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    • 专利摘要:
    The present invention relates to dispersants that can be adsorbed onto hydrophobic particle surfaces in aqueous media. Dispersants include dendritic moieties having at least one ionizable moiety and at least one terminal hydrophobic long chain hydrocarbon moiety. The invention also relates to dispersions and inks in which the dispersant acts alone or as a codispersant.
    公开号:KR20010093836A
    申请号:KR1020017007476
    申请日:1999-04-19
    公开日:2001-10-29
    发明作者:아부엘리아만아메드에스；라오프라바카라；가담바부엔
    申请人:캐롤린 에이. 베이츠；쓰리엠 이노베이티브 프로퍼티즈 캄파니；
    IPC主号:
    专利说明:

    DENDRITIC POLYMER DISPERSANTS FOR HYDROPHOBIC PARTICLES IN WATER-BASED SYSTEMS}
    [2] When hydrophobic particles are placed in water, they tend to agglomerate. This tendency makes it difficult to obtain a dispersion of hydrophobic particles in an aqueous system. In order to reduce this aggregation tendency, a dispersant may be added to the mixture. If the dispersant has both hydrophobic and hydrophilic moieties, the hydrophobic moiety will adhere to the hydrophobic particle surface and the hydrophilic moiety will be solvated by water.
    [3] In recent years, the use of thermal inkjet printers has been greatly increased in various fields. Such printers use liquid ink that is sprayed onto the receptor, usually onto a sheet of paper or film to produce an image. By using the base ink colors (black, yellow, cyan and magenta, or black, red, green and blue, as well as white pigments (eg TiO 2 )) in various combinations and concentrations, almost all colors can Can be created as part. In addition, inkjet technology is well suited for high resolution graphic images, in particular images created using electronic printing systems. Such systems typically use computer technology to create, modify, and store images, documents, graphics, and the like.
    [4] Many inks, which have been used in inkjets and other printers in the past, mainly consist of dyes contained in organic carrier liquids. Such inks may provide satisfactory performance in certain applications, but the current trend is that such systems tend to yield images lacking the optical stability and durability required for outdoor and similar applications requiring such conditions. Do not use In addition, the use of an organic carrier liquid causes numerous environmental and material handling difficulties. For this reason, the printing industry is mainly developing water-based inks to reduce or eliminate the problems associated with organic solvent systems.
    [5] The ink may comprise a suspension of pigment particles in an aqueous carrier. However, suspended pigments may have a propensity to aggregate. Since inkjet printers use very small spray nozzles (about 40 micrometers or less in picoliter droplet volume) to provide a high resolution image, pigment agglomeration limits or clogs the print head. This effect is called "obstruction." In addition, in thermal inkjet systems, the ink is exposed to high temperatures (approximately 350 ° C.) due to the heating elements in the nozzles. Typically, the ink has a tendency to agglomerate at a higher speed at higher temperatures, and may be fixed on the heating member of the printer head to cover it. This reduces the thermal efficiency of the print head so that smaller ink droplets are formed and the image quality is degraded. This effect is called "kogation". In order to overcome the above-mentioned problems, pigment particles have been stabilized (from flocculation). In one approach, a dispersant was formed from a surfactant having a hydrophilic portion and a hydrophobic portion, and the hydrophobic segments adsorbed to the pigment surface having different hydrophobicity. Another approach used copolymers with hydrophilic and hydrophobic segments. Examples of this approach are described in US Pat. No. 4,597,794 and US Pat. No. 5,085,698.
    [6] In the aforementioned approach, the hydrophobic segment of the surfactant or polymer can be adsorbed to the pigment by hydrophobic interaction between the dispersant molecule and an organic pigment having a tendency to hydrophobic the surface. This hydrophobic interaction is usually not very strong. Because of this weak attraction, pigment particles may aggregate by dispersing the dispersant molecules at the pigment surface. During printing, this may cause clogging of the print head spray nozzle. Although the heat generated in a thermal inkjet system may enhance the stability of the ink by enhancing the adsorption of dispersant on the hydrophobic pigment surface, occlusion and coagulation remain a problem.
    [1] The present invention relates to dispersants for hydrophobic particles and particulates, including pigments in water-based inks. Also disclosed are methods of making and using dispersants.
    [32] 1 is a schematic diagram illustrating a dendritic polymer according to the present invention having four terminal long chain hydrocarbon moieties,
    [33] FIG. 2 is a schematic diagram illustrating the use of the dispersant of the present invention with a first dispersant as a co-dispersant, with both dispersants having hydrophobic segments adsorbed onto hydrophobic particles.
    [34] Detailed description of the invention
    [35] In general, the present invention consists of a dendritic structure which may have various branches. This structure includes hydrophilic or amphiphilic dendritic polymers having ionizable groups and nonpolymerized hydrocarbon hydrophobic moieties at the terminal sites. The hydrocarbon moiety can typically interact in a hydrophobic state with the hydrophobic particle surface in an aqueous dispersion system. Even if the dispersant contains a water insoluble segment, the dispersant is water soluble, ie they will form an aqueous dispersion.
    [36] Dendritic polymer
    [37] In general, examples of dendritic polymers that may be used to practice the present invention include any of the known dendritic structures, including dendrimers, regular dendrons, dendrigrafs, and hyperbranched polymers. Dendritic polymers are polymers with a dense branched structure with a plurality of terminal reactive groups. Dendritic polymers include several layers or generations with repeating units all containing one or more branch points. Dendritic polymers, including dendrimers and hyperbranched polymers, can be prepared by condensation, addition or ionic reaction of monomer units having two or more different kinds of reactive groups.
    [38] Dendritic polymers consist of a plurality of dendrons branched from a common core, and typically, the core comprises atomic groups. In general, dendritic polymers are composed of terminal surface groups, internal branch junctions having two or more branching functional groups, and bivalent linkages that covalently link adjacent branch junctions.
    [39] Dendrimers can be prepared by convergent or divergent synthesis. Divergence synthesis of dendrimers involves the process of molecular growth that occurs by adding branches in a series of geometric incremental steps in the radially outward direction of the molecule to create an ordered array of multilayered branch generations, each macromolecular At least one inner generation layer and an outer layer of the surface generation, each generation comprising a single branch junction. Generation may be the same or different chemical structures and branching functional groups. Surface branch generations may contain chemically reactive or passive functional groups. Chemically reactive surface groups can be used to further extend dendritic growth or modify dendritic molecular surfaces. Chemical passive groups can be used to physically modify the dendritic surface, for example to adjust the ratio of hydrophobic ends to hydrophilic ends. Convergent synthesis of the dendrimer involves a process of growth starting from the portion that becomes the surface of the dendrimer, and proceeds in the direction of the radial molecules to the focal point or core.
    [40] Dendrons and dendrimers may be ideal or non-ideal, ie incomplete or defective. Incompleteness is usually the result of an unterminated chemical reaction or an unavoidable competitive side reaction.
    [41] Hyperbranched polymers include a single type of monomer having a single reactive group of type (B), a plurality of (y) second type (A) reactive groups initiated by a core having multiple (x) type A reactive groups, That is, it can be prepared by the one-pot polymerization of the B-Ay type monomer, the A group can react with the B group other than the other A group, the B group can not react with the other B group. One-pot synthesis for hyperbranched polymers is simpler and less expensive than convergence and divergence synthesis for dendrimers. However, the one-pot synthesis method is difficult to control the reaction, resulting in a product with a higher polydispersity that deviates significantly from the ideal dendron structure.
    [42] Hyperbranched polymers are dendritic polymers that contain a high degree of non-ideal irregular branching arrangements compared to more nearly complete regular structural dendrimers. In particular, hyperbranched polymers contain a relatively large number of irregular branched arrangements in which all repeat units do not contain branched junctions. As a result, hyperbranched polymers may be regarded as intermediates between straight chain polymers and dendrimers. Nevertheless, due to their relatively high branch junction content per individual macromolecule they become dendritic.
    [43] Methods and features for preparing dendrimers, dendrons, dendrigrafts and hyperbranched polymers are well known. Examples of dendrimers and dendrons, and methods of their synthesis, are described in U.S. Patent Nos. 4,507,466, 4,558,120, 4,568,737, 4,587,329, 4,631,337, 4,694,064, 4,713,975, 4,737,550,1,779,550,1 And 4,857,599. Examples of hyperbranched polymers and methods for their preparation are described, for example, in US Pat. No. 5,418,301. In addition, some dendritic polymers are commercially available. For example, third and fifth generation hyperbranched polyester polyols are available from Perstop Polyols Incorporated, Toledo, Ohio.
    [44] More generally, dendritic polymers or macromolecules are characterized by a relatively high degree of branching (DB) and are the number average fraction of branching groups per molecule, ie end groups plus branching groups for the total number of end groups, branching groups and straight chain groups. It is defined as the ratio of. For dendrimers, the degree of branching is one. For straight chain polymers, the degree of branching is close to zero. Hyperbranched polymers have a degree of branching between the linear polymer and the ideal dendrimer. It is preferable that the dendritic polymer used for this invention has a branching degree of 0.1 or more, 0.4 or more is more preferable, and 0.5 or more is the most preferable.
    [45] In addition, examples of suitable dendritic polymers for use in the present invention include macromolecules, arborol, dendritic graft molecules, and the like, commonly referred to as cascade molecules. Examples of suitable dendritic polymers are also bridge-bonded dendritic polymers (ie dendritic macromolecules linked together via surface functional groups or linking molecular interface functional groups) and dendritic polymer aggregates. The dendritic polymers of the invention can be used together to form mixtures that are generational monodispersion or generational polydispersion. Dendritic polymers that are monodisperse are substantially all of the same generation, and therefore are identical in size and shape. Dendritic polymers that are polydispersed include a distribution of different generation polymers. Moreover, dendritic polymer molecules can be a mixture of different internal and external compositions or functional groups. Different generations and polymers with different degrees of derivatization can be mixed to obtain the optimum polarity needed to stabilize the dispersion.
    [46] Generally, any known dendritic polymer having an ionic, preferably anionic end group, or end group capable of reacting with another compound to provide an ionic, preferably anionic end group It is suitable for use to prepare a dendritic dispersant. Suitable examples of dendritic polymers include poly (ether), poly (ester), poly (thioether), poly (arylalkylene), poly (silane), poly (amide), poly (urethane) and other condensation polymers.
    [47] The dendritic polymer of the present invention may comprise any number of generations, preferably 3 to 5 generations.
    [48] Dispersant
    [49] Dispersants of the present invention include dendritic polymers modified by chemical reaction (s) to attach ionizable moieties to terminal nonpolymerized nonpolar hydrocarbon hydrophobic moieties. Dispersants of the present invention may be reaction products of dendritic polymers comprising reactive terminal functional groups with reactive compounds comprising hydrophobic hydrocarbon group (s) and reactive compounds comprising ionizable group (s). The hydrocarbon group may for example be aliphatic, cycloaliphatic or aromatic. These may be substituted or unsubstituted as long as the substituents are nonpolar.
    [50] In general, ionizable functional groups on the dendritic polymer are arranged in a branched chain structure that provides a high charge density compared to the charge density of straight chain polymers having the same molecular weight. Ionic groups may be anionic or cationic, but typically all should have the same type of charge. The same charge causes the dispersant / particle complex to repel each other, thus inhibiting aggregation. It is desirable for multiple solvated, ionizable moieties to provide a high charge density. As mentioned above, the prevention of particle agglomeration allows the high thermal energy generated during the injection to prevent frequent and powerful particle interactions resulting in agglomeration. Since agglomeration can shorten ink stability and shelf life, it is more desirable to reduce particle agglomeration. The mutual repulsive force of the dispersant molecules can facilitate providing dispersion stability for a long time, for example for at least one year. The ionic group is preferably anionic. Suitable examples of anionic functional groups are those derived from carboxylates, sulfonates, sulfinates, phosphonates and phosphinates, and functional groups that ionize over a wide pH range.
    [51] In addition to the dispersion stability provided by the high density of ionic charge on the dendritic dispersant, the hydrophobic hydrocarbon moiety may be bound to the hydrophobic particle surface through hydrophobic interactions to facilitate imparting stability to the colloidal dispersion of the particles. In general, the hydrophobic interactions that can be achieved by the dispersant and the hydrophobic particles depend on the number of useful hydrophobic groups on the dispersant that can diffuse to the surface of each particle through hydrophobic interactions. The hydrocarbon portion may contain about 6 to about 100 carbon atoms, preferably 8 to 20 carbon atoms.
    [52] Derivatized dendritic dispersants can be planned based on the composition of the dispersion to be stabilized, most importantly the properties of the particles or particulates to be dispersed. Certain ionizable groups and hydrophobic hydrocarbon groups can be attached to the dendritic polymer to provide dispersant molecules with optimal equilibrium of hydrophilicity and hydrophobicity in view of the desired properties of the dispersion.
    [53] Methods for optimizing dispersant efficacy include designing the dispersant to have an optimal number of ionizable and hydrophobic moieties, wherein the hydrophobic moiety may have an even more optimal length. The dispersant must not only be hydrophobic enough to maintain dispersibility and electrostatic repulsive force, but must also have enough hydrophilic moieties to interact with the hydrophobic particles. If the size and charge density of the dendritic structure allow to have a high solubility degree by the carrier liquid of the dispersion, more or larger hydrocarbon chains may be attached to the dendritic structure while maintaining solubility.
    [54] The hydrophobicity or hydrophilicity of the dispersant molecule may vary based on the relative weight percentages of the hydrophilic and hydrophobic portions comprising the dispersant. Equilibrium can be influenced by selecting the number of generations comprising the dendritic polymer portion of the dispersant and the type, number and location of functional groups on its terminal sites. These functional groups can then be reacted to provide the desired equilibrium of the ionizable and hydrophobic portions on the dendritic dispersant polymer. The number of generations substantially determines the number of reactive functional groups on the dendritic polymer. The number and composition of polymer generations can be controlled by tailoring the reaction used to form the dendritic polymer. For example, US Pat. No. 5,418,301 discloses the synthesis of hyperbranched polyols.
    [55] Dispersants of the present invention can be prepared to be high charge as evidenced by a high charge to mass ratio. For example, in the case of a third generation polyol having 32 unreacted terminal hydroxyl groups, 28 to 29 of the hydroxyl groups can react to provide anionic succinate functional groups. The remaining 3 to 4 hydroxyl groups can be reacted to give a hydrophobic long chain alkyl ester. For fifth generation polyols having 128 unreacted hydroxyl groups, 115 to 116 of the hydroxyl groups can react to provide anionic succinate groups. The remaining 12 to 13 hydroxyl groups can be reacted to give hydrophobic long chain hydrocarbon alkyl esters. The polyanionic succinate groups on the dispersant allow the dispersant / particle complex to effectively carry a high negative charge. The negative charge provides some electrostatic charge repulsion between the individually charged colloidal dispersant / particle complexes of the dispersion system.
    [56] The functional groups on the reactants that do not directly intervene in the reaction step to form the dispersant compound of the present invention can react to meet the desired physicochemical properties of the final dispersant. This provides additional margin in forming a well-woven dispersant.
    [57] Other factors considered in the fit of the dispersant structure include the number and size of all added substituents and the viscosity of the dispersant, which can affect the overall molecular weight.
    [58] When used as a codispersant, compatibility and interaction with the primary dispersant (s) are also important considerations in the design of dispersant polymers.
    [59] Ink system
    [60] Dispersants of the invention have the use as sole pigment dispersants or codispersants (primary or secondary) in inkjet inks and other printing inks. As the secondary dispersant, the dispersant of the present invention can improve the stabilizing effect of the primary dispersant.
    [61] The ink of the present invention can be formed from various pigments. In particular, the ink of the present invention may be provided with black, cyan, yellow, magenta, red, blue, green and white pigments. By varying individual color densities and superimposing monochromatic phases, almost any color can be provided on a suitable substrate. When combined with an electronic graphics imaging system, an inkjet printer can be used to reproduce virtually any image that can be created or stored electronically. Of course, the present invention is not intended to be limited to the inks of the aforementioned colors. Rather, it is possible to use inks that utilize any pigment or combination of pigments that are compatible with the electronic graphics imaging system.
    [62] For black ink, carbon black can be used as a black pigment. The choice of carbon black suitable for use in the present invention is primarily based on the surface oxidation and blackness (also called blackness) consideration of the pigment. Acidic or surface treated pigments provide suitable interaction sites for strong dispersant adsorption. Pigments with high blackness or jet blackness provide high quality print images.
    [63] For yellow inks, the use of nickel azo yellow pigments provides several advantages. First, such pigments provide highly durable inks in the external environment. Second, such pigments contain nickel ions that may form complex bonds with the novel dispersants. Finally, it is believed that such pigments provide high thermal conductivity. As a result, if particle deposition occurs on the heater member during the spraying process, the attached film will form a suitable bubble without significantly reducing the thermal efficiency of the ink.
    [64] For magenta inks, the main consideration is light fastness, because it is very desirable to produce graphic images that are adopted for outdoor applications. Quinacridone magenta pigments are known to have good light resistance and are therefore one of the preferred magenta pigments.
    [65] The above considerations (ie, light fastness, durability, etc.) also apply to cyan inks. Since the use of copper phthalocyanine as a cyan pigment results in various satisfactory properties, an ink containing such a pigment is one of the preferred embodiments.
    [66] Dispersant Selection
    [67] Typically, the pigment particles contain hydrophobic moieties that interact with the hydrophobic solid pigment surface in an aqueous environment because the pigment particles lack surface functional groups that provide a binding site for the dispersant. The dispersant of the present invention interacts with the pigment particles to provide a hydrophobic portion that is adsorbed thereto. The hydrophilic segment of the dispersant can provide effective electrostatic and steric stabilization for the colloidal pigment dispersion.
    [68] Usually, the pigment particles do not carry a single dispersant molecule but carry multiple layers of dispersant molecules. This phenomenon occurs because when the hydrocarbon portion of the dispersant is adsorbed on the particles, it promotes the adsorption of the second dispersant molecule and continues until the equilibrium thickness of the adsorbed dispersant layer is reached.
    [69] The compatibility between dispersants, pigments and other components of the ink should also be considered. Dispersants used for different colored pigments applied to the same receptor surface should be thermodynamically miscible and have the same ionic charge to prevent solidification of the ink when attached to the receptor surface.
    [70] When used as a codispersant, the dendritic dispersant must be compatible with other dispersants. Dendritic dispersants may be derivatized to be compatible with other dispersants. As all dispersants intended to be used together, the primary and secondary codispersants preferably have similar ionic charges, ie similar structural groups such as hydrocarbon-hydrocarbons and anion-anions, so that they do not neutralize each other. These primary and codispersants are preferably thermodynamically miscible and soluble in the same solvent.
    [71] It has been found that adding a dispersant as a codispersant to the pigment dispersion ink reduces the viscosity of the ink. It is sprayed through the printhead of a wide format thermal drop-on-demand inkjet printer, such as Encard Novajet III, available from Encard Inc., San Diego, California, USA. It is preferable.
    [72] ink
    [73] The ink preferably comprises water as a medium in which the pigment can be dispersed. In addition, such inks typically include additives to provide various properties. For example, additives such as polyols can be used to control the drying rate of the ink. Examples of suitable polyols include polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Alkylene glycols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, hexylene glycol and diethylene glycol; Glycerol; And lower alkyl ethers of polyols such as ethylene glycol monomethyl or monoethyl ether, diethylene glycol methyl or ethyl ether and triethylene glycol monomethyl or monoethyl ether. Diethylene glycol is a preferred polyol. Surfactants useful for wetting the ink system or reducing its surface tension can also be provided. In addition to the above, other ink additives commonly known in the art may also be used. These are water soluble organic cosolvents, wetting agents (other than the polyols listed above), biocides, antifungals, antifoams, corrosion inhibitors, viscosity modifiers, pH buffers, wetting agents, sequestering agents and the like.
    [74] Ink processing
    [75] The total pigment particle size in the ink is preferably 70 to 1000 nm, more preferably 70 to 250 nm. When used in an inkjet system, the particles are preferably less than 250 nm. In the ink processing method, for example, a grinding method can be used to obtain small particles.
    [76] Current compounding techniques for the processing of pigment dispersions utilize a number of process techniques. One such technique is the use of ultrasonic energy to achieve mixing and particle bridges. Another technique involves the use of medium mills, such as ball mills, sand mills or abrasion machines. The media mill makes it possible to obtain an acceptable pigment dispersion by disintegrating the pigment particles by high intensity microshear and cascade treatment of the pigment mixture. However, media mill processing systems often have disadvantages, including media wear product contamination. In addition, if the flow rate of the media mill rises above a certain level, the resulting grinding and dispersion becomes non-uniform and most materials are released from the system without being sufficiently processed.
    [77] As another processing method, the pigment dispersion may be forced through a series of small nozzles having a diameter of about 150 micrometers to about 1000 micrometers. Such a system must be able to withstand very high pressures at high flow rates. Three different structures can be used for such a system: a) "wedge" type with reduced orifice diameter, b) "wedge" type with orifice cavitation enhancer, and c) two dispersion streams. A "collision jet" type structure in which a stream is divided into at least two elements, each stream passing through an orifice to form jets, which jets collide with each other to recombine. Each of these systems has been shown to provide satisfactory results when processing water based coloring inks.
    [78] In the present invention, colored ink preparations comprising pigments, dispersants, co-surfactants, water, DEG and other additives, including a spiral propeller with a " grapefruit " head for greater suction through the head of the propeller The mixture was mixed under high shear conditions in a Hill mixer (Model # 4000, plus AC drive), commercially available from Hill Mixer, Inc., Paterson, NJ, which is a crash homogenizer. Shear mixing was performed at a medium speed of about 2000 rpm. After dilution to 15-25% solids concentration for any ink, the ink was finely ground by the "collision jet" method generally described in PCT application WO 96/14925. The processed concentrate was conventionally diluted to 4% by weight solids with a mixture of diethylene glycol and water having a DEG: water ratio of 20:80 to 12.5: 87.5, preferably 12.5: 87.5.
    [7] Summary of the Invention
    [8] In view of the above, there is a need for a dispersant that is strongly adsorbed to hydrophobic particles in an aqueous medium to inhibit particle aggregation. There is also a need for water based inks with increased stability. The present invention relates to such a need. One embodiment of the invention provides a dispersant for dispersing hydrophobic particles in an aqueous system comprising derivatized dendritic polymers having at least one ionizable moiety and at least one terminal non-polar non-polymerizable hydrocarbon hydrophobic moiety. do. Preferred are dendritic polymers having multiple ionizable moieties and multiple terminal hydrocarbon hydrophobic moieties.
    [9] Another embodiment of the invention relates to a stable aqueous system in which the dispersant of the invention is incorporated into an aqueous dispersion of hydrophobic particles. Collectively, the dispersant has both hydrophobic segments that can be adsorbed onto the hydrophobic surface of the particles and hydrophilic ionizable segments that exhibit mutual electron repulsion to inhibit particle aggregation. Such dispersion systems include a) hydrophobic particles and b) one or more ionizable moieties and substitution, derivatization with one or more terminal long chain (e.g., eight or more carbon atoms) hydrocarbon moieties that can be adsorbed to the hydrophobic particles or particulates. An aqueous suspension of a water-soluble dispersant comprising the dendritic polymer.
    [10] Another embodiment of the present invention includes third or fifth generation hyperbranched polyester polyols having one or more ionizable groups (preferably anions) and one or more terminal hydrocarbon groups. The hydrocarbon group is preferably a long chain aliphatic group.
    [11] The dendritic dispersants of the present invention are particularly useful for stabilizing dispersions of hydrophobic materials, including pigments, in liquid dispersions and suspensions, especially aqueous dispersions and suspensions. Ionizable groups on the dense surface of the hyperbranched polymer provide high charge density in polar solvents such as water. This high charge density significantly enhances the interparticle repulsion, which promotes stabilization of the dispersion.
    [12] Certain embodiments of the present invention relate to stable waterborne coloring inks that meet the stringent requirements of the inkjet and other printing arts. In such inks, the dispersant of the invention is incorporated into an aqueous pigment dispersion to exclude or reduce the possibility of aggregation of hydrophobic pigment particles. Generally, such inks comprise an aqueous suspension of a dispersant comprising a) pigment particles and b) at least one ionizable portion and a dendritic polymer having at least one terminal hydrophobic hydrocarbon portion that can be adsorbed onto the pigment particles. When used to disperse hydrophobic pigment particles in an ink dispersion, the dispersant will improve the colloidal stability of the ink, especially under high temperature conditions. Dispersants also reduce the viscosity of the ink.
    [13] In another embodiment, the dispersants of the invention may be used as binders to form suspensions by dispersing hydrophobic particles of silica, titania or zirconia, for example, in an aqueous medium. The suspension can then be applied to the substrate to form a film by conventional coating methods such as gravure, rolls, dies and coextrusion.
    [14] Dispersants of the invention may be used alone or in combination with other dispersants such as primary or secondary dispersants. Inks containing the dispersant of the present invention as a co-dispersant can provide printing with excellent properties in terms of color uniformity, absence of band formation, and adhesion to a printing substrate.
    [15] As used in the present invention:
    [16] "Adsorption" means that atoms, ions or molecules are attached to the surface of another material;
    [17] "Banding" means visible lines or lines of lower optical density that can occur when ink is printed on a substrate;
    [18] "Derivatize" or "derivatize" means to produce or obtain a material from a precursor material by a chemical action of adding or modifying a functional group on the precursor material;
    [19] "Dispersant / particle composite" means a dispersant molecule and particles or particulates to which the dispersant is adsorbed; Typically, the composite comprises a layer and a particle of dispersant molecules;
    [20] "Aliphatic group", "aliphatic moiety" or "long chain aliphatic group or moiety" means a straight, branched, cyclic, unsubstituted or substituted, nonpolar hydrocarbon having approximately 6 to 100, preferably 8 to 20 carbon atoms To;
    [21] "Aromatic group" or "aromatic moiety" means a nonpolar hydrocarbon having approximately 6 to 100, preferably 8 to 20 carbon atoms, consisting of one or more ring structures containing one or more [i] conjugate ring structures;
    [22] "Hydrocarbon group" or "hydrocarbon moiety" means an aliphatic or aromatic group or moiety;
    [23] "Ionizable" means a neutral molecule that contains atoms that can become ions with a pure electrical charge by losing or gaining electrons when placed in a polar medium such as, for example, water;
    [24] "Monodispersion" means particles having the same or substantially the same size or shape, or polymer molecules having substantially the same molecular weight;
    [25] "Polydispersion" means particles of various sizes or shapes, or polymer molecules having a distribution of molecular weights;
    [26] "End" means any branch or stem end end on a dendritic polymer;
    [27] "Hydrophobic moiety" or "hydrophobic segment" means a nonpolar, water insoluble hydrocarbon moiety capable of combining or bonding with the surface of hydrophobic particles; The hydrophobic segment is not polymerized but is derived from a single aliphatic or aromatic precursor such as n-octyl mercaptan;
    [28] "Hydrophobic particles" means particles that are nonpolar or particles having a nonpolar surface;
    [29] "Solvation" means a phenomenon whereby particles have a tightly held film of solvent on their surface due to the strong affinity of a solvent, such as water, for particles of dissolved or suspended material;
    [30] "Water soluble" means a material that can be homogeneously distributed in water, such as an aqueous solution or a material that forms an aqueous dispersion.
    [31] Further aspects of the present invention will become apparent upon reference to the following drawings, detailed description and claims.
    [79] The present invention is illustrated by the following examples.
    [80] Test Methods
    [81] Thermal stability
    [82] The processed ink was at 4 wt% solids concentration unless otherwise specified. Solids include pigments, surfactants and any other nonvolatile additives such as auxiliary dispersants. The ink obtained after processing and filtration is poured into glass vials (8.9 cm long by 2.54 cm diameter) and loosely covered with a metal lid so that most of the liquid (typically 12.5% by weight of diethylene glycol (DEG) in water) is retained in the ink. It was. The vial was left undisturbed for one week (unless specifically described in the examples) in an oven at 60 ° C to 65 ° C. If no solids separation occurred at 60 ° C., the ink was considered thermally stable. If visual inspection showed no flocculation of the separated solids floating on the ink, or even a small layer, the vials were transferred to a 120 ° C. oven and allowed to stand for at least two days to check for solids separation. If after 2 days the ink appeared to have no solids separation, it was considered very stable.
    [83] Print Quality on Encard Novajet III Printers
    [84] On a vinyl receptor sheet sold under the trade name Scotch from 3M Company, St. Paul, Minn., Using a thermal inkjet printer sold under the tradename Novajet III from Encard Inc., San Diego, California, USA. The ink was printed. In print preparation, the printheads were cleaned, the printer was checked for leaks, and the cartridges were filled with the ink to be tested. The print quality was visually judged for the color uniformity to the large format block (30 cm x 90 cm), the absence of band formation, and the adhesive force to the substrate.
    [85] The materials mentioned in these examples are from Aldrich Chemical Company, Wisconsin, unless otherwise noted.
    [86] Synthesis of Hyperbranched Chain Dispersant Polymer
    [87] Derivatized third and fifth generation hyperbranched polymers were synthesized using the following procedure and obtained from Perstop Polyols Incorporated, Toledo, Ohio. Commercially available perstop third and fifth generation polyols have a hydroxyl number of 500 to 470 ( Perstorp Polyols Bulletin , p. 1, June 1994). Since the hydroxyl numbers for the third and fifth generations are essentially the same, the amount of reactants used in the fifth generation is the same as for the third generation. In the following examples, third and fifth generation dispersants refer to dispersants prepared in the following manner.
    [88] 200 g of a third generation hyperbranched polyester polyol (nominal Mw 3570, and -OH functionality 32) sold under the trade name Bolton H30 from Tostopol, Toledo, Ohio, USA, and 1% by weight of p-toluenesulfonic acid Was placed in a three-necked reactor equipped with a stirrer and a nitrogen gas inlet. The reactor was heated to 140 ° C. until the polymer melted (see Malmstrom, E., Johansson, M., and Hult, A., Macromolecules , 28, 1698-1703 (1995)). To the stirred molten polymer was then added 3.2 molar equivalents of the polymer or 25% by weight stearic acid, which was 10 mole% of the free hydroxyl groups of the polymer. The mixture was kept stirring and the mixture was left to react with occasional xylene addition to promote azeotropy removal. A continuous stream of nitrogen was blown into the reactor during the reaction time to promote xylene / water azeotrope removal. After 2 hours of reaction, nitrogen was stopped and the reactor was connected to a vacuum to remove small molecules and volatiles. The resulting viscous brown liquid was cooled to room temperature to solidify on its own. Approximately 100% yield was obtained.
    [89] From the reaction 150 g of a solidified stearyl derivative of the third generation polyester polyol was mixed with an equal weight of diglyme in a three neck flask equipped with a stirrer, a condenser and a nitrogen gas inlet. The mixture was heated to 100 ° C. until the solids dissolved to form a clear solution. To the clear solution is added 63% by weight of succinic anhydride (1 equivalent of the residual free —OH groups), followed by 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) based on the total solids weight. ) (1-2 mol) was added. The mixture was heated with continuous stirring at 100 ° C. for 36 hours. The clear liquid was then coagulated in excess hexane (25 ° C.). The resulting yellow paste was washed several times with warmed (45 ° C. to 50 ° C.) hexanes to ensure unreacted anhydride. The resulting residue was air dried for 48 hours and then further dried under vacuum at 60 ° C. for 24 hours. A fifth generation HB polymer was prepared using a similar procedure except the starting stopstop polyol was Volton H50, the fifth generation polyol. The resulting solids (prepared functionalized hyperbranched polymer) were dissolved in water, neutralized by addition of a sufficient amount of ammonia and reacted with the remaining hydroxyl groups. A 30 to 40 wt% solution of solids was thus prepared. Sufficient ammonia was added to the solution to bring the pH to 9-10.
    [90] Preparation of Primary Codispersant
    [91] Suitable primary dispersants may be dispersants having an AB n structure, as disclosed in pending US patent application Ser. No. 09 / 216,161 (Agent No. 54278USA3A), which is incorporated herein by reference, wherein A contains an ionizable moiety. Is a hydrophilic (co) polymer segment, terminated with a polyfunctional chain transfer agent, B is a nonpolar non-polymeric hydrocarbon hydrophobic portion, n is greater than 1, and the B portion forms a forked segment at the CTA terminal end of the A segment.
    [92] The hydrophilic A segment comprises ionizable monomers such as acrylic acid (AA), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), itaconic acid, propenoic acid and anhydrides such as maleic anhydride and itaconic anhydride. It may include. The copolymer may optionally include nonionic monomers such as isobornyl acrylate (IBA) and isooctyl acrylate, alkyl acrylates such as ethyl, butyl and isobutyl acrylate, and styrene. In order for the dispersant to be water soluble, it is preferred that the content of the nonionic monomer in the A segment does not exceed 40% by weight. Typically, the molecular weight of the dispersant is 100,000 or less, preferably 50,000 or less, most preferably in the range of 15,000 to 35,000.
    [93] Suitable chain transfer agents include mercaptodicarboxylic acid, mercaptopolyol, halopolyol or any other moiety capable of terminating the hydrophilic segment and providing a reaction site for the hydrophobic portion of the hydrophobic segment.
    [94] The hydrophobic moiety preferably comprises an aliphatic or aromatic hydrocarbon chain, more preferably an aliphatic having 6 to 100 carbon atoms, preferably 8 to 22 carbon atoms.
    [95] Another suitable primary dispersant is a nonpolar, non-polymeric hydrocarbon hydrophobic linked to one or more terminal polymer hydrophilic segments composed of a polymer electrolyte, as disclosed in pending US patent application Ser. No. 09 / 216,657 (Rep. Dispersants comprising segments.
    [96] The hydrophilic segment is, for example, acrylic acid (AA), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), salts of sulfopropyl acrylate, maleic anhydride, itaconic anhydride, β-carboxyethylacrylic Water soluble monomer units such as late, vinylazlactone-glycolic acid adduct, sodium styrene sulfonate or a combination of these materials.
    [97] The hydrophilic segment is preferably reacted with a chain transfer agent comprising a hydrophobic hydrocarbon group. Suitable examples of monofunctional and polyfunctional hydrophobic chain transfer agents include alkyl substituted phenyl mercaptans, alkyl mercaptonaphthalenes, alkyl mercaptothiophenes, alkyl halides or combinations of these materials. Specific examples of these materials include n-octanethiol, isooctyl mercaptopropionate, n-tetradecylmercaptan, trimethylpropane, tri (3-mercaptopropionate) and pentaerythritol tetra (3-mer Captopropionate). The hydrocarbon group preferably comprises an aliphatic or aromatic hydrocarbon chain, preferably aliphatic having 6 to 100 carbon atoms, preferably 8 to 22 carbon atoms in total.
    [98] Preparation of ink
    [99] The ink preparation method illustrates the use of derivatized dendritic polymers as pigment dispersants. Inks include third and fifth generation stopstop polyols that are derivatized with stearyl hydrophobic and modified by reacting with succinic anhydride to provide a high charge density of -COO - at the branched chain ends.
    [100] In order to evaluate the efficacy of the dispersant, a generalization procedure was applied to prepare pigment inks. Pigments are typically dispersed in an aqueous solution of diethylene glycol (DEG) in the presence of a cosurfactant and a dispersant. Usually, the pigment to dispersant weight ratio was 3: 2 to 2: 1. A cosurfactant was added to control the surface tension of the ink, which aids in spraying through the printer nozzle and wets the receptor surface. In addition, the surfactant may provide for adding stability to the dispersion system. The superdispersant, which was designed to wet the pigment surface, was optionally included. Diethylene glycol served as humectant.
    [101] Crushing of ink
    [102] A high speed impact homogenizer comprising a spiral propeller with a "grapefruit" type head that provides greater suction through the head of the propeller, corresponding to each ink formulation that holds approximately 10% of the amount of water to be used. The mixture was mixed at ambient temperature and pressure under high shear conditions in a Hill mixer (Model # 4000, plus AC drive) commercially available from Hill Mixer, Inc., Paterson, NJ. The mixer is equipped with a 1 horsepower (HP) rated motor with a performance of 10,000 revolutions per minute (rpm). Propeller speeds up to 2,000 rpm (forward and reverse modes) were used to grind. The retained water was used to wash the mixture to collect stuck ink concentrate after the grinding operation. The resulting concentrate was preferably from 15 to 20% by weight in order to avoid high viscosity paste formation which is difficult to grind.
    [103] Then, after preparing the primary ink concentrate, the hyperbranched (HB) third generation or fifth generation polyol modified by derivatization with hydrophobic stearyl groups and ionic succinic anhydride was added to the ink concentrate. This solution was then further ground with a hill mixer under high shear conditions.
    [104] Inks from Examples 2 to 4 were prepared using only the grinding process described above. The ink was not filtered. The ink of Examples 1 and 5 to 7 was subjected to two steps, first, the above-mentioned grinding process step, followed by a jet collision process involving ink jet at high speed by passing the concentrate through a nozzle of several microns in diameter. By processing the ink. The jet impingement process shears aggregates of pigment crystals into smaller aggregates and can adsorb an additional amount of dispersant as a result of increased surface area. The resulting concentrate is typically further diluted to 4% by weight solids in a 12.5-15% DEG solution of water.
    [105] Example 1 (magenta ink)
    [106] Primary Dispersant
    [107] 75 g of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and 75 g of potassium sulfopropyl acrylate were dissolved in a mixture of 400 g of dimethyl formamide (DMF) and 100 g of water. After flushing the monomer mixture with nitrogen at a rate of 50 bubbles / min for 20 minutes, 1.5 g isooctyl mercaptopropionate available from Evans Chemicals, Hampshire Chemical Corporation, Lexington, Mass., USA It was dissolved in the monomer mixture with 7 g of azo thermal initiator, marketed as Bajo 52, at DuPont Chemical Company, Wilmington, Were. The vessel holding the monomer solution was mechanically stirred at 55 ° C. for 36 hours. The resulting polymer solution was added to 2 liters of acetone to precipitate the polymer. The polymer was then washed in two increments of about 300 ml of acetone. After removal of the solvent (DMF), the remaining solids are dissolved in water and 30 to 35 of the dispersant isooctyl-S-poly (2-acrylamido-2-methyl-1-propanesulfonic acid-co-potassium sulfopropyl acrylate). A wt% solution was obtained.
    [108] ink
    [109] 200 g of quinacridone fuchsia pigment sold under the trademark Sunfast Magenta Presscake (428-5024; 40.5% solids) at Sun Chemical Corporation, Cincinnati, Ohio, was suspended in 107 g of DEG and 410 g of water. 12 g of a 22.8 wt% solution of a primary dispersant (25.53 g solids) were added, followed by 12 g of an alkali polyether alcohol surfactant sold under the trade name Triton X-100 by Union Carbide & Plastics Company, Gary, Indiana, USA Was added. The resulting mixture was triturated with a hill mixer at approximately 2000 rpm for 3 hours. Thereafter, 61.6 g of a 36 wt% aqueous solution of the third-generation hyperbranched dispersion described above was added. 100 g of water were added and grinding continued for another 1 hour.
    [110] The resulting ink concentrates were finely ground for 30 to 45 minutes in a crash jet process as generally described in PCT Publication WO 96/14925. The resulting concentrate is filtered through a 0.5-1.0 μm filter, such as a Wattman Polycap 36 HD cartridge type filter available from Avo Technologies, Ann Avo, MI, and filtered approximately with a DEG: water mixture of 12.5: 87.5. Diluted further with 4 wt% solids ink.
    [111] The particle size measured by N + submicron particle analyzer commercially available from Coulter Corporation, Hyalis, FL, was 100-150 nm.
    [112] The ink was stable at 60 ° C and 120 ° C.
    [113] Ink was sprayed onto the scotch acceptor sheet through the printhead of an Encard Novajet III wide format printer to obtain a 30 cm x 90 cm magenta print, with uniform color, no banding, and adhesion to the substrate. Indicated.
    [114] Example 2 (magenta ink)
    [115] Primary Dispersant
    [116] 12.5 g AMPS and 12.5 g potassium sulfopropyl acrylate were dissolved in 100 g of a 1: 1 weight ratio solvent mixture of DMF and acetonitrile and flushed with nitrogen for 20 minutes. A mixture of 0.23 g trifunctional mercaptan and 0.024 g monofunctional mercaptan was added, followed by 1.24 g of Bajo 52 initiator. The homogeneous solution was stirred for 36 hours at 55 ° C. in a water bath to obtain a polymer. The polymer solution was added to 500 ml of acetone to precipitate the polymer. The polymer was then washed in two increments of about 100 ml of acetone. The solvent was removed and the polymer dissolved in water to give trimethylolpropane tri (3-mercaptopropionate) -terminated poly (AMPS-co-potassium sulfopropyl acrylate) / n-octyl mercaptan-terminated poly (AMPS- Approximately 30% by weight solution of the dispersant containing a mixture of co-potassium sulfopropyl acrylate) was obtained.
    [117] The dispersing agent is three small polymerization copolymers (poly (AMPS-co-potassium sulfopropyl acrylate) linked in three -SH units of two or more structures, namely (1) trimethylolpropane tri (3-mercaptopropionate) ) And (2) a mixture of n-octyl-mercaptan-terminated small polymerization copolymers. Monofunctional n-octyl-mercaptan-terminal chains are believed to provide hydrophobic segments with which hydrophobic particles can interact. Hydrophilic multifunctional copolymers are believed to provide the addition of static and steric stability to the dispersant. It is also believed that multifunctional chains dilute the concentration of the multifunctional copolymer to reduce molecular entanglement or crosslinking of the multifunctional copolymer, which can lead to insoluble network (gel) formation.
    [118] ink
    [119] 20 g of quinacridone fuchsia pigment, commercially available from Sun Chemicals under the trade name Sunfast Magenta 428-5024 (40.5% solids presscake), was suspended in a mixture of 30 g of DEG and 160 g of water. About 30 g of a 25% solution of primary dispersant was added. The resulting mixture was triturated with a hill mixer at approximately 2000 rpm for 2 hours. To this mixture was added 19.5 g of a 38% by weight aqueous solution of a fifth generation hyperbranched dispersion (equivalent to 7.4 g of solids). Grinding was continued for another 1 hour, then the mixture was diluted with approximately 4% by weight solid ink with 12.5% DEG aqueous solution.
    [120] The resulting ink appeared to be a stable, non-aggregating dispersant after thermal testing at 60 ° C. for one week.
    [121] Example 3 (magenta ink)
    [122] Primary Dispersant
    [123] 12.5 g AMPS and 12.5 g potassium sulfopropyl acrylate were dissolved in a solvent mixture of 75 g DMF and 25 g water. The resulting solution was flushed with nitrogen at a rate of 50 bubbles / min for 20 minutes. Next, 0.1858 g of pentaerythritol tetra (3-mercaptopropionate) and 0.2782 g of n-octyl mercaptan were added, followed by addition of 1.24 g of a VAZO 52 initiator. After all the solids were dissolved to make the solution homogeneous, the solution was stirred at 55 ° C. for 2 hours in a water bath to obtain a polymer. The polymer solution was added to 500 ml of acetone to precipitate the polymer. The precipitate was then washed in two increments of about 100 ml of acetone. The solvent was removed by decantation and the polymer was dissolved in water to pentaerythritol tetra (3-mercaptopropionate) -terminated poly (AMPS-co-potassium sulfopropyl acrylate) / n-octyl mercaptan-terminated Approximately 30% by weight solution of the dispersant with a mixture comprising poly (AMPS-co-potassium sulfopropyl acrylate) was obtained.
    [124] Dispersants include two or more structures, namely (1) four hydrophilic small polymer copolymers (poly (AMPS-co-potassium sulfopropyl acrylate)) linked to four sulfur atoms on the pentaerythritol chain by a chain transfer process and (2 a) a mixture of n-octyl-mercaptan-terminal chains. Monofunctional n-octyl-mercaptan-terminal chains are believed to provide hydrophobic segments with which hydrophobic particles can interact. Hydrophilic multifunctional copolymers are believed to provide the addition of static and steric stability to the dispersant. Monofunctional chains are also believed to dilute the concentration of the multifunctional copolymer to reduce molecular entanglement or crosslinking of the multifunctional copolymer, which can lead to insoluble network (gel) formation.
    [125] ink
    [126] 20 g of magenta pigment, approximately 200 g of a 12.5 wt% aqueous solution of DEG, approximately 30 g of a 25% solution of a first dispersant (7.5 g solids), 2 g of Triton X-100, 38% solution of a third generation dendritic dispersant (2.5 g solids) An ink concentrate was prepared in the same manner as in Example 2 except that it was prepared at 6.6 g.
    [127] A stable non-agglomerate dispersion was obtained.
    [128] Example 4 (Cyan Ink)
    [129] Primary Dispersant
    [130] 20 g of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and 10 g of NNDMA were dissolved in a mixture of 50 g of dimethyl formamide (DMF) and 50 g of acetonitrile. After flushing the monomer mixture with nitrogen at a rate of 50 bubbles / min for 20 minutes, 0.69 g of n-octadecyl mercaptan, commercially available from Evans Chemicals, Hampshire Chemical Corporation, Lexington, Mass., USA It was dissolved in the monomer mixture with 1.24 g of an Azo thermal initiator, available as a Bajo 52, from DuPont Chemical Company, Wilmington, USA. The vessel holding the monomer solution was mechanically stirred at 55 ° C. for 36 hours. The resulting polymer solution was added to 2 liters of acetone to precipitate the polymer. The polymer was then washed in two increments of about 300 ml of acetone. After removal of the solvent by decantation, the remaining solid was dissolved in water to obtain a 30 to 35 wt% solution of dispersant n-octadecyl-S-poly (AMPS-co-NNDMA).
    [131] ink
    [132] A mixture of 27 g of copper phthalocyanine cyan pigment and 18 g of a 25% solution of a primary dispersant (4.5 g of solid) sold under the tradename Cyan Presscake 499-1281 (36% solids) at Sun Chemical Corporation, a mixture of 27 g of DEG and 160 g of water Suspended in. 2 g of an acetylenic diol-anionic surfactant mixture (which acts as a grinding aid / surfactant) sold by Air Products, Allentown, Pennsylvania, under the tradename Surfinol CT-136 was added. The mixture was triturated with a heel mixer at approximately 2000 rpm for 2 hours. Thereafter, 6.6 g of a 38 wt% solution of a third generation dendritic dispersant solution (2.5 g of solid) was added. Grinding was continued for another 1 hour to obtain approximately 15% by weight solid ink concentrate.
    [133] The ink was thermally stable at 60 ° C.
    [134] Example 5 (yellow ink)
    [135] Primary Dispersant
    [136] A mixture of 250 g of isobornyl acrylate (IBA) and 250 g of acrylic acid (AA) was dissolved in 450 g of methyl ethyl ketone in a 32 oz glass bottle. 50 g of dimethyl-formamide was added to the mixture, followed by 7.5 g of 3-mercapto-1,2-propanediol (MPD) and under the trade name KB-1 from Sartomer Company, Exton, Pa. Photoinitiator diethoxyphenylacetophenone 0.12% by weight (based on total monomer concentration) was added. The resulting homogeneous reaction solution was flushed with nitrogen at a rate of approximately 50-100 bubbles / minute for 20 minutes. Then, while the nitrogen flush treatment was continued, the reaction solution was exposed to a 300 to 365 nm UV black light source to cause a polymerization reaction. Polymer conversion of the monomers was monitored by gravimetric analysis (vacuum drying the sample of known weight at 160 ° C. to evaporate the monomers in the sample, then weighing the dry sample to determine the polymer content). After reaching nearly 100% conversion, 40.9 g of octadecyl isocyanate (double the molar ratio of MPD) was added to the polymer solution followed by 1-2 drops of dibutyltin dilaurate (from the eye dropper). The polymer solution was stirred overnight at ambient temperature. End of reaction between IBA, AA and octadecyl isocyanate was monitored by infrared spectrometer. The reacted polymer was then isolated by neutralizing the carboxyl groups in the polymer with ammonia and then precipitating in acetone (2 L). Acetone was removed and the polymer was suspended in water to give a 25 wt% solids solution.
    [137] ink
    [138] 100 g of nickel azo complex yellow pigment, sold under the trade name Panchon Past Y-5688 at Bayer Corporation, Rock Hill, SC, USA, was suspended in 100 g of DEG and 500 g of water. 22 g of nonionic aromatic ethoxylated polymer superdispersant, sold under the trade name Solsperz 27000 by Geneca Pigments & Additives, Manchester, Blackley, UK, and trade name Alcamuls EL- 10 g of a nonionic ethoxylated fatty ester surfactant (dispersant) sold as 620 was added. Next, 211.4 g of an aqueous 31.5% by weight solids solution of the primary dispersant was added and the grinding continued for another 2 hours. Thereafter, the crushing apparatus was further washed with 155 g of water and the ink was collected (and diluted) by collecting the wash water. A 20 wt% solids ink concentrate was produced.
    [139] The entire amount of the 20 wt% ink concentrate from above was mixed with 58.4 g of a 38 wt% solids aqueous solution of the fifth generation functionalized hyperbranched dispersant polymer. The resulting mixture was triturated with a heel mixer at approximately 2000 rpm for 1 hour and then diluted with 12-15 weight percent solids ink concentrate, subjected to a crash jet process, filtered and approximately 4 weight as described in Example 1 Dilution with% solids ink.
    [140] The particle size of the pigment particles in the ink ranged from 100 to 150 nm as measured by the Coulter N + Submicron Particle Analyzer.
    [141] The ink was stable at 60 ° C and 120 ° C.
    [142] Ink was sprayed onto the scotch acceptor sheet through the printhead of an Encard Novajet III wide format printer to obtain a 30 cm x 90 cm yellow print, with uniform color, no banding, and adhesion to the substrate. Indicated.
    [143] Example 6 (Cyan Ink)
    [144] Primary Dispersant
    [145] A mixture of 300 g of IBA and 200 g of AA was dissolved in 450 g of methyl ethyl ketone in a 32 oz glass jar. 50 g of dimethyl-formamide was added to the mixture, followed by 10 g of 3-mercapto-1,2-propanediol (MPD) and 0.12% by weight of the photoinitiator diethoxyphenylacetophenone (KB-1) (based on total monomer concentration). ) Was added. The resulting homogeneous reaction solution was flushed with nitrogen at a rate of approximately 50-100 bubbles / minute for 20 minutes. Then, while the nitrogen flush treatment was continued, the reaction solution was exposed to a 300 nm UV black light source to cause a polymerization reaction. Polymer conversion of the monomers was monitored by gravimetric analysis (vacuum drying the sample of known weight at 160 ° C. to evaporate the monomers in the sample, then weighing the dry sample to determine the polymer content). After reaching nearly 100% conversion, 40.9 g of octadecyl isocyanate (double the molar ratio of MPD) was added to the polymer solution followed by 1-2 drops of dibutyltin dilaurate (from the eye dropper). The polymer solution was stirred overnight at ambient temperature. End of reaction between IBA, AA and octadecyl isocyanate was monitored by infrared spectrometer. The reacted polymer was then isolated by neutralizing the carboxyl groups in the polymer with ammonia and then precipitating in acetone (2 L). Acetone was removed and the polymer was suspended in water to give a 25 wt% solids solution.
    [146] ink
    [147] 200 g of copper phthalocyanine cyan pigment sold under the trade name 751-91A by Sun Chemical were suspended in a mixture of 160 g of DEG and 1 liter of water. 21 g of copper phthalocyanine derivative superdispersant and 21 g of grinding aid / surfactant Surfinol CT-136, sold by Genca Pigments and Additives under the trade name Solsperz 12000, were added. The resulting mixture was triturated with a hill mixer at approximately 2000 rpm for 2 hours. Then approximately 67.2 g of an aqueous 35.5 wt% solids aqueous solution of the primary dispersant was added to the mixture and grinding continued for another 2 hours.
    [148] To the ink concentrate was added approximately 50 g of an aqueous 38% by weight solids solution of third generation hyperbranched dispersion (provided 11 g of solids). The mixture was triturated with a heel mixer for 1 hour. The resulting mixture was subjected to a crash jet process, filtered and diluted with approximately 4 wt% solids ink as described in Example 1.
    [149] The particle size of the pigment particles in the ink ranged from 100 to 150 nm as measured by the Coulter N + Submicron Particle Analyzer.
    [150] The ink was thermally stable at 60 ° C and 120 ° C.
    [151] Ink was sprayed onto the scotch acceptor sheet through the printhead of an Encard Novajet III wide format printer to obtain a 30 cm x 90 cm cyan print, with uniform color, no banding, and adhesion to the substrate. Indicated.
    [152] Example 7 (magenta ink)
    [153] Primary Dispersant
    [154] A mixture of 250 g of isobornyl acrylate (IBA) and 250 g of acrylic acid (AA) was dissolved in 450 g of methyl ethyl ketone in a 32 oz glass bottle. To this mixture was added 50 g of dimethyl-formamide, followed by 10 g of 3-mercapto-1,2-propanediol (MPD) and under the trade name KB-1 from Sartomer Company, Exton, Pa. Photoinitiator diethoxyphenylacetophenone 0.12% by weight (based on total monomer concentration) was added. The resulting homogeneous reaction solution was flushed with nitrogen at a rate of approximately 50-100 bubbles / minute for 20 minutes. Then, while the nitrogen flush treatment was continued, the reaction solution was exposed to a 300 to 365 nm UV black light source to cause a polymerization reaction. Polymer conversion of the monomers was monitored by gravimetric analysis (vacuum drying the sample of known weight at 160 ° C. to evaporate the monomers in the sample, then weighing the dry sample to determine the polymer content). After reaching nearly 100% conversion, 40.9 g of octadecyl isocyanate (double the molar ratio of MPD) was added to the polymer solution followed by 1-2 drops of dibutyltin dilaurate (from the eye dropper). The polymer solution was stirred overnight at ambient temperature. End of reaction between IBA, AA and octadecyl isocyanate was monitored by infrared spectrometer. The reacted polymer was then isolated by neutralizing the carboxyl groups in the polymer with ammonia and then precipitating in acetone (2 L). Acetone was removed and the polymer was suspended in water to give a 25 wt% solids solution.
    [155] ink
    [156] Water containing DEG 120 g and 15 g of surfactant Triton X-100 dissolved 405 g of quinacridone fuchsia pigment sold by Sun Chemicals under the trade name Magenta 122 press cake (428-5024; 29.6% solids press cake). Suspended in 450 g of the mixture. Then 202 g of a 24.7 wt% solution of solid dispersion (49 g of solids) were added. The resulting mixture was triturated with a hill mixer for 2 hours. Thereafter, 90 g of a 30 wt% solid solution of solids (approximately 32 g of solids) of the third generation hyperbranched chain dispersant was added to the mixture, and further grinding was continued for 2 hours at approximately 2000 rpm. The resulting ink concentrate was triturated with a crash jet process, filtered, and diluted with approximately 4% by weight solids ink as described in Example 1.
    [157] The particle size of the pigment particles in the ink ranged from 100 to 150 nm as measured by the Coulter N + Submicron Particle Analyzer.
    [158] The ink was heat stable at 60 ° C. and after 120 days at 120 ° C.
    [159] The mixture was diluted with approximately 4% by weight solid ink with 12.5% DEG aqueous solution.
    [160] Ink was sprayed onto the scotch acceptor sheet through the printhead of an Encard Novajet III wide format printer to obtain a 30 cm x 90 cm magenta print, with uniform color, no banding, and adhesion to the substrate. Indicated.
    [161] Hydrophilic Secondary Codispersant (Water-Soluble Polymer without Nonpolar Unit)
    [162] In the two examples below, the dendritic dispersant is a primary dispersant. Secondary codispersants are completely water soluble. It does not have a hydrophobic moiety that can be adsorbed onto hydrophobic particles. Examples 8 and 9 provide the case where the nonpolar moiety is provided only by the hydrocarbon groups on the dendritic polymer and not by the codispersant.
    [163] Example 8
    [164] 237 g of copper phthalocyanine cyan pigment surface-modified with adsorbed polyethylene glycol material (54.6% solids presscake), sold under the trade name 751-91A from Sun Chemical, was suspended in 188 g of DEG and 900 g of water. To this was added 26.8 g of a 30% ammonium hydroxide solution, followed by a 33% solution of a 100% water soluble copolymer of acrylic acid / itaconic acid (solids 42.2 g) sold under the trade name Spurs 8845 by Kempal Corporation, Palatin, Ill. g was added. Also 2 g of cosurfactant Triton X-100 and 26.8 g of grinding aid / surfactant Surfinol CT-136 were added. The resulting mixture was triturated with a hill mixer at approximately 2000 rpm for 2 hours. Then approximately 67 g of an aqueous 38% by weight solids solution (provided 25.5 g of solids) of the fifth generation dendritic dispersant described in this example were added to the mixture and the grinding continued for another hour.
    [165] The resulting mixture was subjected to a crash jet process, filtered and diluted with approximately 4% by weight solids ink as described in Example 1.
    [166] The particle size of the pigment particles did not exceed 100 nm as measured by the Coulter N + submicron particle analyzer.
    [167] The ink was thermally stable at 60 ° C and 120 ° C.
    [168] Ink was sprayed onto the scotch acceptor sheet through the printhead of the Encard NovaJet III wide format printer to obtain a 30 cm x 90 cm cyan alone, as well as a combination of cyan, magenta, yellow and black, with uniform color , No band formation, and adhesion to the substrate.
    [169] Example 9
    [170] Example 8 except that 134 g of a 33% by weight solution of acrylic acid / styrene sulfonic acid 100% water soluble copolymer dispersant, sold under the trade name Spurs 8145, at Kempal Corporation, Palatin, Ill., Was used instead of Spurs 8845. Example 9 was prepared and tested in a similar manner.
    [171] The particle size of the pigment particles did not exceed 100 nm as measured by the Coulter N + submicron particle analyzer.
    [172] The ink was thermally stable at 60 ° C and 120 ° C.
    [173] Ink was sprayed onto the scotch acceptor sheet through the printhead of an Encard Novajet III wide format printer to obtain a 30 cm x 90 cm cyan alone, as well as a combination of cyan, magenta, yellow and black, with uniform color , No band formation, and adhesion to the substrate.
    [174] The present invention provides a dispersant that can be adsorbed to the surface of hydrophobic particles in an aqueous medium. The present invention also provides dispersions and inks in which the dispersant acts alone or as a codispersant.
    [175] Other embodiments of the invention are within the scope of the following claims.
    权利要求:
    Claims (21)
    [1" claim-type="Currently amended] A dispersant for dispersing hydrophobic particles in an aqueous system, comprising a derivatized dendritic polymer having at least one terminal ionizable moiety and at least one terminal nonpolymerizable hydrocarbon hydrophobic moiety.
    [2" claim-type="Currently amended] The dispersant of claim 1 wherein each hydrocarbon moiety comprises 8 to 20 carbon atoms.
    [3" claim-type="Currently amended] The dispersant of claim 1 wherein the hydrocarbon moiety is aliphatic.
    [4" claim-type="Currently amended] The dispersant of claim 1 wherein the hydrocarbon moiety comprises a stearyl group.
    [5" claim-type="Currently amended] The dispersant of claim 1 wherein the ionizable moiety is an anion.
    [6" claim-type="Currently amended] The dispersant of claim 1 wherein the dendritic polymer comprises a third generation hyperbranched chain dendritic polymer.
    [7" claim-type="Currently amended] 2. The dispersant of claim 1 wherein the dendritic polymer comprises a fifth generation hyperbranched dendritic polymer.
    [8" claim-type="Currently amended] The dispersant of claim 1 wherein the dendritic polymer comprises a third generation or fifth generation hyperbranched polyester polyol and the hydrocarbon moiety comprises a stearyl group.
    [9" claim-type="Currently amended] An aqueous suspension comprising hydrophobic particles and a dispersant according to claim 1.
    [10" claim-type="Currently amended] The aqueous suspension of claim 9 wherein the hydrophobic particles are selected from the group consisting of silica, titania and zirconia.
    [11" claim-type="Currently amended] a) pigment particles, and
    b) a dispersant comprising a derivatized dendritic polymer having at least one terminal ionizable moiety and at least one terminal nonpolymerizable hydrocarbon hydrophilic moiety
    Aqueous coloring ink containing suspension of the.
    [12" claim-type="Currently amended] 12. The aqueous coloring ink according to claim 11, further comprising a second dispersant, wherein the second dispersant is a secondary dispersant and the dendritic dispersant is a primary dispersant.
    [13" claim-type="Currently amended] 13. The aqueous coloring ink of claim 12 wherein the secondary dispersant is a 100% water soluble polymeric material.
    [14" claim-type="Currently amended] 12. The aqueous coloring ink according to claim 11, further comprising a second dispersant, wherein the second dispersant is a primary dispersant and the dendritic dispersant is a secondary dispersant.
    [15" claim-type="Currently amended] 15. The aqueous ink of claim 14, wherein the primary dispersant comprises a hydrophobic segment composed of nonpolar, nonpolymerized hydrocarbon moieties linked to one or more terminal polymer hydrophilic segments composed of a polymer electrolyte.
    [16" claim-type="Currently amended] The method of claim 14, wherein the primary dispersant comprises a polymer having an AB n structure, where A is a hydrophilic (co) polymer segment containing an ionizable moiety, terminated with a polyfunctional chain transfer agent, and B is a nonpolar specific gravity The water-based ink according to claim 1, wherein n is greater than 1, and the B portion forms a fork segment at the CTA terminal end of the A segment.
    [17" claim-type="Currently amended] The water-based ink according to claim 14, wherein the ratio of the primary dispersant to the secondary dispersant is 1.2 to 2.
    [18" claim-type="Currently amended] 12. The aqueous coloring ink according to claim 11, wherein the pigment is selected from the group consisting of black, yellow, magenta, cyan, red, blue, green and white pigments.
    [19" claim-type="Currently amended] 19. The aqueous coloring ink according to claim 18, wherein the yellow pigment comprises a nickel azo compound.
    [20" claim-type="Currently amended] 19. The aqueous coloring ink of claim 18, wherein the cyan pigment comprises a copper phthalocyanate compound.
    [21" claim-type="Currently amended] 19. The water based coloring ink according to claim 18, wherein the magenta pigment comprises a quinacridone compound.
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    同族专利:
    公开号 | 公开日
    EP1157060B1|2006-03-01|
    AU3654299A|2000-07-12|
    EP1157060A1|2001-11-28|
    DE69930111T2|2006-09-07|
    US6518370B2|2003-02-11|
    US20010020062A1|2001-09-06|
    JP2002533198A|2002-10-08|
    KR100629703B1|2006-09-29|
    US6258896B1|2001-07-10|
    WO2000037542A1|2000-06-29|
    DE69930111D1|2006-04-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-12-18|Priority to US09/216,165
    1998-12-18|Priority to US09/216,165
    1999-04-19|Application filed by 캐롤린 에이. 베이츠, 쓰리엠 이노베이티브 프로퍼티즈 캄파니
    2001-10-29|Publication of KR20010093836A
    2006-09-29|Application granted
    2006-09-29|Publication of KR100629703B1
    优先权:
    申请号 | 申请日 | 专利标题
    US09/216,165|US6258896B1|1998-12-18|1998-12-18|Dendritic polymer dispersants for hydrophobic particles in water-based systems|
    US09/216,165|1998-12-18|
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