Table 6).

[0227] [Table 6]

[0228] Example 6: Formulations for ink fixers In this example, an ink fixer formulation is provided that includes a surfactant, which may be one or more of Surfactants 1-5 described herein. The components of the formulation are shown in Table 7 below.

[0229] [Table 7]

[0230] Example 7 Formulations for paints In this example, a formulation for use as a paint is provided that includes a surfactant, which may be one or more of Surfactants 1-5 described herein. The formulation is shown in Table 8 below.

[0231] [Table 8]

[0232] Example 8 Compounds for adhesives In this example, a formulation for use as an adhesive is provided that includes a surfactant, which may be one or more of Surfactants 1-5 described herein. The formulation is shown in Table 9 below.

[0233] [Table 9]

[0234] Example 9 Formulations for paint strippers In this example, a formulation for use as a paint stripper is provided that includes a surfactant, which may be one or more of Surfactants 1-5 described herein. The formulation is shown in Table 10 below.

[0235] [Table 10]

[0236] form Form 1 is a compound of formula I

[0237] [ka]

[0238] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; an optional counterion associated with said compound, when present, selected from the group consisting of chloride, bromide, iodide, and hydroxide; a fixing agent; and water.

[0239] Form 2 is a formulation of Form 1 in which the adhesion promoter is a metal carboxylate.

[0240] Form 3 is a formulation of either Form 1 or Form 2 further comprising a moisturizer.

[0241] Form 4 is a formulation of any of Forms 1-3 further comprising an acid.

[0242] Form 5 is a formulation of any of Forms 1-4 further comprising an aqueous vehicle.

[0243] Form 6 is a formulation of any of Forms 1-5 further comprising a colorant dispersed in the aqueous vehicle.

[0244] Form 7 is a surfactant having the formula:

[0245] [ka]

[0246] The formulation according to any of Forms 1 to 6 is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula:

[0247] Form 8 is a surfactant having the formula:

[0248] [ka]

[0249] Form 1, which is dodecyl 6-(dimethylamino)hexanoate N-oxide having the formula It is a blend of any of the following:

[0250] Form 9 is a surfactant having the formula:

[0251] [ka]

[0252] The formulation according to any of Forms 1-6 is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0253] Form 10 is a surfactant having the formula:

[0254] [ka]

[0255] The formulation according to any of Forms 1-6 is 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0256] Form 11 is a surfactant having the formula:

[0257] [ka]

[0258] The formulation according to any of Forms 1 to 6 is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

[0259] Form 12 is a compound of formula I

[0260] [ka]

[0261] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; optionally present counterions associated with the compound, when present, selected from the group consisting of chloride ions, bromide ions, iodide ions, and hydroxide ions; latex; and water.

[0262] Form 13 is a formulation of Form 12 further comprising one or more desiccants.

[0263] Form 14 is a formulation of either Form 12 or Form 13 further comprising one or more solvents.

[0264] Form 15 is a formulation of any of Forms 12-14 further comprising one or more pigments.

[0265] Form 16 is a surfactant having the formula:

[0266] [ka]

[0267] 16. The formulation according to any of Forms 12-15, wherein the compound is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula:

[0268] Form 17 is a surfactant having the formula:

[0269] [ka]

[0270] Form 1, which is dodecyl 6-(dimethylamino)hexanoate N-oxide having the formula It is a blend of any of 2 to 15.

[0271] Form 18 is a surfactant having the formula:

[0272] [ka]

[0273] 16. The formulation according to any of Forms 12-15, wherein the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0274] Form 19 is a surfactant having the formula:

[0275] [ka]

[0276] 16. The formulation according to any of Forms 12-15, wherein the compound is 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0277] Form 20 is a surfactant having the formula:

[0278] [ka]

[0279] 16. The formulation according to any of Forms 12-15, wherein the compound is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

[0280] Form 21 is a compound of formula I

[0281] [ka]

[0282] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; optionally present counterions associated with the compound, which, if present, are selected from the group consisting of chloride ions, bromide ions, iodide ions, and hydroxide ions; a binder; and water.

[0283] Form 22 is a formulation of Form 21 further comprising one or more desiccants.

[0284] Form 23 is a formulation of either Form 21 or Form 22 further comprising one or more solvents.

[0285] Form 24 is a formulation of any of Forms 21-23 further comprising one or more pigments.

[0286] Form 25 is a surfactant having the formula:

[0287] [ka]

[0288] 25. The formulation according to any of Forms 21-24, wherein the compound is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula:

[0289] Form 26 is where the surfactant has the formula:

[0290] [ka]

[0291] Form 2, which is dodecyl 6-(dimethylamino)hexanoate N-oxide having the formula It is a combination of any of 1 to 24.

[0292] Form 27 is where the surfactant has the formula:

[0293] [ka]

[0294] 25. The formulation according to any of Forms 21-24, wherein the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0295] Form 28 is where the surfactant has the formula:

[0296] [ka]

[0297] 25. The formulation according to any of Forms 21-24, wherein the compound is 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0298] Form 29 is a form wherein the surfactant has the formula:

[0299] [ka]

[0300] 25. The formulation according to any of Forms 21-24, wherein the compound is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

[0301] Form 30 is a compound of Formula I

[0302] [ka]

[0303] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; optionally present counterions associated with the compound, which, if present, are selected from the group consisting of chloride ions, bromide ions, iodide ions, and hydroxide ions; an adhesive; and water.

[0304] Form 31 is a formulation of Form 30 further comprising a filler.

[0305] Form 32 is where the surfactant has the formula:

[0306] [ka]

[0307] Form 30 or Form 31, which is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula:

[0308] Form 33 is where the surfactant has the formula:

[0309] [ka]

[0310] Form 3, which is dodecyl 6-(dimethylamino)hexanoate N-oxide having the formula Form 31.

[0311] Form 34 is where the surfactant has the formula:

[0312] [ka]

[0313] Form 30 or Form 31, which is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0314] Form 35 is where the surfactant has the formula:

[0315] [ka]

[0316] Form 30 or Form 31, wherein the compound is 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0317] Form 36 is where the surfactant has the formula:

[0318] [ka]

[0319] Form 30 or Form 31, which is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

[0320] Form 37 is a compound of formula I

[0321] [ka]

[0322] (In the formula, R 1 and R 2may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, and C1-C6 alkyl is and optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; optionally present counterions associated with the compound, when present, selected from the group consisting of chloride, bromide, iodide, and hydroxide; 1,2-dichloroethylene; and water.

[0323] Form 38 is the formulation of Form 37 further comprising a wax.

[0324] Form 39 is a formulation of either Form 37 or Form 38 further comprising a corrosion inhibitor.

[0325] Form 40 is a formulation of any of Forms 37-39 further comprising an organic solvent.

[0326] Form 41 is a formulation of any of Forms 37-40 further comprising a thickener.

[0327] Form 42 is a form wherein the surfactant has the formula:

[0328] [ka]

[0329] 42. The formulation according to any of Forms 37-41, wherein the compound is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula:

[0330] Form 43 is where the surfactant has the formula:

[0331] [ka]

[0332] Form 3, which is dodecyl 6-(dimethylamino)hexanoate N-oxide having the formula It is a compound of any of 7 to 41.

[0333] Form 44 is a form wherein the surfactant has the formula:

[0334] [ka]

[0335] The formulation according to any of Forms 37-41, wherein the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0336] Form 45 is where the surfactant has the formula:

[0337] [ka]

[0338] 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0339] Form 46 is where the surfactant has the formula:

[0340] [ka]

[0341] 42. The formulation according to any of Forms 37-41, wherein the compound is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

[0342] Form 47 is a compound of formula I

[0343] [ka]

[0344] (In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; optionally present counterions associated with the compound, when present, selected from the group consisting of chloride ions, bromide ions, iodide ions, and hydroxide ions; 1,2-dichloroethylene; one or more cosolvents; and water.

[0345] Form 48 is the formulation of Form 47, wherein the one or more co-solvents are selected from aromatic alcohols, aromatic ethers, and aliphatic alcohols.

[0346] Form 49 is a formulation of either Form 47 or Form 48 further comprising a wax. .

[0347] Form 50 is the formulation of any of Forms 47-49 further comprising a corrosion inhibitor.

[0348] Form 51 is a formulation of any of Forms 47-50 further comprising an organic solvent.

[0349] Form 52 is a formulation of any of Forms 47-51 further comprising a thickener.

[0350] Form 53 is where the surfactant has the formula:

[0351] [ka]

[0352] 53. The formulation according to any of Forms 47-52, wherein the compound is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula:

[0353] Form 54 is where the surfactant has the formula:

[0354] [ka]

[0355] Form 4, which is dodecyl 6-(dimethylamino)hexanoate N-oxide having the formula It is a compound of any of 7 to 52.

[0356] Form 55 is where the surfactant has the formula:

[0357] [ka]

[0358] 53. The formulation according to any of Forms 47-52, wherein the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0359] Form 56 is where the surfactant has the formula:

[0360] [ka]

[0361] 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio) butane-1-sulfonate.

[0362] Form 57 is where the surfactant has the formula:

[0363] [ka]

[0364] 53. The formulation according to any of Forms 47-52, wherein the compound is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

[0365] Form 58 is where the surfactant has the formula:

[0366] [ka]

[0367] 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula The following formula:

[0368] [ka]

[0369] Dodecyl 6-(dimethylamino)hexanoate N-oxide; The following formula:

[0370] [ka]

[0371] 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride; The following formula:

[0372] [ka]

[0373] 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate; The following formula:

[0374] [ka]

[0375] 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula: The formulation of any of Forms 1 to 6, comprising at least one of:

[0376] Form 59 is a compound of formula I

[0377] [ka]

[0378] (In the formula, R 1 and R 2may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; optionally present counterions associated with the compound, which, if present, are selected from the group consisting of chloride ions, bromide ions, iodide ions, and hydroxide ions; at least one of a latex and a binder; and water.

[0379] Form 60 is the formulation of Form 59 further comprising one or more desiccants.

[0380] Form 61 is a formulation of either Form 59 or Form 60 further comprising one or more solvents.

[0381] Form 62 is a formulation of any of Forms 59-61 further comprising one or more pigments.

[0382] Form 63 is where the surfactant has the formula:

[0383] [ka]

[0384] 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula The following formula:

[0385] [ka]

[0386] Dodecyl 6-(dimethylamino)hexanoate N-oxide; The following formula:

[0387] [ka]

[0388] 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride; The following formula:

[0389] [ka]

[0390] 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate; The following formula:

[0391] [ka]

[0392] 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula: 63. The formulation of any of forms 59-62, comprising at least one of:

[0393] Form 64 is where the surfactant has the formula:

[0394] [ka]

[0395] 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula The following formula:

[0396] [ka]

[0397] Dodecyl 6-(dimethylamino)hexanoate N-oxide; The following formula:

[0398] [ka]

[0399] 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride; The following formula:

[0400] [ka]

[0401] 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate; The following formula:

[0402] [ka]

[0403] 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula: Form 30 or Form 31, comprising at least one of:

Claims

1. The following formula: 【Chemistry 1】 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula: The following formula: 【Chemistry 2】 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula: The following formula: 【Transformation 3】 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula The following formula: 【Chemistry 4】 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula: Combinations of these, at least one surfactant selected from Fixative; and water, 1. A formulation for an ink fixer comprising:

2. The formulation of claim 1 wherein the adhesion promoter is a metal carboxylate.

3. 3. The formulation of claim 1 or claim 2, further comprising a moisturizer.

4. 4. The formulation of claim 1, further comprising an acid.

5. 5. The formulation of claim 1, further comprising an aqueous vehicle.

6. 6. The formulation of claim 1 further comprising a colorant dispersed in the aqueous vehicle.

Images