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    • 专利摘要:
    inkjet ink, ink cartridge, inkjet recording device, and inkjet printed matter inkjet ink contains a pigment, a water-soluble solvent, and water, wherein the pigment is represented by the following formula chemistry 1 and has a cuka x-ray diffraction spectrum having a wavelength of 1541 å such that no main peak is observed at a bragg angle (2? ± 0.2°) in a range of 2? from from 28.0° to 29.0°, chemical formula 1wherein r represents a hydrogen atom, a methyl group, or a chlorine atom.
    公开号:BR102013023049B1
    申请号:R102013023049-9
    申请日:2013-09-09
    公开日:2021-09-21
    发明作者:Akihiko Matsuyama；Mitsuru Naruse；Masayasu Nonogaki；Minoru Hakiri；Keita Katoh
    申请人:Ricoh Company, Ltd.；
    IPC主号:
    专利说明:

    FUNDAMENTALS Technical Field
    The present invention relates to inkjet ink and an ink cartridge, an inkjet recording device, and inkjet printed matter using inkjet ink. TECHNICAL BACKGROUND
    Inkjet printers are widely used because of their advantages such as low noise and low running costs, and many printers capable of printing color images on plain paper are now widely available on the market.
    However, it is extremely difficult to satisfy all the necessary properties of images produced using such printers, such as good color reproducibility, abrasion resistance, durability, light resistance, drying property, plumage, color bleed, double printing, and ink discharge stability. As a result, the ink used is selected based on the particular application.
    In general, the ink used in inkjet recording is mainly composed of water, with a colorant and a water-soluble solvent such as glycerin added to prevent clogging.
    Like the colorant, colorants are widely used because of their coloring and stability. However, the light fastness and water resistance of images produced using such a dye-based ink are inferior. Water resistance can be improved to some degree by using specialized recording medium having an ink absorbing layer, but it is not at all satisfactory when it goes to plain paper.
    To compensate for such defects, ink that uses a pigment as a colorant (pigment ink) began to be used extensively.
    Although pigment ink is successful and superior to dye ink with respect to light resistance, water resistance, etc., pigment ink coloration is degraded by the coherence of light beams having different wavelengths and produced phases through multiple reflections of light beams within the pigment. For this reason, pigment ink is considered to be inferior to dye ink in general with regard to coloration.
    In an attempt to compensate for such degradation of pigment ink coloration, pigment particulates that are coated with a resin are used.
    Through this coating, the fixing ability and the gas resistance of the pigment ink are further improved and the dispersion stability of the same is also improved.
    However, currently, even such pigment ink is still not on the same level as dye ink with regard to gloss.
    In addition, JP-2003-003110-A describes recording quality with a high color density that exhibits fineness and high saturation using a pseudo-one-dimensional crystalline organic color pigment as a dye, which has an X-ray diffraction spectrum. having a diffraction line that shows the maximum intensity and its nth order ("n" is an integer of 2 or greater) diffraction lines as major peaks. SUMMARY
    The present invention provides inkjet ink containing a pigment, a water-soluble solvent, and water, wherein the pigment is represented by the following chemical formula 1 and has an X-ray diffraction spectrum of CuKα having a wavelength of 1,541 Â such that no major peaks are observed at a Bragg angle (2θ ± 0.2°) over a 2θ range from 28.0° to 29.0°,
    wherein R represents a hydrogen atom, a methyl group, or a chlorine atom. BRIEF DESCRIPTION OF THE DRAWINGS
    Various other objectives, features and inherent advantages of the present invention will be better understood as they become better understood from the detailed description when considered in connection with the accompanying drawings, in which similar reference characters designate similar corresponding parts throughout and on what:
    FIG. 1 is a perspective view illustrating an example of an ink jet recording device in which the cover of the ink cartridge installing unit is open;
    FIG. 2 is a cross-sectional view illustrating the entire configuration of the ink jet recording device;
    FIG. 3 is a schematic diagram illustrating an example of an ink cartridge ink pouch according to an embodiment of the present disclosure;
    FIG. 4 is a schematic diagram illustrating an example of the ink cartridge that accommodates the ink pouch illustrated in FIG. 3 in the case of the cartridge;
    FIG. 5 is a schematic diagram illustrating how peak intensity is obtained from the X-ray diffraction spectrum of Example 3 described below; and
    FIG. 6 is a schematic diagram illustrating how peak intensity is obtained from the X-ray diffraction spectrum of Comparative Example 2 described later. DETAILED DESCRIPTION
    The present disclosure provides:
    1. Inkjet ink that contains a pigment; a water-soluble solvent; and water, wherein the pigment is represented by the following chemical formula 1 and has an X-ray diffraction spectrum of CuKα having a wavelength of 1.541 Â such that no major peak is observed at a Bragg angle (2θ ± 0, 2°) in a 2θ range from 28.0° to 29.0°
    wherein R represents a hydrogen atom, a methyl group, or a chlorine atom.
    Ink jet ink is described in detail below and the present disclosure also includes the following 2 to 9, which are also described below.
    2. The above mentioned inkjet ink, wherein the pigment satisfies the following ratio 1: 0.000 <Y/X <0.800 Ratio 1 where in an X-ray diffraction spectrum of CuKα having a wavelength of 1.541 Â, X represents a peak intensity at a Bragg angle (2θ ± 0.2°) over a 2θ range of from 5.5° to 6.0° and Y represents a peak intensity at a Bragg angle ( 2θ ± 0.2°) in a 2θ range from 26.5° to 27.5°.
    3. The inkjet ink mentioned above, wherein the pigment has a volume mean particle diameter of from 30 nm to 150 nm.
    4. The above mentioned inkjet ink, which additionally contains a dispersing agent represented by the following chemical formula 2: A1-O-B1 Chemical formula 2 where A1 represents a linear or branched alkyl group having 8 to 12 carbon atoms, a β-naphthyl group, a styrenized phenolic group, or a distyrenized phenolic group and B1 represents a COOM1, a SO3M1, or a PO3M12, where M1 represents Na, K, tetramethyl ammonium, or ethanol amine.
    5. The inkjet ink mentioned above, which additionally contains a dispersing agent represented by the following chemical formula 3:
    where each of R1, R2, and R3 represents a hydrogen atom or a methyl group, each of R4 and R5 represents an NH2 group, a benzyl group, and a stearyl group, B1 represents a COOM1 or a SO3M1, where M1 represents Na, K, tetramethyl ammonium, or ethanol amine, and each of p, q, and r independently represent an integer from 5 to 50.
    6. The above mentioned inkjet ink, wherein the water soluble solvent is at least one of 3-ethyl-3-hydroxymethyl oxetane, isopropylidene glycerol, N,N-dimethyl-β-methoxy propionamide, and N,N-dimethyl -β-butoxy propionamide.
    7. An ink cartridge including a container; and the aforementioned inkjet ink accommodated in the container.
    8. An inkjet recording device including the above mentioned ink cartridge.
    9. An inkjet printed matter containing a recording medium; and the aforementioned inkjet ink applied to the recording medium. JP-2003-003110-A describes recording quality with a high color density that exhibits fineness and high saturation using a pseudo-one-dimensional crystalline organic color pigment as a colorant, which has an X-ray diffraction spectrum having a diffraction line which shows the maximum intensity and its nth order ("n" is an integer of 2 or greater) diffraction lines as major peaks. The pseudo-one-dimensional crystal means one-axis direction, which is different from the pigment used in the present disclosure that has no diffraction peak at n = 5 (2θ diffraction angle from 28° to 29°).
    Pigment (hereinafter also referred to as pigment A) having a quinacridone skeleton represented by chemical formula 1 exhibits excellent color and light fastness and has been widely used. However, being a pigment, it is inferior to a dye in terms of coloration. Reducing pigment particle size is one of the efforts to improve pigment coloration. Although this succeeds in improving transparency, which contributes to improved gloss and color, it is still not satisfactory. In addition, it is possible to make the coloration of a pigment closer to that of a dye by reducing the crystallinity of the pigment. However, if a pigment loses crystallinity as a dye and becomes non-crystalline, a problem of drastic degradation of characteristics such as lightfastness occurs, which is not preferable in terms of a practical use of such a pigment. In view of this, the present inventors have found that pigment A for inkjet ink (hereafter also referred to as ink) exhibits the same energy of crystallinity while maintaining the crystal structure of pigment A to prevent degradation of lightfastness. "the reduction of crystallinity while maintaining the crystal structure of pigment A" means to reduce an nth (n > 1) peak intensity relative to the first peak intensity in an X-ray diffraction spectrum. In pigment A, it is appropriate to reduce the peak intensity at a 2θ diffraction angle of from 28.0° to 29.0° or the Y peak intensity at a 2θ diffraction angle of from 26.5° to 27.5° against the X intensity of the first peak at a 2θ diffraction angle of from 5.5° to 6.0°. The color of pigment A is improved by not making any peaks at a 2θ diffraction angle from 28.0° to 29.0° or satisfying the ratio 1:0.000 <Y/X <0.800.
    One method of reducing crystallinity while maintaining the crystal structure of pigment A is, for example, to dissolve pigment A in an acid or a solvent temporarily and position the solution thus obtained in a poor solvent for recrystallization. In this method, to prevent the crystals from growing excessively, the pigment is quickly precipitated in a small reaction field. However, in conventional methods, in which a solution of a pigment is poured into a lean solvent being stirred, the size of a reaction field for precipitation is 1 cm or greater and the stirring speed is limited, which leads to crystals that grow to large sizes. As a consequence, pigment particles having a reduced crystallinity are not formed.
    However, a microreactor for precipitating dissolved pigments in minute reaction fields has been developed recently, which makes it possible to precipitate pigment particles in minute reaction fields at a high speed while suppressing crystal growth.
    A microreactor is a reaction device for conducting mixing and precipitation for chemical reaction or material production in a micro space having sides of 1 mm or less.
    Specific examples thereof include, but are not limited to, mikroSyn (manufactured by SIBATA SCIENTIFIC TECHNOLOGY LTD.) having minute tubes having a size of from 50 µm to 500 µm as a reaction field, MiChS System (manufactured by MiChS Co ., Ltd.), and ULREA (manufactured by M Technique Co., Ltd.) having an ultra-thin layer forced as a reaction field formed from a gap of from 1 µm to 30 µm between the two reaction discs.
    In general, the efficiency of the chemical reaction is determined by the collision frequency and energy applied to the system. As molecules and heat are no longer transferred in a microspace, increasing the collision frequency of molecules and rapid heat transfer is possible, which allows for rapid mixing, rapid preparation, rapid heat exchange, and rapid diffusion. Therefore, to prepare a pigment having a reduced crystallinity while maintaining the pigment crystal structure, the reaction field is preferably 100 µm or less and more preferably 30 µm or less.
    An acid or an organic solvent is used to dissolve pigment A. A strong acid such as strong sulfuric acid, hydrochloric acid, and nitric acid can be used. Strong sulfuric acid is particularly suitable in terms of solubility and dissolves pigment A in a concentration of from 3 wt% to 5 wt%.
    Specific examples of the organic solvent include, but are not limited to, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethyl formamide, and N,N-dimethyl acetamide. Dimethyl sulfoxide is suitable in particular.
    However, as pigment A has a solubility of 1% by weight or less at room temperature and normal pressure, strong sulfuric acid is preferable to dissolve pigment A. The temperature of the pigment solution can be raised to the boiling point of dissolved acid or organic solvent at maximum to increase solubility.
    Specific examples of the poor solvent include, but are not limited to, water, methanol, ethanol, isopropanol, or liquid mixture in which methanol, ethanol, and/or isopropanol is dissolved in water. If a solvent containing water is cooled to -20 °C to -50 °C, the solvent may coagulate. Considering that the reaction is fast when the temperature difference between the pigment solution and the solvent is large, it is preferable to use methanol, ethanol, or isopropanol that does not contain water as these can be cooled to lower temperatures.
    The size and crystallinity of pigment particles formed using a microreactor depend on the ratio of the pigment solution flow rate to the lean solvent flow rate. The ratio of the flow rate (ml/minute) of the pigment solution to the flow rate (ml/minute) of the lean solvent is preferably from 0.005 to 0.5 and more preferably from 0.01 to 0. 1. When the ratio is small, the reaction speed is high, which means that the pigment crystallinity can be decreased. When the ratio is, for example, 0.5 or less, pigment particles having low crystallinity can be formed. When the ratio is, for example, 0.005 or greater, it is easy to collect pigment particles from which solvents are removed.
    Pigment particles that are dispersed in the liquid mixture of an acid and a lean solvent formed by a microreactor as described above are recovered as a pigment slurry after removing the acid and solvent using a centrifuge followed by washing with deionized water several times. Pigment
    Specific examples of pigment A for use in the present disclosure include, but are not limited to, unsubstituted Pigment Violet 19 CI represented by the following chemical formula 1-1, Methyl-modified Pigment Red 122 CI represented by the following chemical formula 1-2 , and Chlorine-modified Pigment Red 202 CI represented by the following chemical formula 1-3.


    To obtain the ink satisfying the relation 1 described above, it is suitable to use pigment crystals having a smaller size than conventional pigments to decrease the pigment crystallinity. As described above, this size reduction is made possible by a microreactor to precipitate dissolved pigment in minute reaction fields.
    The pigment particle diameter dispersed in the ink of the present disclosure is preferably from 30 nm to 15 to 150 nm. The pigment particle diameter can be controlled within this range through the use of, for example, a mixing and kneading and dispersing machine using spheres such as a bead mill or a ball mill, a mixing and kneading and dispersing machine using a shear force such as a roller mill, or an ultrasonic dispersion machine. In the present disclosure, an ultrasonic dispersion machine is particularly suitable. When the pigment particle diameter is 30 nm or greater, the light fastness of the pigment is improved, thereby reducing the change in color. This is advantageous for a pigment. In addition, when the pigment particle diameter is, for example, 150 nm or less, the image brightness becomes high so that it is possible to produce images with good saturation and good brightness.
    The concentration of a pigment in the ink is preferably from 1 wt% to 15 wt%, more preferably from 2 wt% to 12 wt%, and further preferably from 3 wt% to 9 wt% by weight. When the pigment density is 1% by weight or greater, the coloring energy becomes sufficient and images having a high saturation and a high image density are obtained. In addition, when the pigment density is 15% by weight, the ink is stabilized for a long period of time. dispersing agent
    In the present disclosure, it is suitable to use a dispersant (dispersing agent) when dispersing a pigment. There is no specific limit on the dispersing agent for use in the present disclosure. Any of the dispersing agents for use in preparing the liquid pigment dispersion can be suitably selected. Specific examples thereof include, but are not limited to, nonionic surfactants such as polyoxyethylene isodecyl ether, polyoxyethylene lauryl ether, polyoxyethylene-β-naphthyl ether, polyoxyethylene styryl phenyl ether, and polyoxyethylene distyryl phenyl ether, and anionic surfactants such as salts of polyoxyethylene lauryl ether sulfate, polyoxyethylene-β-naphthyl ether sulfate salts, polyoxyethylene styryl phenyl ether phosphorate salts, lauryl ether phosphorate salts, octyl ether carbonate salts, disyryl phenyl ether sulfate salts, styryl phenyl ether phosphorate salts, and β-naphthyl ether carbonate salts.
    In the present disclosure, the dispersing agent represented by chemical formula 2 or 3 illustrated above is particularly suitable. Such a dispersing agent can maintain the viscosity and particle diameter of dispersed pigment A, thereby greatly stabilizing ink discharge when used in an inkjet printer. The dispersing agent represented by the following chemical formula 3 illustrated above is obtained through the copolymerization of acrylic monomers or methacrylic monomers.
    Specific examples of the dispersing agents represented by chemical formula 2 include, but are not limited to, the compounds represented by chemical formula 2-1 to 2-4 shown in Table 1. Table 1

    Specific examples of the dispersing agents represented by chemical formula 3 include, but are not limited to, compounds represented by chemical formula 3 1 to 3-3 shown in Table 2. Table 2
    It is also possible to use polymeric dispersing agents such as polyacrylic acids, polymethacrylic acids, copolymers of acrylic acid and acrylonitrile, copolymers of vinyl acetate and an ester of acrylic acid, copolymers of acrylic acid and an alkyl ester of acrylic acid, copolymers of styrene and acrylic acid, copolymers of styrene and methacrylic acid, copolymers of styrene, acrylic acid, and an alkyl ester of acrylic acid, copolymers of styrene, methacrylic acid, and an alkyl ester of acrylic acid, copolymers of styrene, α-methyl styrene, and an acrylic acid, copolymer of styrene, α-methyl styrene, and acrylic acid - copolymers of an alkyl ester of acrylic acid, copolymers of styrene and maleic acid, copolymers of vinyl naphthalene and maleic acid, copolymers of vinyl acetate and ethylene, vinyl acetate and ethylene vinyl acetate copolymers of aliphatic acid, vinyl acetate copolymers and an ester of maleic acid, acetate copolymers vinyl and crotonic acid copolymers, vinyl acetate and acrylic acid copolymers, acrylic acid and silicone copolymers, and modified polyurethane resins.
    These dispersing agents can be used alone or in combination. A pigment dispersing element can be prepared by dissolving the aforementioned dispersing agent in an aqueous medium, adding the pigment to the solution followed by sufficient wetting, and mixing, kneading and dispersing the resultant by high speed stirring through a homogenizer, a disperser using beads such as a bead mill and a ball mill, a mixing and kneading disperser using a shear force such as a roller mill, or an ultrasonic disperser.
    However, after such a dispersion process, coarse particles are contained in most cases, which easily clog the inkjet nozzle or the supply route. Therefore, it is suitable to remove such coarse particles (eg particle diameter: 1 µm or larger) through a filter or centrifuge.
    In the present disclosure, the mixing ratio of a dispersing agent to a pigment is preferably from 10 wt% to 100 wt% and more preferably from 20 wt% to 50 wt%.
    When the mixing ratio is 10% by weight or greater, the pigment particles can be finely dispersed. When the mixing ratio is 100% by weight or less, the dispersing agent is effectively adsorbed to the surfaces of the pigment particles, thereby improving the ink preserving ability so that bleed-free images can be printed. In addition, the particulate content dispersed in the ink is preferably from about 2% by weight to about 20% by weight and more preferably from 3% by weight to 15% by weight based on the total amount of pigment and the dispersing agent. Self-dispersing type pigment
    In the present disclosure, pigment particles having hydrophilic surfaces can be used. The surface of the pigment particle can be treated by a known method such as oxidation treatment, azo reaction, plasma treatment, etc. Through surface treatment, hydrophilic groups such as a carbonyl group, a carboxylic group, a hydroxyl group, or a sulfone group can be introduced onto the surface of a pigment particle.
    Polymer Coated Pigment Particle
    To disperse pigments in an aqueous system, a method is known in which pigments are encapsulated in polymer particulates. Specific examples of polymers that form polymer emulsions include, but are not limited to, vinyl-based polymers, polyester-based polymers, and polyurethane-based polymers. In particular, the polymers specified in JP-2000-53897-A and JP-2001-139849-A can be used suitably. Among these, vinyl-based polymers and polyester-based polymers are particularly preferable. Vinyl based polymer
    There is no specific limit for the vinyl-based polymer. For example, polymers formed from the following monomers that can be polymerized alone or in combination can be used.
    These are: vinyl-based aromatic hydrocarbons such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, p-tert-butyl styrene , p-chloro styrene, and divinyl benzene; (meth)acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, neopentyl acrylate, 3-( methyl)butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, phenyl acrylate, methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, neopentyl methacrylate, 3-(methyl)butyl methacrylate, 2-ethyl hexyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, and dodecyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; (meth)acrylamide, N-substituted maleimide, maleic anhydride, (meth)acrylonitrile, vinyl ketone, vinyl acetate, and vinylidene chloride. Polyester based polymer
    Polyester-based polymers are made from a polycarboxylic acid and a polyalcohol.
    Specific examples of polycarboxylic acids include, but are not limited to, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diphenic acid, sulfoterephthalic acid, acid 5-sulfoisophthalic acid, hexahydrophthalic anhydride, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5, [4-sulfophenoxy]isophthalic acid, and sulfoterephthalic acid; aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecane dicarboxylic acid; aromatic oxycarboxylic acids, alicyclic dicarboxylic acids; and tri or more carboxylic acids.
    Specific examples of polyols include, but are not limited to, aliphatic polyols such as ethylene glycol, propylene glycol, 1,3-propane diol, 2,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentane diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylol ethane, trimethylol propane, glycerin, pentaerythritol, 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, spiroglycol, tricyclodecane diol, tricyclodecane dimethanol, metaxylene glycol, orthoxylene glycol, 1,4-phenylene glycol, bisphenol A, and lactone-based polyester polyols ; alicyclic polyols and aromatic polyols.
    Polymer particulate
    In the present disclosure, microencapsulation to coat organic pigment particles with hydrophilic polymers or emulsification of the organic pigment particles can be suitably employed for dispersion in an aqueous medium. Any known method can be employed to conduct microencapsulation or emulsification. Such known methods are, for example, chemical manufacturing methods, physical manufacturing methods, physicochemical manufacturing methods, mechanical manufacturing methods. Specific examples thereof include, but are not limited to, acid deposition methods, phase transfer emulsification methods, interfacial polymerization methods, in-situ polymerization methods, submerged cured coated film methods, coacervation (separation of stages), solvent evaporation methods, melt distribution cooling methods, air suspension coating methods, and spray drying methods.
    Polymer particulates exhibit excellent dispersibility in water all the more through the introduction of an anionic group on the surface of the polymer. Specific examples of such anionic groups include, but are not limited to, a sulfonic group, a carboxylic group, a sulfate group, a phosphoric acid group, and a phosphine acid group, an alkali metal salt group, or a basic ammonium group. thereof, and a primary to tertiary amine group. Among these, a carboxylic alkali metal basic group, a carboxylic ammonium group, a sulfonic alkali metal basic group, and a sulfonic ammonium basic group are preferable, and in particular, a sulfonic alkali metal basic group and a sulfonic ammonium basic group are preferred in terms of stability of aqueous dispersion. The anionic group is introduced by adding a monomer having an anionic group when synthesizing a resin. Specific examples of such salts include, but are not limited to, Li, Na, K, Mg, Ca, Cu, and Fe. Li, Na, and K are particularly preferred. Water Soluble Solvent
    The ink of the present disclosure is prepared using water as a liquid medium. A water-soluble solvent is used in combination to prevent the ink from drying out, improve dispersion stability, and prevent common paper curl. Specific examples of such water-soluble solvents include, but are not limited to the following. These can be used alone or in combination.
    Polyols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, dipolypropylene glycol, tripolypropylene glycol, polypropylene glycol, 1,3-butane diol, 3-methyl-1,3-butane diol, 1, 5-pentane diol, 1,6-hexane diol, glycerin, isopropylidene glycerol, trimethylol ethane, trimethylol propane, 1,2,3-butane triol, 1,2,4-butane triol, 1,2,6-hexane triol, and petriol;
    Alkyl polyol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether.
    aryl polyol ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether;
    Nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazoline, ε-caprolactam, and y-butyllactone;
    Amides such as formamide, N-methyl formamide, N,N-dimethyl formamide, N,N-dimethyl-β-methoxy propionamide, and N,N-dimethyl-β-butoxy propionamide;
    Amines such as monoethanol amine, diethanol amine, triethanol amine, monoethyl amine, diethyl amine, and triethyl amine;
    Sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; 3-ethyl-3-hydroxymethyl oxetane, propylene carbonate, and ethylene carbonate.
    Among these water-soluble solvents, 3-ethyl-3-hydroxy-methyloxetane, isopropylidene glycerol, N,N-dimethyl-β-methoxy propionamide, and N,N-dimethyl-β-butoxy propionamide are particularly preferable.
    These are excellent for preventing plain paper curl.
    The ink of the present disclosure optionally contains sugar groups. Such sugar groups serve as water-soluble agents and/or wetting agents. Specific examples of sugar groups include, but are not limited to, monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and polysaccharides. Specific preferred examples thereof include, but are not limited to, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose. Polysaccharides represent sugar in a broad sense and contain materials that are widely present in nature, for example, α-cyclodextrin and cellulose.
    Specific examples of derivatives of these sugar groups include, but are not limited to, reducing sugars, oxidized sugars, amino acid, and thio acid for the sugar groups specified above. Sugar alcohols are particularly preferable and specific examples thereof include, but are not limited to, maltitol and sorbitol.
    The mixing ratio of pigment and water soluble agent has a great impact on the discharge stability of ink discharged from a head. If the mixing amount of water soluble agent is too small while the solid pigment portion ratio is high, the evaporation of water around an ink meniscus from the nozzles tends to be accelerated, resulting in poor discharge performance.
    The mixing ratio of the water soluble agents is preferably from 10% by weight to 70% by weight and more preferably from 20% by weight to 50% by weight based on all paint. Drying property, preserveability, and ink reliability are extremely good in this range. Penetration Agent
    By adding an ink penetration agent, the surface tension decreases so that the ink filling property of the ink to the nozzles and the discharge stability is improved. In addition, as ink droplets quickly penetrate a recording medium after ink droplets have landed on it, smudging and color bleed is reduced.
    Surfactants and solvents having a penetration property are used as the penetration agent.
    Specific examples of solvents having a penetration property include, but are not limited to, polyols having eight or more carbon atoms such as 2-ethyl-1,3-hexane diol and 2,2,4-trimethyl-1,3- pentane diol and glycol ethers.
    Surfactants are classified into anionic surfactants, nonionic surfactants, and ampholytic surfactants by hydrophilic group or fluorine-based surfactants, acetylene-based surfactants, etc. per hydrophobic group.
    Specific examples of anionic surfactants include, but are not limited to, polyoxyethylene alkyl ether acetates, dodecyl benzene sulfonates, laurates, and polyoxyethylene alkyl ether sulfates.
    Specific examples of nonionic surfactants include, but are not limited to, polyols, glycol ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, aliphatic polyoxy ethylene sorbitan esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, and acetylene glycol .
    Specific examples of fluorine-based surface active agents include, but are not limited to, perfluoroalkyl sulfonic acid salts, perfluoroalkyl carboxylic acid salts, perfluoroalkyl phosphoric acid esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaine, perfluoro oxide alkyl amine, and perfluoro alkyl ether compounds. The fluorine-containing surfactant represented by the following chemical formula 4 is more preferable.

    Specific examples of acetylene based surfactants include, but are not limited to, acetylene glycols such as 2,4,7,9-tetramethyl-5-desine-4,7-diol, 3,6-dimethyl-4-octin-3 ,6-diol, and 3,5-dimethyl-1-hexine-3-ol { (eg, SURFYNOL® 104, 82, 465, 485, and TG, all manufactured by AIR PRODUCTS and CHEMICALS, INC. (US) } Among these, SURFYNOL® 104, 465, and TG are particularly good at demonstrating good print quality.
    These surfactants can be used alone or in combination.
    The penetration agent content for the entire ink is preferably from 0.01% by weight to 5% by weight, more preferably from 0.03% by weight to 2% by weight. When the penetration agent content is too small, the scattering of dots after printing tends to be poor, that is, resulting in dots having reduced diameters so that the fill in a solid image is poor, thus degrading the density of image and color saturation. When the penetration agent content is too large, the ink tends to foam, which leads to clogging in the next path in the nozzle, resulting in the prevention of ink discharging.
    Known additives such as pH control agents, antiseptic and antifungal agents, anticorrosive agents, antioxidants, ultraviolet absorbers, oxygen absorbers, light stabilizers, and antiKogation agents can optionally be added to the ink of the present disclosure.
    pH control agent
    A pH control agent is optionally added to keep the ink in the alkaline state, thereby stabilizing the dispersion state and the ink discharge. However, when the pH is too high, the inkjet head and an ink supply unit tend to dissolve easily, which results in modification, leakage, poor ink discharge performance, etc.
    It is more desirable to add a pH control agent when a pigment is mixed and kneaded and dispersed together with a dispersing agent in water than when additives such as a water-soluble solvent and a penetration agent are added after mixing, kneading, and dispersal. This is because such a pH control agent can break the dispersion.
    It is preferable to use a pH control agent that contains at least one of an amine alcohol, an alkali metal hydroxide, ammonium hydroxide, a phosphonium hydroxide, and an alkali metal carbonate.
    Specific examples of amine alcohols include, but are not limited to, diethanol amine, triethanol amine, and 2-amino-2-ethyl-1,3-propane diol.
    Specific examples of alkali metal hydroxides include, but are not limited to, lithium hydroxide, sodium hydroxide, and potassium hydroxide.
    Specific examples of ammonium hydroxides include, but are not limited to, ammonium hydroxide and quaternary ammonium hydroxide.
    A specific example of phosphonium hydroxides is quaternary phosphonium hydroxide.
    Specific examples of metal carbonates include, but are not limited to, lithium carbonate, sodium carbonate, and potassium carbonate. Antiseptic and antifungal agent
    Specific examples of antiseptic and antifungal agents include, but are not limited to, dehydrosodium acetate, sodium sorbinate, sodium 2-pyridine thiol-1-oxide, sodium benzoate, and sodium pentachlorophenol. anti-corrosive agent
    Specific examples of anti-corrosive agents include, but are not limited to, acid bisulfite, thiosodium sulfate, ammonium thiodiglylate, diisopropyl ammonium nitrite, quaternary pentaerythritol nitrite, and dicyclohexyl ammonium nitrite. Antioxidant
    Specific examples of antioxidants include, but are not limited to, phenol-based antioxidants (including hidden phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. Ultraviolet Absorber
    Specific examples of ultraviolet absorbers include, but are not limited to, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and salt-based ultraviolet absorbers. nickel complex. Anti-kogation agent
    The ink of the present disclosure optionally contains an anti-kogation agent. Kogation is a problematic phenomenon in which ink components modified by the application of heat by a heater adhere to the heater, which occurs until a thermal head discharges ink through a foaming force of the ink by instantaneous heating by the application of a electric current to a heater.
    Specific examples of anti-kogation agents include, but are not limited to, polyphosphoric acid, polyamino carboxylic acid, aldonic acid, hydroxy carboxylic acid, polyol phosphoric acid esters, and salts thereof, acids having an amino group and salts thereof, and ammonium salts of acids having a methyl group or a methylene group and a carboxylic group. recording device
    The ink of the present disclosure can be applied to recording systems that employ an inkjet recording system such as printers, fax machines, photocopiers, multifunction machines (which serve as a printer, a fax machine, and a photocopier) for inkjet recording in particular.
    Inkjet recording devices, which were used in the Examples described later, are described below.
    The ink jet recording device 101 illustrated in FIG. 1 has a sheet feed tray 102 positioned on the ink jet recording device 101, a feed recording medium, a discharge tray 103 installed on the ink jet recording device 101 for storing the recording medium on which images are engraved (formed), and an ink cartridge installing unit 104. On the upper surface of the ink cartridge installing unit 104 an operating portion 105 including operating keys, a display, etc. is arranged. The ink cartridge installation unit 104 has a front cover 115 that can be opened and closed to detach and attach an ink cartridge 200, 111 represents the top cover of the recording device 101 and 112 represents the front surface thereof.
    Within the ink jet recording device 101, as illustrated in FIG. 2, a guide rod 131 on a support 132 serving as guide members laterally connecting side plates provided on the right and on the left holds a carriage 133 slidingly movable in the main sweep direction. A main scan motor moves cart 133 to scan.
    Cart 133 has a recording head 134 having four inkjet recording heads that discharge ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk) as multiple nozzles. Discharge drops are arranged in the direction that crosses the main scan direction with the ink droplet discharge direction down.
    As the ink jet recording heads forming the recording head 134, it is possible to use a device having a power generating device for discharging ink such as a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses the change phase changes caused by liquid film boiling using an electrical thermal conversion element such as a heating element, a shape memory alloy actuator that utilizes the metal phase change due to temperature change, and an electrostatic actuator that utilizes an electrostatic force.
    Cart 133 has a sub-tank 135 for each color to supply each color ink to the recording head 134. The ink of the present disclosure is supplied and replenished to sub-tank 135 from the ink cartridge 200 mounted in the recording unit. installation of ink cartridge 104 through an ink supply tube.
    A sheet feed unit for feeding a recording medium (sheet) 142 loaded into a sheet feeder (press plate) 141 of the sheet feed tray 103 includes a half-moon shaped roller (sheet feed roller 143 ) for separating and feeding the sheet 142 one by one from the sheet feeder 141 and a separation block 144 which is made of a material having a large friction index and arranged facing the sheet feed roller 143 while biased towards to the sheet feed roller 143.
    A transfer unit for transferring sheet 142 fed from the sheet feed unit on the underside of recording head 134 includes a transfer belt 151 for electrostatically absorbing and transferring sheet 142, a counter roller 152 for transferring sheet 142 fed from the sheet feed unit through a guide 145 while compressing sheet 142 with transfer belt 151, a transfer guide 153 to make sheet 142 follow on transfer belt 151 by changing the transfer direction of sheet 142 being substantially 90°, a front end pressure roller 155 biased towards the transfer belt 151 by a pressure member 154, and a change roller 156 for loading the surface of the transfer belt 151.
    The transfer belt 151 is an endless format belt, stretched between a transfer roller 157 and a tension roller 158 and rotatable in the belt transfer direction.
    This transfer belt 151 includes, for example, a top layer which serves as a sheet adsorption surface which is made of a resin material such as an unstretched ethylene and tetrafluoroethylene (ETFE) copolymer and has a thickness of about 4 µm and a bottom layer (moderate strength layer, earth layer) which is made of the same material as the top layer with carbon strength treatment.
    At the rear side of the transfer belt 151, a guide member 161 is arranged corresponding to the print area by the recording head 134.
    A discharge unit for discharging the sheet 142 onto which images are recorded by the recording head 134 includes a separator claw 171 for separating the sheet 142 from the transfer belt 151, a discharge roller 172, and a discharge roller. 173. An unloading tray 103 is arranged below the unloading roller 172.
    The dual print sheet feed unit 181 is detachably attached to the rear side of the inkjet recording device 101.
    The double printing sheet feeding unit 181 takes and reverses the sheet 142 which is returned by the reverse rotation of the transfer belt 151 and feeds it back between the counter roller 152 and the transfer belt 151.
    The manual sheet feed unit 182 is provided on the upper surface of the dual print sheet feed unit 181.
    In this inkjet recording device, the sheet 142 is separated and fed from the sheet feed unit one by one substantially vertically upwards, guided by the guide 145, and transferred while being compressed between the transfer belt 151 and the counter roller 152. Additionally, the front end of the sheet 142 is guided by the transfer guide 153 and pressed against the transfer belt 151 by the front end pressure roller 155 to change the transfer direction substantially by 90°.
    As transfer belt 157 is loaded by load roller 156 at this point in time, sheet 142 is electrostatically adsorbed to transfer belt 151 and transferred. By actuating the recording head 134 in accordance with the image signal while moving the carriage 133, the ink droplet is discharged onto the non-moving sheet 142 to record an image by an amount corresponding to one line and then the sheet 142 is transferred in a predetermined amount to drive the recording to the next line.
    Upon receipt of a signal indicating that recording has been completed or the trailing end of sheet 142 has reached the image recording area, the recording operation stops and sheet 142 is discharged to the discharge tray 103.
    When the amount of ink jet recording ink remaining in sub-tank 135 is detected as "approaching empty", a predetermined amount of ink is refilled to sub-tank 135 from ink cartridge 200.
    In this inkjet recording device, it is possible to disassemble the chassis of the ink cartridge 200 and replace the ink pockets of the same when the ink is used in the ink cartridge 200.
    In addition, the ink cartridge 200 stably supplies the ink even when the ink cartridge 200 is positioned up (on its side) and installed by front loading.
    Therefore, even when the upper side of the ink jet recording device 101 is blocked, for example, it is accommodated in a holder or something is positioned on the upper surface of the ink jet recording device 101, the ink cartridge 200 is easily exchanged.
    A series type (translation type) in which carriage sweep is used in this description, but this is true of an inline type inkjet recording device having a line type head. Cartridge
    The ink of the present disclosure can be accommodated in a container for an ink cartridge. The ink cartridge optionally has other members.
    There is no specific limit for the container. Any shape, any structure, any size, and any material can be selected. For example, an ink pouch formed from aluminum laminate film, a resin film, etc. can be properly used as a container.
    FIG. 3 is a schematic diagram illustrating an example of an ink cartridge container (ink bag) 241 of the present disclosure.
    FIG. 4 is a schematic diagram illustrating the ink cartridge 200 that accommodates the ink pouch 241 of FIG. 3 in a cartridge housing 244.
    As illustrated in FIG. 3, an ink pouch 241 is filled with ink from an ink inlet 242. Subsequent to the evacuation of air, the ink inlet 242 is melt closed. When in use, ink is supplied by perforating the needle provided to the ink jet recording device to an ink outlet 243 made of rubber. Ink pouch 241 is typically accommodated in the case of cartridge 244 made of plastic as illustrated in FIG. 4 and can be detachably attached to various ink jet recording devices such as the ink cartridge 200.
    Having generally described preferred embodiments of this invention, further understanding may be obtained by reference to certain specific Examples which are provided herein for the purpose of illustration only and are not intended to be limiting.
    In the descriptions of the following examples, numbers represent weight ratios in parts, unless otherwise specified. EXAMPLES
    In the following, the present disclosure is described in detail with reference to Examples and Comparative Examples but is not limited thereto. Example 1 Fabrication of Dispersion Element 1
    Using a microreactor (ULREA, manufactured by M Technique Co., Ltd.), methanol at -20 °C was drained at a flow rate of 400 ml/min into the thin layer reactor of the same sandwiched by rotating discs ; and a solution maintained at 25 °C in which 30 parts of a pigment (Hostaperm Pink E02, manufactured by Clariant Japan KK) represented by the chemical formula 1-2 were dissolved in 970 parts of strong sulfuric acid was drained into the same rotating discs at a flow rate of 10 ml/min to precipitate pigment particles. The liquid pigment dispersion thus obtained was condensed by a centrifuge and diluted with deionized water repeatedly to adjust the pH of the resultant to be about 6 to obtain a pigment paste having a pigment concentration of 30% by weight;
    Next, 6 parts of a dispersing agent represented by the chemical formula 3-1 was dissolved in 44 parts of deionized water followed by mixing with 50 parts of the pigment paste prepared as described above. The resultant thus obtained was subjected to one hour of treatment by an ultrasonic homogenizer to obtain Dispersion Element 1 having a pigment concentration of 15% by weight. <Preparation of ink>
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 1 in deionized water, the vehicle was mixed with Dispersing Element 1 and the mixture was filtered through a filter having a 1 µm opening to obtain the Ink of Example 1. Paint Recipe Dispersing Element 1: 40.0 parts Glycerin: 20.0 parts 3-ethyl-3-hydroxymethyl oxetane: 10.0 parts N,N-dimethyl-β-methoxy propionamide: 10.0 parts 2 -ethyl-1,3-hexane diol: 2.0 parts
    Surfactant represented by chemical formula 4:0.05 parts 2-amino-2-ethyl-1,3-propane diol: 0.5 parts Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0 .1 part Deionized water: 17.35 parts Example 2 Fabrication of Dispersion Element 2
    A pigment paste having a pigment concentration of 30% by weight was prepared in the same manner as in Example 1 except that the pigment was changed to CINQUASIA Violet R RT-101-D (manufactured by BASF Japan LTD.) represented by the chemical formula 1-1.
    Dispersing Element 2 having a pigment concentration of 15% by weight was manufactured in the same manner as in Example 1 except that the dispersing agent was changed to the dispersing agent represented by chemical formula 3-2. Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 2 in deionized water, the vehicle was mixed with Dispersing Element 2 followed by filtration through a filter having a 1 µm opening to obtain the Ink of Example 2 Paint Recipe Dispersing Element 2: 40.0 parts Glycerin: 20.0 parts 1,3-butane diol 5.0 parts Isopropylidene glycerol: 10 parts N,N-dimethyl-β-butoxy propionamide: 5.0 parts 2 -ethyl-1,3-hexane diol: 2.0 parts Surfactant represented by Chemical Structure 4: 0.05 parts 2-amino-2-ethyl-1,3-propane diol: 0.5 parts Antiseptic and antifungal agents (Proxel ™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water: 17.35 parts Example 3 Fabrication of Dispersion Element 3
    A pigment paste having a pigment concentration of 30% by weight was prepared in the same manner as in Example 1 except that the pigment was changed to CROMOPHTHAL JET MAGENTA DMQ (manufactured by BASF Japan LTD.) represented by chemical formula 1-2 and the following rate of amount of strong sulfuric acid pigment solution flowing into the microreactor rotating discs (ULREA) was changed to 20 ml/min.
    Dispersing Element 3 having a pigment concentration of 15% by weight was manufactured in the same manner as in Example 1 except that the dispersing agent was changed to the dispersing agent represented by Chemical Structure 3-3 and the processing time of the homogenizer ultrasonic was changed to 30 minutes. Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 3 in deionized water, the vehicle was mixed with Dispersing Element 3 followed by filtration through a filter having a 1 µm opening to obtain the Ink of Example 3 Paint Recipe Dispersing Element 3: 40.0 parts Glycerin: 20.0 parts Ethylene glycol monobutyl ether: 10.0 parts 2-pyrrolidone: 10.0 parts 2-ethyl-1,3-hexane diol: 2.0 EMALGEN LS-106 parts (polyoxyethylene polyoxypropylene alkyl ether, manufactured by KAO CORPORATION): 1.0 part 2-amino-2-ethyl-1,3-propane diol: 0.5 parts Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Example 4 Fabrication of Dispersion Element 4
    A pigment paste having a pigment concentration of 30% by weight was prepared in the same manner as in Example 1 except that the pigment was changed to CINQUASIA Violet R RT-101-D (manufactured by BASF Japan LTD.) represented by the chemical formula 1-1 and the following rate of amount of strong sulfuric acid pigment solution flowing into the microreactor spinning discs (ULREA) was changed to 20 ml/min.
    Next, 6 parts of a styrene acrylic resin (JONCRYL® 683, manufactured by BASF Japan LTD.) were dissolved in 44 parts of 0.01 normal aqueous sodium hydroxide.
    The solution was mixed with 50 parts of the pigment paste followed by treatment by an ultrasonic homogenizer for 30 minutes to obtain Dispersion Element 4 having a pigment concentration of 15% by weight. Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 4 having the following recipe in deionized water, the vehicle was mixed with Dispersing Element 4 followed by filtration through a filter having a 1 µm opening to obtain the Ink from Example 4. Ink Recipe Dispersing Element 4: 40.0 parts Glycerin: 20.0 parts 3-methyl-1,3-butane diol: 10.0 parts 1,3-butane diol: 10.0 parts 2 -ethyl-1,3-hexane diol: 2.0 : parts
    Surfactant represented by chemical formula 4: 0.05 parts 2-amino-2-ethyl-1,3-propane diol: 0.5 part Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0 .1 part Deionized water: 17.35 parts Example 5
    Fabrication of Dispersion Element 5
    A pigment slurry having a pigment concentration of 30% by weight was prepared in the same manner as in Example 1 except that the following rate of amount of strong sulfuric acid pigment solution flowing into the microreactor rotating disks (ULREA) was changed to 5 ml/min.
    Dispersing Element 5 having a pigment concentration of 15% by weight was manufactured in the same manner as in Example 1 except that the dispersing agent was changed to the dispersing agent represented by chemical formula 2-1. Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 5 having the following recipe in deionized water, the vehicle was mixed with Dispersing Element 5 followed by filtration through a filter having a 1 µm opening to obtain the Ink from Example 5. Ink Recipe Dispersing Element 5: 40.0 parts Glycerin: 20.0 parts 1,3-butane diol: 10.0 parts Isopropylidene glycerol: 5.0 parts N,N-dimethyl-β-butoxy propionamide: 5.0 parts 2-ethyl-1,3-hexane diol: 2.0 parts Surfactant represented by chemical formula 4: 0.05 parts 2-amino-2-ethyl-1,3-propane diol: 0.5 part Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water: 17.35 parts Example 6 Fabrication of Dispersion Element 6
    A pigment paste having a pigment concentration of 30% by weight was prepared in the same manner as in Example 1 except that the pigment was changed to Red No. 81 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. represented by chemical formula 1-2 and the following rate of amount of strong sulfuric acid pigment solution flowing into microreactor rotating discs (ULREA) was changed to 30 ml/min.
    Dispersing Element 6 having a pigment concentration of 15% by weight was manufactured in the same manner as in Example 1 except that the dispersing agent was changed to the dispersing agent represented by chemical formula 2-2.
    Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 6 in deionized water, the vehicle was mixed with Dispersing Element 6 followed by filtration through a filter having an opening of 1 µm to obtain the Ink of Example 6 Ink recipe Dispersion Element 6: 40.0 parts Glycerin: 20.0 parts 3-methyl-1,3-butane diol: 5.0 parts 3-ethyl-3-hydroxymethyl oxetane: 10.0 parts N,N -dimethyl-β-butoxy propionamide:5.0 parts 2-ethyl-1,3-hexane diol: 2.0 parts EMALGEN LS-106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by KAO CORPORATION):1.0 part 2-amino -2-ethyl-1,3-propane diol: 0.5 part Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water: 16.4 parts Example 7 Fabrication of Dispersion Element 7
    Using the same pigment paste as in Example 1, Dispersing Element 7 having a pigment concentration of 15% by weight was manufactured in the same manner as in Example 1 except that the dispersing agent was changed to the dispersing agent represented by Chemical Structure 2-3 and the treatment time of the ultrasonic homogenizer was changed to 30 minutes. Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 7 having the following recipe in deionized water, the vehicle was mixed with Dispersing Element 7 followed by filtration through a filter having a 1 µm opening to obtain the Ink from Example 7. Ink Recipe Dispersing Element 7: 40.0 parts Glycerin: 20 parts 1,3-butane diol: 20.0 parts 2-ethyl-1,3-hexane diol: 2.0 parts Surfactant represented by chemical formula 4: 0.05 parts 2-amino-2-ethyl-1,3-propane diol: 0.5 parts Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water: 17.35 parts Example 8 Fabrication of Dispersion Element 8
    A pigment paste having a pigment concentration of 30% by weight was prepared in the same manner as in Example 1 except that the pigment was changed to Cinquasia Magenta RT-243-D (manufactured by BASF Japan LTD.) represented by chemical formula 1 -3.
    Dispersing Element 8 having a pigment concentration of 15% by weight was manufactured in the same manner as in Example 1 except that the dispersing agent was changed to the dispersing agent represented by chemical formula 2-4. Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 8 having the following recipe in deionized water, the vehicle was mixed with Dispersing Element 8 followed by filtration through a filter having a 1 µm opening to obtain the Ink from Example 8. Ink Recipe Dispersing Element 8: 40.0 parts Glycerin: 20.0 parts Ethylene glycol monobutyl ether: 10.0 parts Isopropylidene glycerol: 5.0 parts N,N-dimethyl-β-butoxy propionamide: 5.0 parts 2-ethyl-1,3-hexane diol: 2.0 parts EMALGEN LS-106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by KAO CORPORATION): 1.0 part 2-amino-2-ethyl-1,3 -propane diol 0.5 part Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water: 16.4 parts Example 9 Fabrication of Dispersion Element 9
    A pigment paste having a pigment concentration of 30% by weight was prepared in the same manner as in Example 1 except that the pigment was changed to Red No. 81 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. represented by chemical formula 1-2 .
    Dispersing Element 9 having a pigment concentration of 15% by weight was manufactured in the same manner as in Example 1 except that the dispersing agent was changed to the dispersing agent represented by chemical formula 5-1.
    in chemical formula 5-1 Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 9 having the following recipe in deionized water, the vehicle was mixed with Dispersing Element 9 followed by filtration through a filter having a 1 µm opening to obtain the Ink from Example 9. Ink Recipe Dispersing Element 9: 40.0 parts Glycerin: 20 parts Ethylene glycol monobutyl ether: 10.0 parts 2-pyrrolidone: 2-ethyl-1,3-hexane diol: 2.0 parts EMALGEN LS—106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by KAO CORPORATION): 1.0 part 2-amino-2-ethyl-1,3-propane diol: 0.5 part Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water: 16.4 parts Example 10 Fabrication of Dispersion Element 10
    A pigment paste having a pigment concentration of 30% by weight was prepared in the same manner as in Example 1 except that the pigment was changed to Cinquasia Magenta RT-243-D (manufactured by BASF Japan LTD.) represented by chemical formula 1 -3 and the following rate of amount of strong sulfuric acid pigment solution flowing into the microreactor spinning discs (ULREA) was changed to 5 ml/min.
    Dispersing Element 10 having a pigment concentration of 15% by weight was manufactured in the same manner as in Example 1 except that the dispersing agent was changed to the dispersing agent represented by chemical formula 5-2.
    Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 10 in deionized water, the vehicle was mixed with Dispersing Element 10 followed by filtration through a filter having a 1 µm opening to obtain the paint of Example 10 Paint Recipe Dispersing Element 10: 40.0 parts Glycerin: 20.0 parts 2-pyrrolidone: 5.0 parts 1,3-butane diol: 10.0 parts 3-methyl-1,3-butane diol 5, 0 parts 2-ethyl-1,3-hexane diol: 2.0 parts Surfactant represented by chemical formula 4: 0.05 parts 2-amino-2-ethyl-1,3-propane diol: 0.5 part Antiseptic and antifungal (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water: 17.35 parts Example 11 Fabrication of Dispersing Element 11 150 parts of the pigment paste obtained in Example 5 was mixed in 400 ml of sulfolane and the mixture was placed in the Ultra Aspec UAM 015 type Mill (manufactured by KOTOBUKI INDUSTRIES CO., LTD.) for p dispersion. or an hour. Next, 15 parts of amide sulfate were added followed by stirring at 140 °C to 150 °C for 10 hours. The slurry thus obtained was placed in 1000 ml of deionized water to obtain a pigment slurry having a surface sulfonized by a centrifuge. This pigment slurry was re-dispersed in 2000 ml of deionized water followed by pH adjustment by lithium hydroxide. The resultant was subjected to desalting concentration by an ultrafiltration membrane to obtain Dispersion Element 11 having a pigment concentration of 15% by weight. Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersing Element 11 in deionized water, the vehicle was mixed with Dispersing Element 11 followed by filtration through a filter having a 1 µm opening to obtain the Ink of Example 11 Ink Recipe Dispersing Element 11: 40.0 parts Glycerin: 20.0 parts Ethylene glycol monobutyl ether: 5.0 parts 2-pyrrolidone: 5.0 parts 3-methyl-1,3-butane diol: 10.0 parts 2-ethyl-1,3-hexane diol: 2.0 parts EMALGEN LS-106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by KAO CORPORATION): 1.0 part 2-amino-2-ethyl-1,3-propane diol 0.5 part Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water 16.4 parts Example 12 Synthesis of Polymer b
    After sufficient replacement with nitrogen gas in a flask equipped with a mechanical stirrer, a thermometer, a nitrogen gas introduction tube, a reflux tube, and a dip funnel, the following Material 1 was placed in it and heated to 65° Ç.
    Next, the liquid mixture of the following Material 2 was immersed in the heated flask for 2.5 hours. Subsequent to immersion, the liquid mixture of 0.8 parts of azobisdimethyl valeronitrile and 18.0 parts of methyl ethyl ketone was immersed in the flask in 0.5 hours. After one hour aging at 65°C, 0.8 parts of azobisdimethyl valeronitrile was immersed followed by aging for another hour. After completing the reaction, 364.0 parts of methyl ethyl ketone were added to a flask to obtain 800 parts of polymer b (vinyl resin) solution having a concentration of 50%. Material 1 for Polymer b Styrene: 11.2 parts Acrylic Acid: 2.8 parts Lauryl Methacrylate: 12.0 parts Polyethylene Glycol Methacrylate: 4.0 parts Styrene Macromer (AS-6, manufactured by TOAGOSEI CO., LTD. ): 4.0 parts Mercapto ethanol: 0.4 part Material 2 for Polymer b Styrene: 100.8 parts Acrylic acid 25.2 parts Lauryl methacrylate: 108.0 parts Polyethylene glycol methacrylate: 36.0 parts Hydroxy ethyl methacrylate: 60.0 parts Styrene macromer (AS-6, manufactured by TOAGOSEI CO., LTD.): 36.0 parts Mercapto ethanol: 3.6 parts Azobis dimethyl valero nitrile: 2.4 parts Methylethylketone: 18 parts
    Fabrication of Dispersion Element 12 Dispersion Element 12 is manufactured from the following materials. That is, the pigment paste prepared in Example 8, polymer solution b, 1 mol/l potassium hydroxide, and methyl ethyl ketone were mixed and stirred sufficiently followed by mixing and kneading with a three-roll mill (NR- 84A, manufactured by Noritake Co., Ltd.) 20 times. The slurry thus obtained was placed in 200 parts of deionized water and after sufficient stirring, methyl ethyl ketone was distilled by an evaporator to obtain Dispersion Element 12 having a pigment concentration of 15% by weight. Recipe for Dispersing Element Pigment paste prepared in Example 8:50.0 parts Polymer solution b: 12.0 parts Aqueous potassium hydroxide solution 1 mol/l: 14.0 parts Methylethylketone: 20.0 parts Deionized water : Ink Preparation
    Manufacture of a vehicle by dissolving the following materials other than Dispersion Element 12 in deionized water, the vehicle was mixed with Dispersing Element 12 followed by filtration through a filter having a 1 µm opening to obtain the paint of Example 12 . Paint Recipe Dispersing Element 12: 40.0 parts Glycerin: 20.0 parts 1,3-butane diol: 10.0 parts 3-methyl-1,3-butane diol: 10.0 parts 2-ethyl-1, 3-hexane diol: 2.0 : parts EMALGEN LS-106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by KAO CORPORATION): 1.0 part 2-amino-2-ethyl-1,3-propane diol: 0.5 part Agents antiseptic and antifungal (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.): 0.1 part Deionized water: 16.4 parts Example 13 Fabrication of Dispersion Element 13
    Liquid Dispersion 13 having a pigment concentration of 15% by weight was prepared in the same manner as in Example 6 except that the following rate of amount of strong sulfuric acid pigment solution flowing into the microreactor rotating disks (ULREA) was changed to 50 ml/min. Ink Preparation
    The Ink of Example 13 was prepared in the same manner as in Example 6 except that Dispersing Element 6 was changed to Dispersing Element 13. Comparative Example 1
    Fabrication of Dispersing Element 15 6 parts of the dispersing agent represented by chemical formula 3-2 for the use in Example 2 were dissolved in 79 parts of deionized water and the solution was mixed with 15 parts of CINQUASIA Violet R RT-101-D (Manufactured by BASF Japan LTD.). The mixture was placed in the Ultra Aspec UAM 015 type Mill (manufactured by KOTOBUKI INDUSTRIES CO., LTD.) for dispersion for one hour followed by filtration through a filter having an opening of 1 µm to obtain the Dispersing Element 15 having a pigment concentration of 15% by weight. Ink Preparation
    Ink from Comparative Example 1 was prepared in the same manner as in Example 2 except that Dispersing Element 2 of Example 2 was changed to Dispersing Element 15. Comparative Example 2
    Fabrication of Dispersing Element 16 6 parts of the dispersing agent represented by chemical formula 5-1 for the use in Example 9 were dissolved in 79 parts of deionized water and the solution was mixed with 15 parts of pigment Red No. 81 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. for use in Example 9. The mixture was dispersed by Ultra Aspec UAM 015 type mill (manufactured by KOTOBUKI INDUSTRIES CO., LTD.) for thirty minutes to obtain the Dispersing Element 16 having a pigment concentration of 15% by weight. Ink Preparation
    The Ink of Comparative Example 2 was prepared in the same manner as in Example 9 except that Dispersing Element 9 of Example 9 was changed to Dispersing Element 16. Comparative Example 3
    Fabrication of Dispersing Element 176 parts of the dispersing agent represented by chemical formula 2-4 for the use in Example 8 were dissolved in 79 parts of deionized water and the solution was mixed with 15 parts of Cinquasia Magenta RT-243-D ( manufactured by BASF Japan LTD.). The mixture was placed in the
    Ultra Aspec UAM 015 type mill (manufactured by KOTOBUKI INDUSTRIES CO., LTD.) for dispersion for one hour to obtain Dispersing Element 17 having a pigment concentration of 15% by weight. Ink Preparation
    The Ink of Comparative Example 3 was prepared in the same manner as in Example 8 except that Dispersing Element 8 of Example 8 was changed to Dispersing Element 17.
    The dispersion elements and ink prepared in the Examples and Comparative Examples were measured and evaluated as follows: (1) X-ray diffraction spectrum
    To measure X-ray diffraction spectra of pigments for use in Examples and Comparative Examples, X'Pert Pro (manufactured by PANalytical Co.) was used. Using a Cu compartment tube (Kα characteristic X-ray: wavelength 1541 Â) as an X-ray generator, the measurement was conducted under the conditions of a 2θ measuring range from 3.0° to 35 .0°, a sampling width of 0.02°, and a cumulative time of 1.0 second. With respect to the pigments of the examples, pigment powder prepared by removing moisture from the pigment paste before dispersion with a reduced pressure while heating the pastes to 50°C was used for the measurement. With respect to the pigments of Comparative Examples, the pigment powder before dispersion was used for the measurement. FIG. 5 is an X-ray diffraction spectrum from Example 3 and FIG. 6 is an X-ray diffraction spectrum from Comparative Example 2.
    The peak in the present disclosure is determined as a peak having a maximum width of 0.5° or greater on a smoothed data plot and a single local maximum value. To be specific, after smoothing processing to remove noise from the X-ray diffraction intensity data, a smoothing filter by a moving average method was used to average five data sets including the target data from calculation, two sets of data above, and two sets of data below to replace the target calculation data if the data was digital. Smoothing processing was conducted by plotting a smooth curve that passed through the noise averaging if the data were analogous. Next, a straight baseline having a length of 0.5° or greater in the X-axis direction was drawn such that only one peak was present in the smoothed data in the sandwiched range by both ends of the baseline. If a baseline satisfying this condition was drawn and a peak was present within a 2θ range of from 28.0° to 29.0°, the peak was determined to be present. Unless otherwise stated, it was determined that there was no peak.
    In addition, the results from the X-ray diffraction spectra obtained on whether there is a peak in a 2θ range of from 28.0° to 29.0° and the baseline width (°) are shown in Table 4. As illustrated in FIG. 5, the X and Y intensity of the peak attributable to the crystal were obtained based on the halo portion attributable to the non-crystalline portion. The results for X, Y, and Y/X are shown in Table 4. (2) Volumetric Average Particle Diameter
    The volumetric average particle diameter of the ink was measured by UPA-EX 150. manufactured by Nikkiso Co., Ltd. The ink was diluted with deionized water to 600 times and placed in a measuring cell. The measurement was conducted at 25°C for 60 seconds using the 1.40 g/ml density of the pigment represented by chemical formula 1, which was required as a measurement parameter.
    The measurement results are shown in Table 5. (3) Color Saturation
    Inkjet ink was supplied to an IPSiO GX e5500 inkjet printer (manufactured by Ricoh Co., Ltd.) having a structure illustrated in FIGS. 1 and 2 and a solid image was printed with a pass.
    The solid image was printed on the following recording medium A, B, and C. After the images were dried, its luminescence was measured by a reflection-type color spectrodensimeter (X-Rite 938, manufactured by X-Rite Incorporate ).
    The C* saturation was calculated by the relationship: C* = {(a*)2 + (b*)2}1/2 from the values thus obtained a* and b*. The ratio k of the C* saturation value to the C*0 saturation value of the standard color (Color of Japan ver. 2) was calculated by the relationship: k = C* / C*0 and evaluated according to the following criteria of evaluation. The results are shown in Table 5.
    A and B of the evaluation criteria are preferable. Evaluation sheet
    Engraving Sheet A: BP-PAPER GF-500 (A4, manufactured by Canon Inc.) Engraving Sheet B: MIRROR COAT Platinum (manufactured by OJI PAPER CO., LTD.) Engraving Sheet C: Crispia (manufactured by Seiko Criteria of evaluation A: k > 1.1 B: 1.1 > k > 1.0 C: 1.0 > k > 0.9 D: 0.9 > k (4) Light Resistance
    Ink was supplied to an IPSiO GX e5500 inkjet printer (manufactured by Ricoh Co., Ltd.) having a structure illustrated in FIGS. 1 and 2 and a solid image was printed with a pass. Using the following Recording Sheet C, subsequent to printing and drying, the image was irradiated by a xenon feed meter at a black panel temperature of 63°C for 24 hours followed by measuring the change in image density before and after irradiation by a reflection-type color spectrodensimeter (manufactured by X-Rite Incorporated) to obtain a color deterioration ratio t (%) according to the following relationship. A and B are preferred. t (%) = [1 - (image density after irradiation) / (image density before irradiation)] x 100 Evaluation Sheet Etching Sheet C: Crispia (manufactured by Seiko Evaluation criteria A: t <5 % B: 5% < t < 10% C: 10% < t < 20% D: 20% < t (5) Ripple measurement
    Inkjet ink was supplied for the above described IPSiO GX e5500 inkjet printer (manufactured by Ricoh Co., Ltd.) having a structure illustrated in FIGS. 1 and 2 and a solid image was printed across an A4 sheet of the following Recording Sheet A with a recording density of 600 dpi x 300 dpi and one pass. The amount of ink attachment was adjusted from 300 mg/A4 to 340 mg/A4 and the image obtained 10 minutes after printing was placed on a flat table with the image facing down to measure the distance between the edge surface. of the sheet and the reference surface by a scale. The average of the measurement values on the right edge and left edge of the sheet was determined as the amount of curl. The results of evaluation by the following criteria are shown in Table 5.
    A and B are preferred. Evaluation Sheet Engraving Sheet A: BP-PAPER GF-500 (A4, manufactured by Canon Inc.) Evaluation Criteria A: Less than 5mm B: 5mm less than 20mm C: 20mm less than than 50 mm D: Both edges so curled that paper has a cylinder-like shape (6) Discharge Stability Assessment
    The inkjet ink manufactured in Examples and Comparative Examples was provided for the printer described above (IPSiO GX e5500, manufactured by RICOH CO., LTD.) having a configuration illustrated in FIGS. 1 and 2 and evaluated around discharge stability by the following method.
    Images were continuously printed for 10 minutes using the printer on which the nozzle plate was fitted. After leaving the printer at 50 °C and 60% RH for one month with a moisture retaining cap on the head surface to which the ink was attached, the head was returned to the same state as before leaving the head for cleaning. Next, an intermittent print test was conducted under the following conditions and the discharge stability was evaluated.
    That is, a print pattern chart having a print area of 5% for each color was printed continuously on 20 sheets and printing was stopped for 20 minutes. This cycle was repeated 50 times to print the graphic on 1,000 sheets in total and then the print pattern graphic was printed on one more sheet, which was observed with eyes to evaluate the image for streaks while outside, the disturbance of spray solid portion of graph 5%. The printing conditions were that the print density was 600 dpi x 300 dpi with a pass print.
    The evaluation criteria are as follows. The results are shown in Table 5. A and B are preferred. Assessment criteria A: No streaks, no white out, no spray disturbance observed on solid portion B: Light streaks, white out, spray disturbance observed on solid portion C: Streaks, white out, spray disturbance observed on solid portion D: Streaks, white out, spray disturbance observed all over solid portion Table 3



    The unit of compounds in Table 3 is in parts by weight.
    The abbreviations above in Table 3 represent the following: GLY: glycerin EGMBE: ethylene glycol monobutyl ether 2P: 2-pyrrolidone 13 BD: 1,3-butane diol MBD: 3-methyl-1,3-butane diol EHO: 3-ethyl -3-hydroxymethyl oxetane IPG: isopropylidene glycerol DMPA: N,N-dimethyl-β-methoxy propionamide DBPA: N,N-dimethyl-β-butoxy propionamide 2E13HD: 2-ethyl-1,3-hexane diol LS: EMALGEN LS- 106 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by KAO CORPORATION) DSN: surfactant represented by chemical formula 4 AEPD: 2-amino-2-ethyl-1,3-propane diol LV: Antiseptic and antifungal agents (Proxel™ LV, manufactured by ARCH CHEMICALS JAPAN, INC.) Table 4
    Table 5


    According to the present invention, the ink jet ink is provided which has improved coloring property and exhibits good light fastness.
    In addition, using this ink, highly saturated images can be printed not only on plain paper but also on specialized paper such as particular gloss paper and coated paper.
    Having now fully described embodiments of the present invention, it will be apparent to one skilled in the art that many changes and modifications can be made without departing from the spirit and scope of the embodiments of the invention as defined herein.
    权利要求:
    Claims (9)
    [0001]
    1. Inkjet ink comprising: a pigment; a water-soluble solvent; and water, characterized in that the pigment is represented by the following chemical formula 1-3 and has an X-ray diffraction spectrum of CuKα having a wavelength of 1.541 Â, such that no major peak is observed at an angle of Bragg (2θ ± 0.2°) in a 2θ range of 28.0° to 29.0°
    [0002]
    2. Inkjet ink according to claim 1, characterized in that the pigment satisfies the following ratio 1: 0.000 < Y/X < 0.800 Ratio 1 in which in an X-ray diffraction spectrum of CuKα having a wavelength of 1.541 Â, X represents a peak intensity at a Bragg angle (2θ ± 0.2°) over a 2θ range of 5.5° to 6.0° and Y represents a peak intensity at a Bragg angle (2θ ± 0.2°) over a 2θ range of 26.5° to 27.5°.
    [0003]
    3. Inkjet ink according to claim 1 or 2, characterized in that the pigment has a volume mean particle diameter of 30 nm to 150 nm.
    [0004]
    4. Inkjet ink according to any one of claims 1 to 3, characterized in that it additionally comprises a dispersing agent represented by the following chemical formula 2: A1-O-B1 Chemical formula 2 in which A1 represents a linear or branched alkyl group having 8 to 12 carbon atoms, a β-naphthyl group, a styrenized phenolic group, or a distyrenized phenolic group and B1 represents a COOM1, a SO3M1, or a PO3M12, where M1 represents Na, K, tetramethyl ammonium, or amine ethanol.
    [0005]
    5. Inkjet ink according to any one of claims 1 to 4, characterized in that it additionally comprises an agent represented by the following chemical formula 3:
    [0006]
    6. Inkjet ink according to any one of claims 1 to 5, characterized in that the water-soluble solvent is at least one of 3-ethyl-3-hydroxymethyl oxetane, isopropylidene glycerol, N,N-dimethyl- β-methoxy propionamide and N,N-dimethyl-β-butoxy propionamide.
    [0007]
    7. Ink cartridge (200) characterized in that it comprises: a container (241); and the ink jet ink as defined in any one of claims 1 to 6 accommodated in the container (241).
    [0008]
    8. Ink jet recording device (101) characterized in that it comprises the ink cartridge (200) as defined in claim 7.
    [0009]
    9. Inkjet printed matter characterized by the fact that it comprises: a recording medium (142); and the ink jet ink as defined in any one of claims 1 to 6 applied to the recording medium (142).
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    同族专利:
    公开号 | 公开日
    EP2706098A1|2014-03-12|
    BR102013023049A2|2014-10-21|
    CN103666106A|2014-03-26|
    US9267046B2|2016-02-23|
    JP2014065890A|2014-04-17|
    US9150745B2|2015-10-06|
    US20140072779A1|2014-03-13|
    US20150247049A1|2015-09-03|
    EP2706098B1|2019-07-24|
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    法律状态:
    2014-10-21| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-08| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|
    2021-09-21| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-198956|2012-09-10|
    JP2012198956|2012-09-10|
    JP2013139476A|JP2014065890A|2012-09-10|2013-07-03|Ink for inkjet recording, ink cartridge, inkjet recording apparatus and recorded matter|
    JP2013-139476|2013-07-03|
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