• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Summary of the Patent for: IMAGE FORMATION METHOD. An imaging method including adhering a pre-treatment liquid to a surface of a recording medium having a coating layer on it; adhering an ink including a dye, an organic solvent, a surfactant and water to the surface of the recording medium to form an image of the ink; and adhering a post-treatment liquid to the surface containing the image of the recording medium to form a protective layer over at least the image on the recording medium. The paint's organic solvent includes a polyalcohol with an equilibrium moisture content of at least 30% by weight at 23 ° C and 80% RH; a B-alkoxy-N, N-dimethylpropionamide compound and at least one compound selected from 1,3-dioxane-4-methanol compounds, oxetane compounds and sebacic acid dialkyl ester compound.
    公开号:BR102013000712B1
    申请号:R102013000712-9
    申请日:2013-01-10
    公开日:2020-11-17
    发明作者:Hidetoshi Fujii；Hiroshi Gotou
    申请人:Ricoh Company, Ltd.；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    The present invention relates to an imaging method using an inkjet ink. BACKGROUND OF THE INVENTION
    Since inkjet engraving methods have advantages over other imaging methods / color images can be easily formed; c operating costs are low, inkjet engraving methods have been used extensively recently. However, inkjet engraving methods have a disadvantage, so that defective images (such as blurred images, including images with blurred characters) are easily formed depending on the combinations of the ink and the recording medium used.
    For example, when coated papers that are used for commercial printing and printing publications, in which a filler, such as calcium carbonate and kaolin, are used in the coating layer, are used as a recording medium, problems such as images that are seriously blurry, and very low image density are caused. The reasons for the problems are considered as follows. Specifically, since such coated papers cannot absorb a large amount of ink in a short space of the top, unlike inkjet engraving papers, ink delivery, which is not well absorbed, spreads horizontally, thus forming a blurred image. Furthermore, even when the ink penetrates the coating layer of the coated papers, the filling (like kaolin) in the coating layer opacities the ink that has penetrated, thus forming an image of the low density. Therefore, such coated papers, as used for commercial printing and printing of publications, have been considered to be completely unsuitable for inkjet printing.
    As with inkjet inks, water-based pigment inks in which fine pigment particles are dispersed in water attract attention. Since the pigments used 15 for inkjet inks are similar in composition to the dyes of the inks used for commercial printing, it is expected that images with a sensation similar to the images formed by commercial printing can be formed by inkjet inks. . However, even when images 20 are formed on coated coated paper for commercial printing and printing publications by inkjet printing methods using pigment inkjet inks, the blurred image problem and / or other problems, such as pigments that are not attached to coated papers and no glossy image formation tend to occur.
    In an attempt to solve the problems, an ink jet etching method (a first method) using a combination of a pigment ink with a high penetration property and a recording medium with a low ink absorption capacity is proposed. In addition, another method (second method) in which a heating roller is used as a drying aid device to quickly dry ink images is proposed to improve the drying property and the fixing property of ink images. In addition, another method (third method) in which a protective layer is formed on the inkjet images using a UV varnish to protect the ink images, that is, to prevent the occurrence of a problem in which the pigment included in the ink images and the remainder on the surface of a recording paper is scraped when the images are rubbed, it is proposed.
    In commercial printing and printing of publications, hundreds or thousands of print sheets are usually produced in a printing operation. Therefore, printing machines are necessary to stably produce prints without forming defective images. When inkjet printers are used for commercial printing and publication printing, there is a risk of a problem where inkjet nozzles clog with dry inks (ie the nozzle clogging problem) or the inks are ejected in the wrong directions due to the fixation of dry inks around the nozzles of the inkjet nozzles, thus forming images with white lines or images with unwanted lines. The best method to prevent the problem from occurring is to add a water-soluble organic solvent, having a high boiling point to an inkjet ink to provide a relatively low drying property for the ink.
    However, when the first method mentioned above is used when using a combination of an inkjet ink, including a water-soluble organic solvent, with a high boiling point (to prevent the nozzle clogging problem from occurring) ), and a recording medium, such as coated papers, for use in commercial printing, which has an extremely low ink absorption property, another problem is the delay before the ink is fixed to the recording medium to an extent so that the ink image is not blurred even when friction occurs. Therefore, when the first method is used for commercial printing, it takes time before the images are attached to the recording medium, thereby causing a problem in which the resulting prints cannot be distributed with leaflets or catalogs right after the prints are formed. .
    In the second method mentioned above, an oil-based paint, including an aliphatic hydrocarbon as a major component, is used. Therefore, when the ink is heated, an organic compound is evaporated and discharged from the printer, causing environmental pollution.
    In the third method mentioned above, the printer must have a heater to form images. In addition, in the post-treatment section 10 of the printer, a UV varnish is ejected towards the entire surface of a recording medium, and the UV varnish that adhered to the recording medium is cross-linked by a device such as UV lamps. . Therefore, the printer has a complex structure and is not environmentally friendly.
    For these reasons, the inventors have recognized that an image formation method is needed whereby high quality full color images with good drying properties and resistance to friction can be formed on papers for use in high speed commercial printing. BRIEF SUMMARY OF THE INVENTION
    As an aspect of the present invention, an imaging method is provided that includes adhering a Pretreatment Liquid to a surface of a recording medium having a coating layer on it; adhering an ink including a dye, an organic solvent, a surfactant and water to the surface of the recording medium, to which the pre-treatment liquid adhered, to form an image of the ink on it; and adhering a post-treatment liquid to the surface of the etching medium, on which the image is formed, to form a protective layer on at least the surface of the etching medium. The organic solvent of the ink includes: a polyalcohol with an equilibrium moisture content of at least 303 by weight at 23 ° C and 80% RH; an amide compound having the formula mentioned below (D:
    (i.e., the β-alkoxy-N, 8-dittiethylpropionamide compound) where R represents an alkyl group having 4 to 6 carbon atoms; and a compound having a formula selected from the group consisting of the formulas mentioned below (IT} to {IV};
    (i.e., the compound 1,3-dioxane-4-methanol) where Ri represents a hydrogen atom, or an alkyl group having 1 or 2 carbon atoms, and R * represents an alkyl group having 1 to 4 atoms carbon dc;
    (i.e., the oxetane compound) at which RT represents an alkyl group having 1 or 2 carbon atoms, and Ra represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclic alkyl group or a group aromatic; and
    (i.e., compound of the dialkyl ester of sebacic acid) in which each of R1 and Rs independently represents an alkyl group having from 1 to 8 carbon atoms.
    The aspects, characteristics and advantages mentioned above and others will be evident upon consideration 15 of the following detailed description of the preferred modalities, taken together with the associated drawings.
    Figure 1 is a schematic view illustrating an inkjet printer for use in the imaging method of the present invention, which performs natural drying;
    Figure 2 is a schematic view illustrating another inkjet printer for use in the imaging method of the present invention, which performs drying by hot air;
    Figure 3 is a schematic view illustrating another inkjet printer for use in the image forming method of the present invention, which performs drying by hot air and fixing by heating roller;
    Figure 4 is a schematic view illustrating another inkjet printer for use in the imaging method of the present invention, which performs drying by heating roller;
    Figure 5 is a schematic view illustrating another inkjet printer for use in the imaging method of the present invention, which performs drying by infrared irradiation; and
    Figure 6 is a schematic view illustrating another inkjet printer for use in the imaging method of the present invention, which performs microwave drying.
    The image formation method of the present invention is provided to form high quality full color images having good drying properties and resistance to friction in papers for use with high speed commercial printing. In addition, the image formation method avoids the following problems occur. (1) Pearl formation problem, in which a grainy solid image is formed due to the attraction of two or more adjacent dot images, and a color bleeding problem, in 10 which color dot images are adjacent to each other are mixed in the boundary portion of the same, resulting in deterioration of the image quality. These problems are easily caused when images are formed on coated papers with poor ink-absorbing properties, such as 15 printing papers with a coating layer. (2) A fixation problem, when a conventional pretreatment agent, including a polyvalent metal salt, is applied to a recording medium, ink images are not satisfactorily attached to the recording medium. (3) A glare deterioration problem in which, when such a conventional pretreatment agent as mentioned above in paragraph (2) is addressed, the occurrence of the pearl formation problem and the color bleeding problem can be avoided, but the brightness of the image deteriorates. (4) A wrinkling (ripple) problem where a recording medium in which a solid image is formed using an aqueous ink is waved.
    The present invention will be described below with reference to the examples.
    Initially, inkjet ink (hereinafter, sometimes referred to as ink) for use in the imaging method of the present invention will be described.
    The ink for use in the imaging method of the present invention includes at least one dye, an organic solvent, a surfactant and water, and optionally includes other components, such as penetrants and aqueous resin dispersions.
    The organic solvent includes a polyalcohol which has an equilibrium moisture content of at least 30% by weight at 23 BC and 80% RH, an amide compound with the formula mentioned below (I), and at least one compound having one of the following formulas mentioned below (1'0 to (IV).
    (i.e., the compound p-alkoxy-N, N-dimethylpropionamide) where R represents an alkyl group having 4 to 6 carbon atoms.
    (that is, compound 1, 3 "dioxation-4 ~ methanol) where Rj represents a hydrogen atom, or an alkyl group having 1 or 2 carbon atoms, Ra represents an alkyl group having dc 1 to 4 atoms of carbon.
    (i.e., the oxetane compound) where R 'represents an alkyl group having 1 or 2 carbon, and Ra represents a hydrogen atom, alkyl having 1 to 8 carbon atoms, a cyclic alkyl group or an aromatic group.
    atoms of a group (that is, composed of the dialkyl ester of sebacic acid) in which each of RA and R $ independently represents an alkyl group having from 1 to 8 carbon atoms.
    The content of the organic solvent in the paint is preferably 20% to 80% by weight, most preferably 30% to 70% by weight, based on the total weight of the paint. When the content is less than 20% with the effect of curling prevention to prevent a curled impression tends not to be produced. In addition, the stability of the ink ejection tends to deteriorate, and an ink waste problem, which adheres to a maintenance device, which performs a maintenance operation on a recording head to eject the ink, can be caused. In contrast, when the content is greater than 80% by weight, the viscosity of the ink increases to a point such that the ink is hardly ejected by a recording head. In addition, ink tends to have poor drying properties on embossing papers, and the quality of character images tends to deteriorate,
    Specific examples of the amine compound of formula (I) include the following.

    Specific examples of the compound of formula (II) include the following.

    Specific examples of the compounds of formula (III) include the following.

    Specific examples of the compounds with cytotechnology (IV) include the following.

    When an amide compound of formula (I), and at least one of the compounds having formula (II) to (IV) are used when mixed, the resulting paint has a good combination of ejection stability and drying property. the reason is that these compounds include a thihydrophobic group in a relatively large amount in the balance of hydrophilic group - hydrophobic group, and therefore the ink can easily penetrate the recording medium. the total content of the amide compound having the formula (. [) and the compounds having the formulas (II) to (IV) in the paint is preferably from 1% to 50% by weight, more preferably from 2% to 40%, by weight, and even more preferably from 3% to 30%, in position, based on the total weight of the paint. When the total content is less than 1%, the ripple prevention effect cannot be satisfactorily produced, and the image quality improvement effect cannot be produced. In addition, the drying properties of ink adhered to general purpose printing papers are hardly improved. In contrast, when the total content is greater than 505 by weight, the viscosity of the ink increases dramatically, thereby deteriorating the ink's ejection stability.
    An alkylalkanediol can be used as an organic solvent to accelerate the ripple prevention effect. Among alkylalkanedioles, alkalodiols including an alkanediol having 3 to 6 carbon atoms as a main chain, while including an alkyl group having 1 to 2 carbon atoms as a branched chain are preferable because the compounds have a good balance of hydrophilic group - hydrophobic group c has adequate water solubility, while at the same time including a hydrophobic group in a large rolling amount, thereby imparting good penetration property to the resulting ink.
    Among these somealcanialodiols, 2-methanol-1,3-butanediol (214 ° C boiling point), 3-methyl-1,3-butanediol (203 ° C boiling point), 3-methanol- 1.5-pentanediol (boiling point 250 ° C) and 2-ethyl-1,3-hexanediol (boiling point 243.2 ° C) are preferable. n
    The content of such alkylalkanediol in the paint is preferably from 2% to 40% by weight, and most preferably from 5% to 30% by weight, based on the total weight of the paint. When the content is less than 2% by weight, the effect of improving the penetration property and the effect of improving image quality are hardly produced, and the drying property of ink adhered to general purpose printing papers is hardly enhanced. Conversely, when the content is greater than 40% by weight, the ink viscosity increases, thereby often deteriorating the ink ejection stability. A polyalcohol with an equilibrium moisture content of at least 30% in place at 23 ’C and 80% RH is included in the paint as a wetting agent. By including such a polyalcohol in the ink, the ink ejection stability can be improved, and the effect of preventing the occurrence of the problem of fixing the residual ink on a recording head maintenance device can be produced.
    Specific examples of such a polyalcohol include 1,2,3-20 butanotriol (with a boiling point of 175 ° C at 33 hPa and a moisture content of 38% by weight), 1,2,4-butanotriol (with a boiling of 190-191 ° C at 24 hPa and equilibrium moisture content of 41% by weight), glycerin (with a boiling point of 290 ° C and equilibrium moisture content of 49% by weight), diglicerlná (with dot boiling point of 270 ° C at 20 hPa and equilibrium moisture content of 385 wt.%, trict.il enoglycol (with a boiling point of 235 ° C and equilibrium moisture content of 395 cm. weight), tetraethylglycol (with boiling of 324-330 ° C and equilibrium moisture content of 37% by weight), diethylene glycol (with boiling point of 245 ° C and equilibrium moisture content of 43% by weight) and 1,3-butanediol (with boiling point of 203-204 ° C and equilibrium moisture content of 35% by weight). Among these polyalcohols, glycerin and 1,3-butanediol are preferable.
    The content of such polyalcohol in the paint is preferably 2% to 50% by weight, and more preferably 5% to 40% by weight based on the total weight of the paint. When the content is less than 2% by weight, the hydrating effect can hardly be produced. Conversely, when the content is greater than 50% by weight, the drying properties of the ink on the embossing papers cannot be improved and therefore the image quality of the images of the characters formed on the plain papers often deteriorates.
    The method of measuring the equilibrium moisture content of an organic solvent is as follows.
    A sample (organic solvent) of about 1 g is fed into a petri dish while it is precisely placed (Wl), and the petri dish is left to stand for 240 hours in a dryer, since an aqueous solution of chloride potassium sodium chloride is contained to control the atmospheric condition in the dryer at 23 i 1 ”C and 80 t 3% ÜR. After that, the sample is weighed again (W2). The equilibrium moisture content (EMC) is determined by the following equation. EMC (% by weight) - ((W2-W1) / W2) x 100 where W1 represents the weight of the sample before the test, and W2 represents the weight of the sample after the test (that is, the weight of the water absorbed by sample). In this respect, (W2-W1) represents the weight of the water that the sample absorbs.
    The araid compound having the formula mentioned below (I — 1) has a relatively high boiling point of 216 ° C or a relatively high equilibrium moisture content of 39.2% by weight, while having a very low viscosity 1.48 mPa.s at 25 ° C. In addition, the amide compound has good solubility in other timid compounds with formula (I), compounds with formula (II) to (IV), alkylalkanol and water. Therefore, it is preferable to include this compound as an organic solvent in the ink, because the resulting ink has low viscosity and a good combination of preservation stability and ejection stability without causing the problem of fixing the residual ink in a maintenance device.
    the content of the amide compound having Formula (i-1) is preferably from 1% to 50% by weight, and more preferably from 2% to 40% by weight. When the content is less than 1% by weight, the viscosity-reducing effect can hardly be produced. Conversely, when the content is greater than 50% by weight, the ink tends to have poor drying properties on embossing papers, and the quality of the character images tends to deteriorate.
    The ink for use in the inkjet etching method of the present invention can include an organic solvent other than the organic solvents mentioned above, and an insoluble agonizer.
    For example, polyalcohols, aryl polyalcohol ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonates, ethylene carbonate or other wetting agents can be included in the paint.
    Specific examples of such polyalcohols include dipropylene glycol (boiling point 232 ° C), 1,5-pentanediol (boiling point 242 ° C), propylene glycol (boiling point 187 ° C), 2-methyl-2,4 -pentaoediol (197 ** boiling point C> z ethylene glycol (196-190 UC boiling point), tripropylene glycol (267 ° C boiling point), hexiienoglycol (197 "C boiling point), polyethylene glycol (liquid viscous or solid) / polypropylene glycol (boiling point 187 '' CJ, 1/6-hexanediol (boiling point 253-260 ° C), 1,2,6-hexanotriol (boiling point 178 ° C), trimethylolotane (COTO solid melting point 199-201 ° C) and trimethylolpropane (solid GOTO melting point 61 ° C).
    Specific examples of such polyalkyl alkyl ethers include ethylene glycol monoethyl (boiling point 135 ° C), ethylene glycol monobutyl ether (boiling point 171 ° C), diethylene glycol monoethyl ether (194 QC boiling point), diethylene glycol ether (197 boiling point) 0C}, cholinonobutyl diethyl ether (231 ° C boiling point), ethylene glycol mono-2-ethylhexyl ether (229 ° C boiling point) and propylene glycol monoethyl ether (132 ° C boiling point).
    Specific examples of such polyaryl aryl alcohol ethers include otylene glycol monophenyl ether (boiling point 237 ° C) and ethylene glycol monobenzyl ether,
    Specific examples of such nitrogen-containing hoterocyclic compounds include 2-pyrrolidone (boiling point 250 ° C, melting point 2515 * 0 and equilibrium moisture content 47-48% by weight), N-methyl-2- pyrrolidone (boiling point 202 ° C), 1,3-dimethyl-2-injidazolidinone (boiling point 226 ° C), ε-caprolactam (boiling point 270 ° C) and y-butyrolactone (boiling point 204-205 ° C).
    Specific examples of such amides include formaraide (210 ° C boiling point), N-methylformamide (199-201 ° C boiling point), N, N-dimethylformamide (153 ° C boiling point) and N, N -diethylformamide (boiling point 176-177 ° C).
    Specific examples of such amines include monoethanolamine (boiling point 170 ° C), diethanolamine (boiling point 260 ° C), triethanolamine (boiling point 360 ° C), N, W-dimethylmonoethanolamine (boiling point 139 ° C), N-methyldiethanolamine (boiling point of 243 ° C), N-methylethylethanolamine (boiling point of 159 ° C), N-phoni.letanolamine (boiling point of 282-287 ° C) o 3-amihopropildietilamiπa (boiling point 169 ° C).
    Specific examples of such sulfur-containing compounds include d.i methyl Isoxide (139 ° C boiling point), sulfolane (285 ° C boiling point) and thiodiglycol (282 ° C boiling point),
    Solid wetting agents, such as saccharide, can be used. Examples of saccharides include monosaccharide, disaccharide, oilgoasaccharide (including tri tetrasaccharides) and polysaccharides.
    Specific examples thereof include glucose, 5 mannose, fructαsc, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose and maltotriosc.
    In this application, polysaccharide means saccharide in a broad sense, and includes materials present in nature such as 10 α-cyclodextrin and cellulose.
    Not only the saccharide mentioned above, but also its derivatives, can be used. Specific examples of such derivatives include saccharide-reducing materials mentioned above (for example, sugar alcohols (having the formula HOCH2 (CBOII) ÜCII2OH, where n is an integer from 2 to 5)}, saccharide oxidation materials mentioned above (for example, aldonic acid and uronic acid), amino acids and thio acids.
    Among these materials, sugar alcohols are preferable. Specific examples of such sugar alcohols include maltitol and sorbite.
    The ratio of the dye to the organic solvent in the ink significantly influences the ejection stability of the ink ejected from the recording head. Furthermore, whether the problem of residual ink therefrom being fixed to a recording head maintenance device occurs to a large extent or not depends on the weight ratio.
    For example # when the dye content in the ink is high and the organic solvent content is low, the water in the vicinity of the ink surface in a nozzle, which forms the meniscus, tends to evaporate easily, causing a defective ejection problem.
    Next, the dye included in the ink will be described.
    The dye in the ink preferably reaches one of the following states (1) to (3). (3.) The dye includes a self-dispersing pigment that has at least one hydrophilic group on its surface and that can be dispersed in water without a dispersant (i.e., self-dispersing pigment). Such dye is hereinafter referred to as a dye in the first state. (2) The dye is a dispersion of the pigment, including a pigment, a pigment dispersant and a polymeric dispersion stabilizer, wherein the polymeric dispersion stabilizer is a selected member of the group consisting of copolymers of o-olefin-anhydride, having the formula mentioned below (a), styrene (meth) acrylic copolymers, water-soluble polyurethane resins and
    water-soluble polyester resins. wherein R represents an alkyl group of from 6 to 30, preferably from 12 to 24, and more preferably from 18 to 22 carbon atoms, and n is an integer from 20 to 100. The average weight molecular weight of the copolymers is 5,000 to 20,000. In formula (a), the alkyl groups R in the repeating units can be the same or different from each other. However, such a dye is referred to as a dye in the second state. (3) The dye is a polymeric emulsion in which fine polymer particles, including a dye, which is insoluble or hardly soluble in water, are dispersed in water. Such dye is hereinafter referred to as a dye in the third state.
    Organic pigments and inorganic pigments can be used for the dye pigment. In this regard, dyes can be used to adjust the color tone, but it is preferable to add a dye in such an amount that it does not deteriorate the weather resistance of the paint.
    Specific examples of inorganic pigments include, but are not limited to, titanium oxide, iron oxide, calcium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow and black smoke. Among these pigments, carbon black is preferable. Carbon blacks prepared by any methods known as contact methods, furnace methods and thermal methods can be used.
    Specific examples of organic pigments include azo pigments, polycyclic pigments, chelated dyes, nitro pigments, nitrous pigments and aniline black.
    Among these pigments, azo pigments and polycyclic pigments are preferable. Specific examples of azo pigments include azo lacquers, insoluble azo pigments, condensed azo pigments and chelated azo pigments. Specific examples of polycyclic pigments include phthalocyanine pigments, 15 pearlene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, d.ioxazin pigments, indigo pigments, thioindigo pigments, isoindo.linone pigments and guinophthalone pigments . Specific examples of chelated dyes include basic dye chelates and acid dye chelates.
    The color of the dye is not particularly limited, and one or more dyes for use in forming black color and chromatic colors are used so that the resulting ink has the desired color.
    Specific examples of black pigments include carbon blacks (i.e. Pigment Black C.I. 7), such as furnace black, lamp black, acetylene black or channel black; metal powders (i.e. Pigment Proto C.I. 11) such as copper and iron; metal oxides such as titanium oxide; and organic pigments such as aniline black (i.e., Pigment Black C.I. 1).
    Specific examples of chromatic color pigments include CI Yellow Pigments 1, 3, 12, 13, 14, 17, 24, 34, 10 35, 37 and 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95 , 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 728, 138, 150, 151, 153 and 183; Orange Pigments C.I. 5, 13, 16, 17, 36, 43 and 51; Red Pigments CI 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (permanent red 2B {Ca}), 48: 3, 48: 4, 15 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Crimson 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (red iron oxide), 104, 105 , 106, 108 (cadmium red), 112, 114, 122 (quinacridone magenta) 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209 and 219; Violet Pigments C.I. 1 (Rhodamine lacquer), 3, 5: 1, 16, 19, 23 and 38; Blue Pigments C.I. 1, 2, 15 (Phthalocyanine Blue), 1.5: 1, 15: 2, 15: 3 (Phthalocyanine Blue) 16, 17: 1, 56, 60 and 63; and Green Pigments C.I. 1, 4, 7, 8, 10, 17, 18 and 36.
    The self-dispersing pigment mentioned above in paragraph (1) means a pigment subjected to surface modification, such that at least one hydrophilic group is connected to the surface of the pigment with or without an intervening group between species. The surface modification is carried out by chemically attaching a specific functional group (such as sulfone and carboxyl groups) to the surface of a pigment, or by treating the wet oxidation using a hypohalous acid or a salt thereof. Among these pigments, pigments in which a carboxyl group is attached to the surface of the pigments and which are dispersed in water are preferable. When using lime surface-modified pigment with a carboxyl group, the pigment can be dispersed in the ink and therefore high quality images can be produced. In addition, the water resistance of images printed on the recording medium can be further improved.
    In addition, an ink including such a self-dispersing pigment as mentioned above (ie the dye in the first state) has good redispability, so that even when the ink was spouted it is not used for a long period of time and water in the ink in the vicinity of the nozzle surface evaporates, the occurrence of the nozzle clogging problem in that inkjet nozzle clogged with dry ink can be avoided or good images can be formed by performing a simple cleaning operation of the recording head.
    The volume of the average particle diameter (050) of such a self-dispersing pigment in a paint is preferably 50z 01 pm to 0.16 pm.
    Among self-dispersing carbon blacks, ionic carbon blacks such as anion carbon blacks or charged cationically are preferable.
    Specific examples of the anionic hydrophilic groups for charging anionically carbon blacks include -COOM, -SO3M, 'PO3HM, -PthM, “SO2NH2 and -SO ^ NíiCOR, where M represents a hydrogen atom, an alkali metal ion, an ammonium ion or an organic ammonium ion, and R represents an alkyl group having from 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group or a substituted or unsubstituted nayl group. Among these groups, -CDOM and -SO3M are preferable. That is, colored pigments in which -CCOM w / or -SO3M are attached to their surface are preferable.
    Specific examples of alkali metals for use as alkali metal M in the hydrophilic groups mentioned above include lithium, sodium and potassium. Specific examples of organic ammonium ions include mono to trimethylarnium ions. mono ions to iriethylamônio and mono ions to trimettanolammonium.
    Specific examples of the method for preparing a union-loaded pigment include a method in which a color pigment is subjected to an oxidation treatment using a sodium drochlorite to form a -COONa group on the pigment surface; a method using sulfonation; and a method using a reaction of a pigment with a diazonium salt.
    Among the cationic hydrophilic groups, quaternary ammonium groups are preferable, and quaternary ammonium groups with the following formulas are more preferable, Carbon blacks in which any such quaternary ammonium groups are bonded to the surface thereof are preferably used for the paint for use in the present invention.
    The pure method of preparing a charged cationication carbon black is not particularly limited. For example, a method in which a carbon black is treated with 3-amine-N-ethylpyridinium bromide to form the N-ethylpyridyl group mentioned below on the surface of the carbon black can be used.

    The hydrophilic groups mentioned above can be attached to the surface of the carbon black with a group between them. Specific examples of such an intervening group include alkyl groups having from 1 to 12 carbon atoms, substituted or unsubstituted phenyl groups and substituted or unsubstituted naphthyl groups.
    Specific examples of hydrophilic groups having such an intervening group include -CjJLjCOOM (M represents an alkali metal ion, or a quaternary ammonium ion), -PhSO ^ N (Ph represents a phenyl group and M represents an alkali metal ion, or an quaternary ammonium ion) and -CsHioNih *.
    The aforementioned dye in the second state is a pigment dispersion, including a pigment (such as inorganic pigments, organic pigments and complex pigments), a pigment dispersant and a polymeric dispersion stabilizer. The polymeric dispersion stabilizer includes at least one member selected from u-polymers of a-olefin-malic anhydride having the aforementioned formula (a), copolymers of (meth) acrylic starch, water-soluble polyurethane resins and polyester resins soluble in water.
    As for copolymers having formula (a), copolymers synthesized using a mixture of several olefins having a different number of carbon atoms can also be used. In this case, the resulting copolymer includes alkyl groups, which have different numbers of carbon atoms and which are randomly incorporated into the main chain. The average molecular weight of the copolymers having formula (a) is measured using a gel permeation chromatography (GPC) system. The procedure is as follows. (1) A sample (copolymer) is dissolved in tetrahydrofuran (THF), { .} A working curve is prepared by subjecting three types of polystyrene (ie, standard materials) with known molecular weights of 1,000, 2,400 and 8,500 to analysis of GPC using a KP-806 L column (for 9'HF) as the GPC column. (3) The sample's THF solution is subjected to GPC analysis to obtain a size exclusion chromatogram (SEC). (4) The average weight molecular weight of the copolymer is determined using SKC, the differential molecular weight distribution curve and the working curve prepared using standard materials.
    The polymeric dispersion stabilizer mentioned above is used to stabilize the fine particles of a pigment, which are uniformly dispersed in water by a dispersant. Copolymers with formula (a), eatirene-acid (meth) acrylic copolymers, water-soluble polyurethane resins and water-soluble polyester resins are solid at room temperature and are hardly soluble in cold water. However, such a polymeric material (copolymer or resin) can be soluble in a liquid or water including an alkali, in such an equivalent amount as being from 1.0 to 1.5 times the acid value of the stabilizer, © the alkaline solution. can be used as the polymeric dispersion stabilizer. When such a polymeric material is dissolved in water or alkaline liquid, the material can be easily dissolved by heating or stirring the mixture. A copolymer having formula (a) and a long oleyl chain cannot be easily dissolved in an alkaline liquid or water, and there is a case where part of the copolymer remains in solution without being dissolved. In such a case, the solution is subjected to filtration and the filtrate can be used as the polymer dispersion stabilizer.
    Specific examples of the alkaline materials used for use in the preparation of the alkaline liquid or water include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; basic materials such as ammonia, triethylamine and morpholine; and alcoholic amines such as triethanolamine, diethanolamine, N-methyldiethanolamine, 2-5 amino-2-ethyl1-1,3-propanediol and choline.
    As for the polymeric dispersion stabilizers, properly synthesized copolymers or commercial products can be used.
    Specific examples of the products marketed for the copolymers of formula (a) include T-YP112, T-YP115, T-YP114 and T-YP116, with Seiko PMC Corp.
    Specific examples of the products marketed for styrene (meth) acrylic copolymers include JC-05, with Seiko PMC Corp .; ARUFONs UC-3900, UC-3910 and ÜC-3920, 15 with TOAGOSEI Co., Ltd.
    Specific examples of products marketed for water-soluble polyurethane resins include TAKELACs W ~ 5025, W-6010 and W-5661, with Mitsui Chemicals, Inc.
    Specific examples of the products marketed for the 20 water-soluble polyester resins include NICHfGO POLYESTERS W-0030, W-0005S30WQ or WR-961, with Nippon Synthetic Chemical Industry Co., Ltd '; and PESRESINs A "210 and A-520 with Takamatsu Oil & Fat CO., Ltd.
    The polymeric dispersion stabilizer included in the ink preferably has an acid value of 40 to 400 mg KOH / g and, more preferably, 60 to 350 mg KOH / g. When the acid value is less than 40 mg KOH / g, its solubility in an alkaline liquid tends to deteriorate.
    Conversely, when the acid value is greater than 400 mg KOH / g, the viscosity of the paint tends to increase, thereby deteriorating the paint's ejection property and the dispersion stability of the pigment included in the paint, The dispersion stabilizer polymeric material included in the ink preferably has an average weight molecular weight of a maximum of 20,000, and more preferably, of 5,000 to 20,000. When the average molecular weight is less than 5,000, the dispersion stability of the pigment and ink dispersion tends to deteriorate. In contrast, when the average molecular weight is greater than 20,000, its solubility in an alkaline liquid or water tends to deteriorate, increasing the viscosity of the paint. The polymeric dispersion stabilizer is included in the ink in an amount of 1 to 100 parts by weight (on a solid basis) and preferably from 5 to 50 parts by weight, based on 100 parts by weight (on a solid base) of the pigment included in the ink. When the content is less than 1 part by weight, the stabilizing effect of the dispersion is hardly produced. In contrast, when the content is greater than 100 parts, the viscosity of the ink tends to increase, thereby commonly deteriorating the ink's ejection property, and the costs of the heating ink increase.
    The dye mentioned above in the second preforoncially state 5 includes a pigment dispersant.
    Materials suitable for use as the pigment dispersant include anionic surfactants, and nonionic surfactants with an HLB value of 10 to 20.
    Specific examples of such arionic surfactants 10 include polyolethylenealkyl ether acetates, 'ilkylbenzene sulfonates (for example, NH4, Na and Ca} salts, alkyldiphenyl ether disulfonates (for example, Nlk, Na and Ca salts), sodium dialkylsuccinatosulfonate , sodium salts of condensate of naphthalenesulfonic acid formalin, salts (for example, salts of Mlg and Na} of sulfuric acid esters of polyoxyethylene poly5.clico-phenyl ethers, laurates, polyoxyethylene alkylethylates and oleates, Among these surfactants, sodium dioctylsulfosuccinate and ammonium salts (NHJ of sulfonic acid salts of styrene polyoxyethylene ether-phynyl ether are preferable.
    Specific examples of the aforementioned non-ionic surfactants having an HLB value of 10 to 20 include polyoxyethylalea ethers, polyoxyalkylalkyl ethers, polyoxyethylenepulicyclic-phenyl ethers, sorbitan fatty acid esters, fatty acid esters. 1 lenos sorbitan, polyoxyethylene ethers, polyoxyethylenealkylamine, polyoxyethylenealkyl and acotylene glycol. Among these surfactants, polyoxyethylnuroyl ether, polyoxyethylpnaphyl ether, polyoxyethylsorbitan mono-oleate and styrene polyoxyethylene ether are preferred,
    Such a pigment dispersant is included in the ink in an amount of 1 to 100 parts by weight, and preferably from 10 to 50 parts by weight, based on 100 parts in position of the pigment included in the paint. When the pigment dispersant content is very low, the pigments cannot be finely dispersed. On the contrary, when the content is very high, the excess of dispersant, which is not adsorbed on pigment particles, negatively affects the properties of the paint, thus causing problems so that blurred images are formed, and water resistance and resistance the friction of the images recorded by the ink deteriorates.
    Pigment particles dispersed in the paint prelaterally have a volume of the average particle diameter (D50) of a maximum of 150 nm, and more preferably of a maximum of 100 nm. When the volume of the average particle diameter is greater than 150 nm, the ink ejection stability deteriorates dramatically thereby causing the nozzle clogging problem and an ink curving problem, in which the ink is ejected while curved. When the volume of the average particle diameter is not greater than 100 nm, the ink has good ejection stability and the saturation of the recorded images improves.
    Such a pigment dispersion in which a pigment is uniformly dispersed in water is prepared by a method 10 including dissolving such pigment dispersant as mentioned above in an aqueous medium; add a pigment to the solution to wet the pigment; c disperse the pigment using a high speed agitator as homogenizers, a dispersing machine using balls like 15 pearl mills and ball mills, a kneader using a shearing force like roller mills or a supersonic dispersing machine, under this aspect, the resulting pigment dispersion tends to include coarse particles even after kneading or treatment. dispersion, 20 I ink often causes the nozzle clogging problem. Therefore, it is preferable to remove coarse particles with a particle diameter dc of at least .1 pm from the pigment dispersion using a centrifugal separator or filter.
    The aforementioned dye in the third state preferably includes a polymeric emulsion containing polymeric particles, including a pigment. Such a polymeric emulsion is a polymeric emulsion in which the polymeric particles including a pigment are dispersed in them, or a polymeric emulsion in which the polymer particles, in which the pigment is adsorbed, are dispersed. In this respect, all polymeric particles do not necessarily include a pigment in them, or a pigment adsorbed to them, and the pigment particles can be dispersed in the emulsion, as long as the effects of the present invention can be produced by using the dye. Polymers suitable for use in the preparation of the polymer emulsion (i.e., polymers that constitute the polymeric particles) include vinyl polymers, polyesters and polyurethanes. Among these polymers, vinyl polymers and polyesters are preferable. Specific examples of the polymers include the polymers described in JP2000 ~ 5339M and JP2001-139849, incorporated herein by reference.
    Complex pigments in which a popular organic or inorganic pigment is covered with an organic or black smoke pigment can preferably be used for the dye in the third state. Such complex pigments can be prepared by a method - in which an organic pigment is precipitated in the presence of an inorganic pigment, or an ittecanochemical method in which a mixture of an inorganic pigment and an organic pigment is mechanically ground. If necessary, a layer of an organosiloxane compound, which is formed from a polysiloxane or alkylsilane, can be formed between the inorganic pigment or the organic pigment to improve adhesion between them.
    Specific examples of organic black pigments for use in the preparation of complex pigments include aniline black, and specific examples of organic color pigments for use in the preparation of complex pigments include anthraquinone pigments, phthalocyanine blue, phthalocyanine green, diazo pigments, monoazo pigments, pyrantrone pigments, perylene pigments, yellow heterocyclic pigments, quinacridone pigments and indigo (uncle) pigments. Among these pigments, carbon black, phthalocyanine pigments, quinacridone pigments, yellow monoazo pigments, yellow dye pigments and yellow heterocyclic pigments are preferable because the resulting coloring has good coloring properties.
    Specific examples of blue phthalocyanine pigments include copper phthalocyanine and its derivatives (Blue pigments C.I. 15: 3 and 15: 4), and aluminum phthalocyanine.
    Specific examples of quinacridone pigments include Orange Pigments C.I. 48 and 49; C.I. the Red Pigments C.I. 122, 192, 202, 206, 207 and 209; and Violet Pigments 19 and 42,
    Specific examples of Yellow Monoazo Pigments include Yellow Pigments C.I. 74, 109, 128 and 151.
    Specific examples of yellow dye pigments include Yellow Pigments C, I. Yellow pigments, 14, 16 and 17.
    Specific examples of the yellow heterocyclic pigments include Yellow Pigments C.I. 117 and 138.
    Other pigments described in the color index, third version, published in 1982 by The Society of Dyers and Colourists, can also be used.
    Specific examples of inorganic pigments for use in the preparation of complex pigments include titanium dioxide, silica, alumina, iron oxide, iron hydroxide and tin oxide. Inorganic pigments preferably have a particle shape with a small aspect ratio, and most preferably a spherical shape. When the inorganic pigment is adsorbed to a color pigment, the color of the inorganic pigment is mainly transparent or white. When the inorganic pigment is absorbed into a black pigment, a black inorganic pigment can be used. The primary particle diameter of Lai inorganic pigment is preferably at most .100 nm, and most preferably at 5 nm to 50 nm.
    The weight ratio (I / C) of an inorganic pigment (I) to a dye (C) (organic pigment or carbon black) is 5 preferably from 3/1 to 1/3, and more preferably from 3/2 to 1/2, When the weight ratio is very large (that is, the weight of the dye is low), the coloring and color-tuning property of the complex pigment resulting from tending to deteriorate. Conversely, when the weight ratio is very small, the transparency and color tone of the resulting complex pigment tends to deteriorate only.
    Among such complex pigments, complex pigments of silica / carbon black, complex of silica / ítalocyanine PB15: 3, complex pigments of silica / yellow dísazo and pigmotos 15 complexes PR122 of silica / quinacridone with Toda Kogyo Corp, are preferable by having a smaller primary particle diameter.
    When an inorganic pigment having an average primary particle diameter of 20 nm is covered with the same amount of organic pigment, the resulting complex pigment has an average primary particle diameter of about 25 nm. If such a complex pigment can be dispersed using suitable dispersants, so as to be primary particles, an ink in which pigment particles dispersed therein having a small mean particle diameter of 25 nm can be prepared. In this respect, not only the organic pigment present in the complex pigment contributes to the dispersion of the dye in the ink, but also the inorganic pigment 5 present within the complex pigment influences the dispersion of the dye in the ink, because the property of the inorganic pigment is exhibited by the layer of organic pigment with a thickness of about 2.5 nm. Therefore, it is preferable to select a suitable dispersant, which can disperse both the organic pigment and the inorganic pigment stably.
    The content (on a dry basis) of the dye in the ink is preferably Intent and from 2% to 15% by weight, and more preferably from 3% to 12% by weight. When the content is less than 2% by weight, the ink tends to have a weak coloring property, and the images recorded by the ink tend to have low image density. Conversely, when the content is greater than 15% by weight, the viscosity of the ink increases, thereby deteriorating the ejection property of the ink and, in addition, the ink costs increase.
    In the following, the surfactant included in the paint will be described.
    As for surfactants, at least one in anionic surfactants, non-ionic surfactants, silicone surfactants and fluorine-containing surfactants, which do not lose their dispersion capacity even when the types of dye and wetting agent used change which have low surface tension and good penetration property and leveling property is preferably used. Among these 5 surfactants, silicone toners and fluorine-containing surfactants are preferable.
    These surfactants can be used alone or together.
    Suitable materials for use as fluorine-containing surfactants include surfactants having a group that has 2 to 16 fluorine-substituted carbon atoms, and preferably 4 to 16 fluorine-substituted carbon atoms. When the number of carbon atoms replaced with fluorine is less than 2, the effects of fluorine are hardly produced. Conversely, when the number of carbon atoms replaced with fluorine is greater than 16, an ink preservation problem is present. ink conservation deteriorates generally occurs. Materials suitable for use as anthonic fluoride-containing surfactants include perfluoralkylsulfonic acid compounds (such as porfluoralkylsulfonic and poftuoralkylsulfonates), and peyluoralkylcarboxylic acid compounds (such as perfluoralkylcarboxylic acid, and perfiuoralkylcarboxates).
    Materials suitable for use as non-ionic fluorine-containing surfactants include perfluoralkyl phosphate compounds, perfluoralkylethylene oxides and polyoxyalkyl ether polymer compounds with a group of perfluoralkyl ether in a side chain thereof.
    Among these surfactants, polyoxyalkyl ether polymer compounds having a pefluoralkyl ether group are preferable because of the difficult foaming. Specific examples thereof include polyoxyalkyl ether polymers with a pefluoralkyl ether group on a side chain thereof, sulphate salts of polyoxyalkyl ether polymers with a pefluoralkyl ether group on a side chain thereof, and salts of polyoxyalkyl ether polymers with a group of pefluoralkytic ether in a side chain thereof. Among these non-ionic fluorine surfactants, surfactants with the following formula (1} are preferable.
    CF3CP2 {CFaCF2) m-Cll2CH3íO (CR .CH2O) AH {D in which each of men is independent 0 or an integer not less than 1 * In this respect, m is preferably 0 or an integer from 1 to 10 , en is preferably 0 or an integer from 1 to 40, to provide good water solubility to surfactants. Materials suitable for use as perfluoralkyl phosphorus compounds include esters of pefluoralkylphosphoric acid and salts of esters of peryluoralkylphosphoric acid.
    Specific examples of the counterions of these anionic fluorine-containing surfactants include the ions of Li, Na, K, NH <j, NH3CH2CH2OH; NH2 (CHÍCR2OH} 2 G NH (CH2CH2OH) 3. y
    Among fluorine-containing surfactants, compounds with the following formulas (2) to (10) are preferable. (1) Surfactants containing fluoride
    where Rf represents a mixture of hydrophobic groups containing fluorine with the formulas mentioned below (2—1) and (2 ~ 2), and A represents ~ SO3X, -COOX, or -PO3X, where X represents a counterion selected from H, Li, Na, K, NB4, NH3CH2CM2OH, Nib, (CH2CH2OH) 2 and NB (C) I2CH2OH) 3.
    where Rf 'represents a fluorine-containing group with the formula mentioned below (3—1), X represents the counterion defined above in formula (2), n is 1 or 2 and m is 2-n.
    where n is an integer of 3a 10.
    where Rf represents the fluorine-containing group, having the aforementioned formula {3-1}, and X represents the counterion defined above in formula (2).
    where Rf 'represents the group containing fluorine, having the aforementioned formula {3-1}, and X represents the counterion defined above in formula {2}. (2) Surfactants containing non-ionic fluorine
    where Rf represents the fluorine-containing group, having the above-mentioned formula (2-1) or (2-2), and n is an integer from 5 to 20. where Rf 'represents the fluorine-containing group having the above-mentioned formula {3-1), and n is an integer from 1 to 40. (3) Surfactants containing fluorine.1.1 ticos
    where Rf represents the fluorine-containing group having the above mentioned formula (2-1) or (2-2). (4) fluorine-containing oligomer surfactants
    where Rf "represents a fluorine-containing group with the formula mentioned below (9-1), n is 0 or an integer from 1 to 10, and X represents the counterion defined above in formula (2).
    where n is an integer from 1 to 4.
    where Rí "represents a fluorine-containing group having the formula mentioned above (9-1)
    , k is 0 or an integer from 1 to 10, m is 0 or an integer from 1 to 10 and n or 0 or an integer from 1 to 10.
    Commercially available fluoride-containing surfactants can be used. Specific examples thereof include SARFRONs S-111, 3-112, S-113, S-121, S-131, S-132, S-141 and 8-145, which are manufactured by Asahi Glass Co., Ltd .; FLUORAbs FC-93, FC-95, EC-98, FC-129, FC-135, FC-170C, FC-430 and EC-431, which are manufactured by Sumitomo 3M Ltd ,; MEGAFACEs F-470, F-1405 and F-474, which are manufactured by DIG Corp .; iYONs TBS, FSP, FSA, FSN-100, FSN, ESC-100, FSO, ES-300 and UR, which are manufactured by Ou Pont; ET-110, FT-250, FT-251, FT-4008, FT-1.50 and FT-400SW, which are manufactured by Neos Co., Ltd .; and POLYt'OXs FF-136A, PF-156A, PF-151N, PF-1.54 and PF-.1.59, which are manufactured by Om Nova Solutions, Inc.
    Among these products, FS-300 (Du Pont); FT-110, FT-250, FT-251, FT-400S, Ft-150 and FT-400SW (Neos co., Ltd.); And POLYFOX PF-151N (Om Nova Solutions, Inc.) are preferable because the images Engraved by ink has good image qualities, particularly, engraved images have good coloring properties and good color uniformity on papers.
    The aforementioned silicon surfactant is not particularly limited. Materials suitable for use as the silicone surfactant include polydimethylsiloxane, whose side chains are modified, polydimethylsiloxane, whose both ends are modified, pol.idimct.xlsiloxane, whose end is modified, and polydyrethylsiloxane, both ends and side chains are modified. Among these surfactants, polio-modified silicone surfactants with a polyoxyethylene group, or a polyethylene polyoxypropylene group are preferable due to the display of good properties as surfactants.
    Synthetic silicone surfactants or commercial products can be used as the silicone surfactant. For example, marketed products may be available from BYK Chemie GmbH, Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nihon Emulsion and Kyoeisha Chemical Co., Ltd.
    The surfactant of the polyether modified silicone mentioned above is not particularly limited. For example, compounds in which a polyalkylene oxide structure is incorporated into a side chain connected with a Si atom and a diinotylpolysiloxane chain, and which has the formula ( 11) can be used below.
    wherein each of II, n, a and b is independently an integer, and each of R and R 'independently represents an alkyl group or an alkylene group.
    As for the polyether-modified silicone surfactants, the marketed products can be used. Specific examples thereof include KB'-618, KF-642 and KF-643, which are manufactured by Shin-Etsu Chemical Co., Ltd .; EMALEXs 33-5602 and SS-1906EX, which are manufactured by Nihon Emulsion CO., Ltd .; FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163 and FZ-2164, which are manufactured by Dow Corning Toray Silicone Co., Ltd .; and BYK.-33 and BYK-387, which are manufactured by HYK Chemie GmbH.
    Specific examples of the anionic surfactants mentioned above include polyoxyethylenealkyl ether acetates, alkoxybenzenesulfonates, laurates and polyoxyethylene alkylthylsulfates.
    Specific examples of the aforementioned non-phonic surfactants include polyoxyethylenealkyl ethers, polyoxypropylene polyoxyethylenealkyl ethers, polyoxyethylenealkyl esters, polyoxyethylalkylamino ethylene ethylene polyoxyethylalkylphenyl fatty acid esters.
    The content of such a surfactant in the paint is preferably from 0.001 to b $ by weight, and more preferably from 0.05 to 1% by weight, based on the total weight of the paint. When the content is less than 0.001 $ cm poso, the effects of the surfactant are hardly produced. Conversely, even when the content is increased to be greater than 5% by weight, effects are almost the same as those in a case where the content is from 0.001 to 5% in weight.
    The ink preferably includes a penetrant to provide a good combination of the penetration property or water solubility for the ink. For example, it is preferable to include one or more of the non-wettable polyol compounds or glycol ether compounds, which have 8 to 11 carbon atoms, in the ink. In this regard, a "non-wettable" compound means a compound with water solubility of 0.2% to 5.0% by weight at 25 ° C.
    Among these compounds, 1,3-diol compounds having the formula mentioned below (12) are preferable as the penetrant. In addition, 2-otyl-1, S-hexanediol (solubility of 4.2% by weight at 25 ° C) and 2,2,4-r.rimethyl- * 1,3 '* pcntanodiol (solubility of 2.0 % by weight at 25 ° C) are more preferable.
    wherein R 'represents a methyl group, or an ethyl group; R represents a hydrogen atom, or a methyl group; and R '''represents an ethyl group, or a propyl group,
    Specific examples of other non-wettable polyol compounds include aliphatic diols, such as 2-ethyl-2-motile, 3-propanediol, 3, 3-dimethyl-1,2, butanediol, 2, 2 "diethyl" 1, 3- propanediol, 2-methyl-2-propyl-1,3-propanediol, 2, u-diraethyl-2,4-pentanediol, 2, S-dimethyl-2,5-hexanedio, and 5-hexene-1,2-diol.
    Other penetrants can be used together with the aforementioned penetrants, as long as the penetrants can be dissolved in the paint, and the properties of the paint can be controlled to fit the desired ranges. Specific examples thereof include alkyl or aryl ethers of polyalcohols such as di-ethylene glycolroonophenyl ether, ethylene glycolraonophenyl ether, ethylene glycol monoamoyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether and glycol ether; and lower alcohols, such as ethanol.
    The penetrant content in the paint is 0.1% to 4.0% by weight, based on the weight of the paint. When the content is less than 0.1% by weight, the fast drying property cannot be imparted to the ink, and therefore, blurred images will tend to form. In contrast, when the content is greater than 4.0% by weight, the stability of the dye dispersion tends to deteriorate, thus causing the nozzle clogging problem. In addition, the Line tends to penetrate excessively into recording papers, thereby forming defective images such as low density images and images penetrated where ink images recorded on a surface of the recording medium penetrate the back side of the recording medium.
    The ink may optionally include a dispersion of aqueous resin (i.e., resin dispersed in water). Among various dispersions of aqueous resin, aqueous resin dispersions with good filmmaking ability (image forming ability), high water repellency and high weather resistance are preferable. When using such aqueous resin dispersions, impressions with good water resistance and high image density (good coloring property) can be produced. Materials suitable for use as the resins of such aqueous resin dispersions include condensation-type synthetic resins, resins addition-type synthetic and natural polymeric compounds.
    Specific examples of such synthetic condensation-type resins include polyester resins, polyurethane resins, cpoxl resins, polyamide resins, polyether resins, acrylic poly (honey) resins, silicone-acrylic resins and fluorine-containing resins.
    Specific examples of such synthetic resins for addition include polyolefin resins, polystyrene resins / polyvinyl alcohol resins / polyvinyl ester resins, acrylic resins and unsaturated carboxylic acid resins.
    Specific examples of such natural polymeric compounds include cellulose resins, rosins and natural rubbers.
    Among these aqueous resin dispersions, aqueous dispersions of fine particles of a polyurethane resin, aqueous dispersions of fine particles of an acrylic-silicone resin and aqueous dispersions of fine particles of a fluorine-containing resin are preferable <These aqueous resin dispersions may be used alone or • together.
    Among the particulate fluorine-containing resins for use as the aqueous resin dispersion, particulate fluorine-containing resins having a fluorolefin unit are preferred, and fluorine-containing vinyl ether resins with a fluorolefin unit and a vinyl ether unit are more preferable.
    Specific examples of the fluorolefin unit include -CL'jCFz-, CFzCFÍCÍSH and - CFZCFC1-.
    The vinyl ether unit is not particularly limited. Specific examples of the vinyl ether unit include groups that have the following formulas.

    Among the above-mentioned particulate fluorine resins having a fluorolefin unit and a vinyl oxide unit, alternative copolymers, in which one alternately bonded, are preferable.
    In this regard, it is possible to use synthesized aqueous resin dispersions or products marketed therefrom. Specific examples of the products marketed include the FLUONATES FEM-500 and FEM-600, DICGUARDs F-52S, F-90, F-90M and F-90N, and AQUAFLAN TE-5A, which are manufactured by DXC Corporation; LÜMIFLONs FF.4300, FE4500 and FE440O, c ASAHJGÜARDs AG-7105, AG-950, AG-7600, AG-7000 c AG-1100, which are manufactured by Asahi Glass Co., Ltd.
    Aqueous dispersions of homopo.l.iπieros, copolymers and complex resins can be used for aqueous resin dispersions. In addition, the type of aqueous dispersions is not particularly limited, and single-phase emulsions, core-shell emulsions and power-supply emulsions can be used.
    Aqueous dispersions of the self-dispersing resins, having a hydrophilic group, and aqueous dispersions of the resins which do not self-disperse and which are dispersed in an aqueous medium using a surfactant or a resin with a hydrophilic group, can be used for resin dispersions above mentioned aqueous solution. Among these aqueous resin dispersions, resin emulsions including particulate resins such as ionomers of polyester resins and polyurethane resins, and resins prepared by subjecting unsaturated monomers to emulsion polymerization or suspension polymerization may be used.
    When preparing resin emulsions by performing emulsion polymerization, methods in which components 5 such as an unsaturated monomer, a polymerization initiator, a surfactant, a bitch transfer agent, a chelating agent and a pH control agent react in water are normally used. Therefore, resin emulsions can be easily prepared. In addition, since the composition of the resins can be easily changed, dispersions of resins with desired properties can be easily prepared.
    Materials suitable for use as the unsaturated monomer include unsaturated carboxylic acid monomers (such as acrylic acid, methacrylic acid, itaoonic acid, fumaric acid and maleic acid) mono- or polyfunctional (meth) acrylate monomers, (meth) acrylate monomers, vylinyl monomers, vinyl monomers, vinyl monomers, allyl compounds, olefin monomers, diene 20 monomers and unsaturated carbon oligomers, which can be used alone or together. Using such monomers alone or in combination, the properties of the resulting resins can be modified flexibly. In addition, by carrying out polymerization reactions or graft reactions using an oligomer-type polymerization initiator, the properties of the resins can be modified.
    Specific examples of the monofunctional (meth) acrylate monomers mentioned above include (methyl) 5-methyl acrylate, (meth) ethyl acrylate, (meth) isopropyl acrylate, (meth) n-butyl acrylate, (ie) butobutyl acrylate , (meth) n-amyl acrylate, (meth) isoamyl acrylate, (mot) n-hexyl acrylate, (meth) 2-ethylhexyl acrylate, (met) octyl acrylate, (meth) decyl acrylate , 10 (meth) dodecyl acrylate, (meth) octadecyl acrylate, (meth) cyclohexyl acrylate, (meth) phenyl acrylate, (meth) benzyl acrylate, (meth) glycidyl acrylate, (meth) acrylate of 2-hydroxyethyl, (meth) acrylate of 2-hydroxypropyl, (meth) acrylate of dimethyl.1 aminoethyl, salt of 15 (meth) acryloxyethyltrimethyl ammonium and 3-methacryloxypropyltrimotoxysilane.
    Specific examples of the aforementioned polyfunctional (mot) acrylate monomers include ethylene glycol dimethacrylate, methylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate; 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, 4-polyethylene glycol, 4-dimethyl glycol, 4-dimethyl glycol; methacryloxydiotoxyphenillopropyl, trimethylolpropane triniethacrylate, trimethylolethane trimethacrylate, polyethylene glycol diacrylate, 5 triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butyl diarylate, diacrylate, 1,4-butyl diarylate, diacrylate, 1,4-butyl diarylate 1,9 "nonanediol, polypropylene glycol diacrylate, 2,2'-bis (4-acryloxypropyloxyphenylOpopane, 2,2'-bis (4-acryloxydiethoxyphnyl) propane, trimethylolpropane triacrylate, trimethylethyl triacrylate, tetramethyl triethyl acetate, tetramethyl triletrate, tetramethyl tetrahydrate. tetramethylolmethane tetracrylate, poπtaerythritol tetracrylate and d.ipentaex itritol hoxacrylate Specific examples of the monomers of (meth) acrylamide mentioned above include acrylamide, methacrylamide, N, N-dimethylacrylamide, meUlenobisacrylamide and 2 * -acrylatin-2-methylpropyl sulfonic acid.
    Specific examples of the aforementioned vinyl aromatic monomers include styrene, α-methylstyrene, vinyl toluene, 4-t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene or djVJnilbenzene. mentioned include acrylonitrile and methacryl onitrile.
    Specific examples of the vinyl monomers mentioned above include vinyl acetate, vinylidene chloride, vinyl chloride, vinyl ether, vinyl ketone, vinyl pyrrolidone, vinyl sulfonic acid and salts thereof, vinyl trimethoxysilane and vinyl triethoxysilane.
    Specific examples of the aforementioned allyl compounds include allylsulfonic acid and salts thereof, alylamine, allyl chloride, diallylamine and diallyldimethylammonium salts,
    Specific examples of the olefin monomers mentioned above include ethylene and propylene.
    Specific examples of the aforementioned diene monomers include butadiene and chloroprene.
    Specific examples of the aforementioned unsaturated carbon oligomers include styrene oligomers having a methacryloyl group, methyl methacrylate ligamers with a methacryloyl group, dimethylsiloxane oligomers with a methacryloyl group or the polyester oligomers with an acrylic ester group.
    When the aqueous resin dispersions mentioned above are present under strong alkaline or acidic conditions, the dispersions are destroyed or cut through the molecular chain, such as powder. hydrolysis. Therefore, the pH of the aqueous resin dispersions is preferably from 4 to 12, and from the point of view of miscibility with dyes that disperse in water, the pH is more preferably from 6 to 11 and even more preferably from 7 to 9.
    The volume of the average particle diameter (D50) of the aforementioned aqueous resin dispersions corresponds to their viscosity, and as the particle diameter of the aqueous dispersions of a resin decreases, the viscosity of the aqueous dispersions increases when the solids content 10 of the aqueous dispersions are the same. In order that a resulting ink does not have an excessively high viscosity, the volume of the average particle diameter (D50} of the dispersion of the aqueous resin used for the ink is preferably not less than 50 nm. When the volume of the average particle diameter 35 (D5Q) is in the order of tens of micrometers, the resin particles are larger than the diameter of the inkjet nozzles and therefore the aqueous resin dispersion cannot be used for the paint, even when the volume of the dc diameter average particle (1) 50) of an aqueous dispersion of resin 20 is smaller than the diameter of the inkjet nozzles, the ink ejection property deteriorates if the resin dispersion includes resin particles with a particle diameter greater than the diameter of the inkjet nozzles. Therefore, the volume of the average particle diameter (D50) of the aqueous resin dispersion used for the paint is initially not greater than 200 nm, and more preferably not greater than 150 nm.
    Such a dispersion of aqueous resin is included in the ink to increase the ability to fix the dye in the ink for the recording medium such as newspapers. Therefore, the aqueous resin dispersion preferably has a minimum film-forming temperature (MFT) of a maximum of 30 ° C. Furthermore, when the glass transition temperature of the resin in the aqueous resin dispersion is less than -40 °, a resin film becomes viscous, and the resulting ink images show adhesion. Therefore, the glass transition temperature of the resin of the aqueous resin dispersion is preferably not less than -40 °. the dry basis content of such an aqueous resin dispersion in the paint is preferably 2% to 30% by weight, and more preferably 5% to 25% by weight, based on the weight of the paint.
    The contents of the dye and resin (included in the aqueous resin dispersion) in the ink, and the content of the pigment in the dye are determined by a method in which only the dye and resin (mixture) are separated from the ink. When a pigment is used as a dye, the mixture is subjected to a thermal mass analysis to determine the ratio of the dye to the resin of the aqueous resin dispersion, based on the rate of decrease in mass. If the molecular structure of the dye is known, the solids content of the dye can be determined by NMR if the dye is a pigment or dye. If the dye is an inorganic pigment, a metal-containing organic pigment or a metal-containing dye, which includes a heavy metal atom in a molecular chain, the mixture is subjected to a fluorescent x-ray analysis to determine the solids content of the dye in the mixture.
    The ink for use in the imaging method of the present invention can optionally include other components such as pH control agents, antiseptics / fungicides, chelating agents, antirust agents, antioxidants, ultraviolet absorbers, oxygen absorbers and light stabilizers.
    The pH control agent is not particularly limited, and the pH control agent. which do not adversely affect the ink and which can control the pH of the ink in a pH range of 7 to 11, can be used for the ink. Materials suitable for use as the pH control agent include alcohol amines, alkali metal hydroxides and ammonium hydroxides, phosphonium hydroxides and alkali metal carbonates.
    When the pH of the ink is less than 7 or greater than 11, the ink tends to easily dissolve the recording heads and ink supply units, thus causing problems as the properties of the ink are changed; ink seeps from recording heads and ink supply units; and the ink is poorly expelled from the recording heads.
    Specific examples of the alcohol amines include diethanolamine, triethanolamine and S-amino-Z-ethyl-1,3-propauodiol.
    Specific examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide and potassium hydroxide.
    Specific examples of ammonium hydroxides include ammonium hydroxide, quaternary ammonium hydroxide and quaternary phosphonium hydroxide.
    Specific examples of alkali metal carbonates include lithium carbonate, sodium carbonate and potassium carbonate.
    Specific examples of antiseptics / fungicides include sodium dehydroacetate, sodium sorbate, sodium salt of 2-pyridinethiol-1-oxide, sodium benzoate and sodium salt of pentachlorophenol.
    Specific examples of chelating agents include sodium salt of ethylenediaminetetraacetic acid, sodium salt of nitrilotriacotic acid, sodium salt of hydroxyethylethylenediaminetriacetic acid, sodium salt of diethylenetriaminopentacetic acid and sodium salt of uramydiacotic acid.
    Specific examples of antirust agents include acid sulfites, sodium thiosulfate, ammonium thioglycolate, dl-isopropylammonium nitrite, pentaerythritol tetraacetate and dicyclohexylammonium nitrite.
    Materials suitable for use as antioxidants include phenolic antioxidants (including hindered phenol-type antioxidants), amine-type antioxidants, sulfur-containing antioxidants and phosphorus-containing antioxidants.
    Specific examples of phenolic antioxidants include butylated hydroxanisol, 2, δ-di-tert-butyl-4-otylphenol, stearyl-β- (3,5 "di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol}, 2,2'-methylenebis (4-ethyl V-6-tert-butylphenol), 4,4'-butylidenobis (3 * -methyl-6-torc-butylphenol}, 3, 9-bis (1,1-dimethyl-2- (β- (3-tert-botyl-4-hydroxy1-5 "methylphonyl) propionyloxycyl) -2,4, U, 10-tetraoxaspiro [5.5] undecane , 1,1,3-tris (2-methyl-4 "hydroxy-5-triethyl butyl) butane, 1, 3, 5-trimetif-2, 4- 6-tris (3, 5-di- tera-butyl-4-hydroxybenzyl) benzene and tetrakis [melylene-3- (3 ', 5'-di-Lerc-butyl-4'-hydroxyphenyl) propionate] methane.
    Specific examples of ainine-type antioxidants include α-naphthylamine, α-naphthylamine, N, N'-di-sec-butyl-p-phenylenediamine, phenothiazine, N, Nz-di-phenyl-p-fonylenediamine / 2,6 -di-tert-butyl-p-crosol, 2,6-di-tert-butylphenol, 2,4 "diraethyl-6-tert-butylphenol / butylhydroxyanisole, 2,2'-methylenebis (4-methyl, -6-terc - butylphenol) t 4,4'-butylidenobis (3-methyl-6-tert-butylphenol}, 4,4'-thiobis (3-methyl-6-tert-butyl phenol), tetrakis [methylene-3- (3, 5-di "tert-butyl-4-dihydroxyphenyl) propionate] motane, and 1,1, 3-tris {2-methyl-4-hydroxy-5 ~ tert-butyphenyl) butane.
    Specific examples of sulfur-containing antioxidants include dilauryl-3,3 '"thiodipropionate, distearl thiodipropionate, laurilstearyl thiodipropionate, dimiristyl-3,3' -thiodipropionate, di-stearyl-β, β'-thiodipropionate, 2-mercaptoethyl deatylate and benzoyl dioxide.
    Specific examples of phosphorus-containing antioxidants include triphenylphosphite, octadecylphosphite, triisodecylphosphite, trilauryltrithiophosphite and trinonylEcnylphosite.
    Materials suitable for use as the ultraviolet absorber include benzophenone-type ultraviolet absorbers, benzotriazole-type ultraviolet absorbers, salicylate-type ultraviolet absorbers, cyanoacrylate-type ultraviolet absorbers and nickel-type ultraviolet absorbents.
    Specific examples of benzophenone-type ultraviolet absorbers include 2-hydroxy-4 - n "Octoxibonzo-enone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 5 2" hydroxy "4-inethoxybenzophenone and 2 , 2 ', 4,4'-tolra * - hydroxybenxophonone.
    Specific examples of benzotriazole-type ultraviolet absorbers include 2- (2'-hydroxy-5'-t-octylphenyl) benzoIriazole, 2- (2'-hydroxy-5 '- methylenyl) benzotriazole, 2- (2'-hydroxy "4'- octoxyphenyl) benzotríazole, and 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.
    Specific examples of salicylate-type ultraviolet absorbers include phenyl salicylate, 15 p-t-butylphenyl salicylate and p-octylphenyl salicylate.
    Specific examples of cyanoacrylate type ultraviolet absorbers include ethyl ~ 2-cyano ^ 3,3'-diphenyl acrylate, methyl-2-cyano'-3-methyl-3- (p-methoxyphonyl) acrylate and buttl- acrylate 2-cyano-3-methyl-3- (p-20 methoxyphenyl).
    Specific examples of the nickel complex type ultraviolet absorbers include nickel sulphide (octllphenyl), 2,2'-thiobis (4-1-octiIferrate) -n ”nickel (II) butilaπdna, 2,2'-thiobis (4- πiqxjel (II) t-octylferrate) -2-hexylamine (II) and nickel (II) 2,2'-thiobie (4-t-octyferrate) triethanolamine.
    The method for preparing the ink for use in the imaging method of the present invention will be described.
    The ink can be prepared by a known method. For example, components of the paint such as a dye, an organic solvent, a surfactant and water (and other optional components) are mixed or stirred using a mixer such as a sand mill, a good mixer, a ball mill, a paint stirrer and a supersonic dispersion machine. The mixing and stirring list can also be performed by a stirrer with a stirring ISmin, a magnetic stirrer and a high speed dispersing machine.
    The resulting ink can be used while contained in a container, such as ink cartridges.
    The property of the ink is not particularly limited, and is suitably determined so that the ink can be used satisfactorily for the targeting apparatus. However, the ink preferably has a viscosity of 5 to 25 mPa.s at 25 ° C. When the ink has a viscosity of at least 5 mPa.s, effects to improve the image density and the image quality of the character can be produced. In addition, when the ink has a viscosity of at most 25 mPa.s, the ink has good ejection properties. In this respect, viscosity is measured at 25 ’c using a viscosimeter like RE-550L, from Toki Sangyo Co., Ltd.
    The paint profferably has a static surface tension of a maximum of 30 mN / m at 25 * C, and more preferably a maximum of 28 mN / m. When the static surface tension is not greater than 30 mN / m, the Lcm ink has good penetration properties, and in this way, the ink images 10 can be quickly dried on embossing papers without causing the problem of pearl formation. In addition, the ink has good wettability against pre-treatment layers, which * are often formed in the recording medium before the ink images are recorded, and therefore the resulting ink images 15 have good coloring properties. without defective images, such as white dot images. When the static surface tension is greater than 30 IRN / HI, the ink cannot be satisfactorily leveled in the recording medium, thus increasing the drying time of the ink images (i.e., 20 deteriorating the ink drying property).
    The aforementioned ink can only be used for any inkjet printers with an inkjet recording head. Specific examples of such printers include the following: (J) Piezoelectric inkjet printers (such as a printer disclosed by JP II2'-51734A) r where a piezoelectric device is used as a pressure generating device to press an ink into a 5 ink pass, and a vibrating plate forming a wall of the ink pass is deformed by the piezoelectric device to change the volume of the ink pass to eject ink droplets from the ink pass, thus forming a tin image on a recording medium ; (2) Thermal inkjet printers (such as a printer disclosed by JP S63.-59911A), where an ink in an ink pass is heated by heating a resistor to form an air bubble in the ink pass, mode ejecting ink droplets from the ink passage, .15 resulting in the formation of an ink image on a recording medium; and (3) Electrostatic inkjet printers (such as a printer disclosed by JP H06-71882A), in which an electrostatic force is formed between a vibrating plate and an electrode opposite the vibrating plate to deform the vibrating plate and alter the volume of the ink pass, in this way ejecting ink droplets from the ink pass, resulting in the formation of an ink image on a recording medium,
    Then, the pre-treatment liquid for the after-treatment of a recording medium will be described.
    The pre-treatment liquid for use in the imaging method of the present invention includes at least water and a water-soluble aliphatic organic acid and, optionally, includes a water-soluble organic tnonoamine compound, an organic acid ammonium salt , a water-soluble cationic polymer, an aliphatic organic acid salt compound, an inorganic metal salt compound, an organic solvent, a surfactant and a penetrant.
    Water soluble aliphatic organic acids have a particle-binding property of a dye available in water. In this respect, "agglutinated" means a phenomenon, such that the particles of a water-dispersible dye are adsorbed with each other and aggregated. Whether a dye clumps or cannot be determined by using an instrument for measuring the particle diameter distribution.
    When an ionic material, such as water-soluble aliphatic organic acids, is added to the pretreatment liquid, ions of the ionic material are adsorbed on the charges on the surface of the water-dispersible dye, thereby intensifying the agglutination effect caused by intermolecular forces , resulting in the agglutination of the dye particles. In order to determine whether a dye in an ink can be bonded, a method in which 30 ml of the pre-treatment liquid is added to 5 μl of the ink, including the dispersive dye! in water, in an amount of 5% by weight, and observing the mixture to determine if the dye is agglutinated at one time, can be used.
    Materials suitable for use as water-soluble aliphatic organic acid include water-soluble organic alpha acids, including a carboxyl group, or a sulfonic acid group »In this regard," aliphatic organic acids "means organic acids with a linear hydrocarbon group or branched, which is saturated or unsaturated. The number of carbon atoms included in the water-soluble aliphatic organic acid is not particularly limited, and the number of carbons is preferably 2 to 6 in a molecule, and more preferably 2 to 4, from the point of view of solvent solubility. . In addition, the number of acid groups included in the water-soluble aliphatic organic acid is preferably 1 to 3 in a molecule, more preferably 1 to 2, and even more preferably 1, from the point of view of the density of Image.
    Among these water-soluble organic uliphalic acids, water-soluble organic aliphatic acids including a carboxyl group, having the formula (V) below, are preferable-
    where RÓ represents a hydrogen atom, or a 5-ractyl group substituted with a hydroxyl group or a carboxyl group, and R represents a methyl group, a methyl group substituted with a carboxyl group or a methyl group substituted with a hydroxy group and a carboxyl group.
    Specific examples of such compounds with formula (V) 10 include Lactic acid (pKa of 3.83), malic acid (pKa of 3.4), citric acid (pKa of 3.13) and tartaric acid (pKa of 2, 93).
    Specific examples of water-soluble aliphatic organic acids having a formula other than formula (V) 15 include gluconic acid (pKa dc 2.2), pyruvic acid (pKa 2.49) and fumaric acid (pKa 3, 02).
    Among the water-soluble aliphatic organic acids with a sulfonic acid group, taurine is preferable.
    The content of such water-soluble allylated organic acid 20 in the pre-treatment liquid is preferably 1% to 40% in weight, and more preferably 3% to 303 weight, based on the total weight of the pre-treatment liquid. . When the content is greater than -10% by weight, it becomes impossible to include a water-soluble organic monoamine in the pretreatment liquid in an amount necessary for neutralization.
    On the contrary, when the content is less than 13 in weight, the effect of improving the image quality is hardly produced.
    The pre-treatment liquid preferably includes a water-soluble organic monoamine compound to control the penetration of the ink into the recording medium and to prevent a metal that constitutes a pre-treatment liquid coating device from being corroded.
    Any primary to quaternary amines and salts thereof can be used as the water-soluble organic monoamine compound 15. In this regard, quaternary amines means compounds in which a nitrogen atom has four alkyl groups as substituents. The carbon number of such water-soluble organic monoamine compounds is not particularly limited, but is preferably from 2 to 12 20 in a molecule, and most preferably from 2 to 6.
    Among the various water-soluble organic monoamine compounds, compounds of formula (VI} or (VII) below are preferred.
    was that each uro of Ha / Rs and independently represents a hydrogen atom, an alkoxyl with 1 to 4 carbon atoms, an alkyl group with 1 to 8 carbon atoms, a hydroxyl group or a hydroxypropyl group, where a case 5 where each of Rδ, Ra ® RÍO 6 a hydrogen atom is excluded,
    where Rn represents a hydroxymethyl group, Ru represents a methyl group, an ethyl group or a hydroxymethyl group, and Ria represents a hydrogen atom, an alkyl group having 10 from 1 to 4 carbon atoms, or a hydroxymethyl group.
    Specific examples of compounds in formula (VI) include dimethylamine, ethylamine, diethylamine, trictylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, n-butylamine, t-butylamine, sec-butylamine, 15 di-n-butylamine, tributylamine, pentylamine, diptylamine, tetraphenolamine, 2-otylhexylamine, di-2-ethylhexylamine, di-n-octylamine, tri-n-oethylamine, 1 - amino-'2-propanol, 3- araJno-1-propanol, N-methylethanolamine, N, N-dictyltanane.amine, N, N-dimotilotanolamine, N-methyldiethanolamine, dietunolamine, triethanolamine, triisopropanolamine, N-butyldiethanolamine and N, N "dibutyl butanolanu na.
    Specific examples of compounds having formula (VII) include Z-amino-Z-ethyl-1,3-propanediol, 2-amino-2- (hydroxymethyl) -1,3-propanediol, Z-amino-Z-nietii -1, 3-propanediol and Z-amino-2-methyl-1-propanol.
    Specific examples of water soluble organic monoaraine 10 compounds with formulas other than formulas (VI) and (VII) include allylamine, diallylamine, 3-ethoxypropylamine, 2- (2-aminoethoxy) ethanol, 3-methoxypropylamine and choline.
    The added amount of such water-soluble organic monoamine 15 is preferably 1.0 to 1.5 mol, and more preferably 1.0 to 1.2 mol based on 1 mol of the acid group of the soluble aliphatic organic acid in water included in the pre-treatment liquid. When the amount added is less than 1.0 mol, the diameters of the 20 dot ink images tend to narrow, making it possible to cause a white line image. Conversely, when the amount added is greater than 1.5 mol, a water-soluble organic monoamine tends to accelerate the penetration of the ink, thereby increasing the density of the image.
    Such a water-soluble organic raonoantine compound is added to the pre-treatment liquid to produce a salt neutralized with a water-soluble aliphatic organic acid and to control the pH of the pre-treatment liquid, so as not to be less than 5. Therefore, it is preferable to determine the added amount of such a water-soluble organic monoamine compound based on the molecular weights of the water-soluble organic monoamine compound and the water-soluble aliphatic organic acid included in the pretreatment liquid.
    The pretreatment liquid can include an ammonium salt of organic acid instead of a water-soluble aliphatic organic acid, or together with a water-soluble aliphatic organic acid. In this case, effects similar to those produced by water-soluble organic aliasic acids can be produced,
    Suitable materials for use as the organic acid ammonium salt include organic acid ammonium salts having the formula mentioned below (13) from the point of view of water solubility, balance between acidity and alkalinity of the ions dissociated therefrom and ability to form chelate.
    did one of Ri and R fall independently represents a lower alkyl group.
    The number of carbons in the organic acid ammonium salt is not particularly limited, but is preferably not greater than 6 in a molecule from the point of view of water solubility.
    Specific examples of the ammonium salt of organic acid include ammonium lactate and ammonium acetate.
    The added amount of the organic acid ammonium salt is preferably 1% to 40% by weight, and more preferably 3% to 30% by weight, based on the total weight of the pre-treatment liquid. Even when the amount added is increased to more than 40% by weight, the effect of improving image quality is hardly improved, and the viscosity of the pre-treatment liquid tends to increase. Otherwise, when the quantity added is less than 1% by weight, the effect of improving image quality is hardly produced.
    The pretreatment liquid may include a water-soluble cut ionic polymer instead of a water-soluble aliphatic organic acid, or in combination with a water-soluble aliphatic organic acid. In this case, affections similar to those produced by water-soluble aliphatic organic acids can be produced.
    Materials suitable for use as a water-soluble cationic polymer include water-soluble cationic polymers prepared by the polymerization of monomers including an alkali and an epihalohydrin. Such water-soluble cationic polymers include a hydroxyl group and an ammonium cation in the main chain of the same which liberate a halogen anion from water, thus reinforcing a buffering effect and a pigment agglutination effect upon contact with the ink,
    Specific examples of the water-soluble cationic polymer include polyiaraine-epi-halohydrin copolymers, polyamide-epi-halohydrin copolymers, poly-afraidopollar na-epi-halohydrin copolymers and glass-amino-epihalohydrin copolymers. Among these water-soluble cationic polymers, copolymers having the formula mentioned below (J4), copolymers including a repeating unit having the formula mentioned below (15) the copolymers obtained from an amine having the formula mentioned below (16), a monomer with u below mentioned formula (17) u a monomer having the below mentioned formula (18) are preferable
    where each one of Ri 'Rzi independently represents an alkyl group having from 1 to 8 carbon atoms, a hydroxyalkyl group, an alkeny group or a benzyl group (Ru to R j are the same or different from each other); X represents a halogen atom 5 and n is an integer from 1 to 4.
    where X represents a halogen atom and is a positive integer.
    where X represents a halogen atom.
    Specific examples of the amine monomers include diethylenetriamine, triethylenetetramine, tetramethylonopentamine and iminobispropylamine. Among the amine monomers, monomers having the formula (14) are preferable.
    Other quaternary ammonium salt-type cationic polymers and water-dispersible cationic polymers can be used as water-soluble cationic polymers.
    The aforementioned water-soluble cationic polymer can be prepared by methods known as a method in which the monomers, including an amine and an epi-halohydrin, are polymerized, and a method in which a monomorine, including an epi-ha.l ohydrin it is polymerized by grafting with a polyamide obtained by polymerizing monomers, including an amine and a carboxylic acid.
    The average molecular weight of the water-soluble cationic polymer included in the pretreatment liquid is preferably 500 to 100,000 when the water-soluble cationic polymer is a polyamine-epihalohydrin copolymer. When the water-soluble cationic polymer is a copolymer of polyamide-epihalohydrin or a copolymer of polyamidopylamine-epihalohydrin, the average weight molecular weight is preferably 10,000 to 5,000,000. When the water-soluble cationic polymer is an amine-epihalohydrin copolymer, the average weight molecular weight is preferably 700 to 50,000. When the weight average molecular weight is greater than the preferred range, there is a case where an aqueous solution of copolymer cannot be prepared. Conversely, when the average molecular weight is less than the preferred range, the pretreatment effects tend not to be produced satisfactorily.
    The amount of such water-soluble cationic polymer added is preferably 1% to 40% by weight, and more preferably 3% to 30% by weight, based on the total weight of the pre-treatment liquid. When the amount added is increased to more than 40% by weight, the effect of improving image quality is hardly improved, and the viscosity of the pre-treatment liquid tends to increase excessively. Conversely, when the amount added is less than 1% by weight, the effect of improving image quality is hardly produced.
    When an aliphatic organic acid salt or a compound of inorganic metal leaves is included in the pre-treatment liquid, the pigment included in the ink tends to remain on the surface of the recording medium, thereby producing a good salting-out effect, resulting in increasing the density of the image.
    Specific examples of such a salt of α-glycatic organic acid include sodium L-aspartate, magnesia l-aspartate, calcium ascorbate, sodium L-ascorbate, sodium succinite, disodium succinate, diamonium succinate, aluminum citrate, potassium citrate , calcium citrate, 5 triamonium citrate, tripotassium citrate, trisodium citrate, diamonium citrate, disodium citrate, zinc lactate, aluminum lactate, ammonium lactate, potassium lactate, calcium lactate, sodium lactate, lactate magnesium, potassium tarlarate, calcium tartrate, DL-10 sodium tartrate and sodium and potassium tartrate.
    Specific examples of such an inorganic metal salt compound include magnesium sulphate, aluminum sulphate, manganese sulphate, nickel sulphate, lining (II) sulphate, copper (II) sulphate, zinc sulphate, sodium sulphate potassium, lithium sulfate, sodium hydrogensulfate, potassium hydrogensulfate, iron (II) nitrate, iron (III) nitrate, cobalt nitrate, strontium nitrate, copper (II) nitrate, nickel (II) nitrate , lead (II) nitrate, manganese (II) nitrate, sodium nitrate, potassium nitrate, nickel (II) chloride, calcium chloride, tin (TI) chloride, strontium chloride, barium chloride, chloride magnesium, sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.
    The pretreatment liquid preferably includes an organic solvent to control penetration of the ink control or to prevent corrosion of the metals that make up the recording heads. Organic solvents similar to those mentioned above for use in the paint can be used for the pre-treatment liquid.
    A voice that such organic solvents can contain water even when they are allowed to decant in an open state, good fluidity can be given to the pre-treatment liquid. In this regard, it is preferable to use an organic solvent with a high equilibrium moisture content in order to avoid excessive increase in the pre-treatment liquid viscosity even when the water in the pre-treatment liquid evaporates. This is because the solvent and water reach an equilibrium state in the pre-treatment liquid.
    The content of such an organic solvent in the pre-treatment liquid is not particularly limited, but is preferably 10% to 80% by weight, more preferably Intent from 1.5% to 60% by weight, based on the total weight of the pre-treatment liquid, When the content is greater than 80% by weight, the recording medium coated with the pre-treatment liquid tends to have a long drying period, although the drying time changes depending on the property of the solvent used. When the content is less than 10% by weight, the water tends to evaporate in the pretreatment process, thus often changing the formula of the pretreatment liquid, the pretreatment liquid may include a surfactant pure improve the wettability of the surfaces of the recording medium, thus improving the image density and saturation of the recorded images without forming white dot images. In this regard, it is preferable that the pre-treatment liquid, including a surfactant, has a static surface tension of a maximum of 30 mN / m to improve the wetting of the surfaces of the recording media and the property of ink penetration into the medium recording.
    The nonionic surfactants, anionic surfactants, 15 betaine surfactants, silicone surfactants or fluoride-containing surfactants mentioned above for use in the paint can preferably be used for the pretreatment liquid. s Among these surfactants, silicone surfactants and fluoride-containing surfactants, which can control the static surface tension so as not to be greater than 30 mN / m, are more preferable. These surfactants can be used alone or together,
    The surfactant content in the pre-treatment liquid is preferably from 0.001 to 5% by weight, and more preferably from 0.05 to 1% by weight, based on the total weight of the pre-treatment liquid. When the content is less than 0.001% by weight, the effects of the surfactant are unlikely to be produced. On the contrary, even when the content is increased by 5 to be greater than 5% by weight, the effects are hardly improved.
    Similar to the aforementioned ink, the pretreatment liquid preferably includes a penetrant such as non-wettable polyether compounds or glycol ether compounds, which have 8 to 11 carbon atoms in order to have a good combination of penetrating properties. solubility in water. The term “non-wetting” is defined above. In addition, preferable penetrants, non-wettable polyol compounds and other penetrants that can be used together with the penetrants are similar to those mentioned above with respect to paint.
    The penetrant content in the pre-treatment liquid is preferably 0.1% to 5% by weight, based on the total weight of the pre-treatment liquid. When the content is less than 20% by weight, the effects of the penetrant are hardly produced. On the contrary, when the content is increased to be greater than 5% by weight, the effects are not improved because the penetrants have low solubility. in solvents they tend to be separated from solvents.
    Other components such as antiseptics / fungicides and antirust agents can optionally be used for the pre-treatment liquid, and the materials mentioned above for use in the paint can also be used for the pre-treatment liquid.
    In the following, the post-treatment liquid used for the inkjet etching method of the present invention will be described. The foot-treatment liquid includes a component capable of forming a transparent protective layer on a surface containing the image of a recording medium. For example, the post-treatment liquid includes a water-dispersible resin, an organic solvent, a penetrant, a surfactant and water, and optionally includes other components. Although the components of the post-treatment liquid are changed depending on the method of application of the post-treatment liquid (such as coating methods or spraying methods), the post-treatment liquid preferably includes a resin component, which it is polymerized when irradiated with ultraviolet rays, 20 to give high brightness to the images recorded in a recording medium, while protecting the images (that is, to improve the brightness and the ability to fix the images). In order to improve the brightness and the fixability of the images, an aqueous resin dispersion (for example, thermoplastic resin emulsions) is preferably included in the post-treatment liquid. When the post-treatment liquid is sprayed by an inkjet engraving apparatus, the after-treatment liquid preferably includes an organic solvent (a wetting agent) in an appropriate amount. The organic solvents mentioned above for use in the paint and the pre-treatment liquid are preferably used for the post-treatment liquid.
    The water-dispersible resin preferably has a glass transition temperature (Tg) of not less than ~ 30 ° C and, more preferably, from -20 ° C to 100 ° C. When Tg is less than -30 ° C, the resin has similar adhesion to the adhesives after the water evaporates, and is therefore difficult to use in a practical way for the post-treatment liquid. In addition, the dispersive resin! in water it has a minimum film formation temperature (Mi-T) of maximum 50 ° C, and most preferably of maximum 35 ° C- When the MFT is greater than 50 ° C, a resin film may not be formed in a short time, even using a dryer as heaters and hot air blowers and, therefore, it is difficult to use such resin in a practical way.
    The Tg of the resin can be measured with a method such as TMA methods, DSC methods and DMA methods (stress methods), and the MFT can be measured with an MFT measuring instrument.
    Resins suitable for use as water dispersible resins include acrylic resins, styrene acrylic resins, urethane resins, silicone acrylic resins and fluorine-containing resins. Among these resins, the water-dispersible resins mentioned above for use in paint are preferably used.
    The solid content of the dispersive resin! in water in the post-treatment liquid is preferably 1% to 50% by weight, and from 1% to 30% by weight, when the after-treatment liquid is applied by a spray method, based on the total weight of the post-treatment liquid. When the content is greater than 50% by weight, the viscosity of the post-treatment liquid tends to increase excessively. When the content is less than 1% by weight, the post-treatment liquid tends to have poor film forming ability, the energy used for drying the coated after-treatment liquid increases excessively.
    The volume of the mean particle diameter (1150) of the aqueous resin dispersions of the water-dispersible resins refers to their viscosity, and as the particle diameters of the aqueous dispersions of a resin decrease, the viscosities of the aqueous dispersions increase when the solid contents of the aqueous dispersions are the same. Unless the resulting post-treatment liquid does not have an excessively high viscosity, the volume of the average particle diameter (D50) of the aqueous resin dispersion used for the post-treatment liquid is preferably not less than 50 nm. When the volume of the average particle diameter 5 (D50) is in the order of dexenas of micrometers, the resin is larger than the diameter of the popular liquid ejection nozzles o, therefore, the dispersion of the aqueous resin cannot be used for the liquid post-treatment dc. Even when the volume of the mean particle diameter (D50) of an aqueous resin dispersion 10 is less than the diameter of the liquid ejection nozzles, the post-treatment liquid ejection property deteriorates if the resin dispersion include resin particles with a pellet diameter greater than the diameter of the liquid ejection nozzles. Therefore, the volume of the medium particle diameter 15 (D50) of the aqueous resin dispersion used for the post-treatment liquid is preferably not greater than 200 nm, and more preferentially not greater than 350 nm.
    The post-treatment liquid may include an organic solvent. The organic solvents mentioned above for use in the paint or in the pre-treatment liquid can be used for the after-treatment liquid. The content of such organic solvent in the post-treatment liquid is not particularly limited, but is preferably from 10% to 80% by weight, and more preferably from 15% to 60% by weight, based on the weight of the powder liquid. -treatment. When the content is greater than 30% by weight, the post-treatment liquid tends to have a long drying time, although the drying time changes depending on the property of the solvent. When the content is less than 10% by weight, the water tends to evaporate in the post-treatment process, thus often changing the formula of the post-treatment liquid seriously.
    The post-treatment liquid may include a penetrant, a surfactant and other components such as antiseptics, antifoam agents and pH control agents. The penetrants and surfactants mentioned above for use in paint and pre-treatment liquid can be used for the post-treatment liquid.
    With respect to such other components, the materials mentioned above for use in the paint and in the pre-treatment liquid can be used for the after-treatment liquid.
    In the following, the recording medium for use in the imaging method of the present invention will be described.
    The recording medium is not particularly limited, as long as the recording medium has a coating layer on at least one side thereof, or the coating layer has a liquid-absorbing property in a predetermined range. Among these recording media, printing papers such as coated papers, glossy papers, art papers and super art papers are preferable from the point of view of the image qualities of ink,
    Among these printing papers, in order to form ink images with better image qualities (such as image density, saturation, pearl formation and color bleeding), at the same time having high gloss and good fixation capacity with little smear Multi-purpose printing papers with a liquid-absorbing property in a predetermined range are preferable. Specifically, printing papers with a liquid-absorbing property so that when pure water is applied to the surface of the recording medium in a contact time of 100 ms using a dynamic scanning absorption meter, quantities of pure water transferred to printing papers vary from 1 to 10 mL / mz, are preferable. When the amount of pure water transferred is very small, the quantities of the transferred pretreatment liquid and ink also decrease, thereby causing the problem of pearl formation and the problem of color bleeding. Conversely, when the amount of pure water transferred is very large, the diameter of an ink dot image becomes smaller than the desired diameter, thereby decreasing the image density of a solid image.
    The aforementioned dynamic scan absorption meter (DSA) is introduced by Shigenori Kuga at JAPAN TAPPI
    JOURNAL Vol. 48, pp 88-92, May 1994. The DSA can accurately measure the amount of a liquid absorbed by a material in a very short time, the USA uses the following method. (1) The rate of absorption of the liquid is measured by observing the movement of the meniscus of a liquid in a capillary. (2) A liquid-supplying head including the liquid is swirled in a disc-shaped recording medium. This scanning operation is performed repeatedly at predetermined times on different portions of the disk recording medium by changing the scanning speed.
    This scanning operation is performed automatically and in a predetermined pattern.
    The liquid supply head includes a capillary to which the liquid is supplied via a TEFLON tube. The position of the meniscus in the capillary is automatically detected by an optical sensor. In this application, a DSA, type D series K350 from Kyowa Seiko is used, and pure water is used for the liquid. The amount of pure water transferred over a 100 ms contact time is determined by an interpolation method based on the adjacent contact times.
    There are commercially available printing papers that have a liquid-absorbing property in the range mentioned above. Specific examples of these include RICOH BUSINESS COAT GLOSSIOO (with Ricoh Co., Ltd.); OK TOP C0AT +, OK KINFÜJ1 + and SA KINFUJIt (with Oji Paper Co., Ltd.) SUPER MI DAT. and AURORA COAT (with Nippon Paper Industries Co., Ltd.) ci MATT cp COAT (with Hokuetsu Kishu Paper Co., Ltd.); RAICHO ART and RΔICHO SUPER ART (with Chuetsu Pulp & Paper Co., Ltd. ); c PEARL COAT N (with Mitsubishi Paper Mills Ltd.)
    The recording medium for use in the imaging method of the present invention preferably has a substrate and a coating layer, which is formed on at least one side of the substrate and which has the aforementioned liquid-absorbing property,
    The substrate of the recording medium is not particularly limited, and any substrates known as papers made of wood fiber and sheets, as well as nonwoven fabrics made of wood fiber and synthesized fiber can be used.
    Specific examples of the materials that constitute such paper substrates include wood pulps and waste paper pulps.
    Specific examples of wood pulps include LBKP-type pulp and NBKP-type kraft pulp, NBSP-type sulfite pulp, LBSP-type sulfite pulp, crushed pulp (GP) and thermomechanical pulp (TMP).
    Residual papers from the papers mentioned below, which are listed on the waste paper quality specification list prepared by the Japan Paper Recyclagcift Promotion Center, can be used as raw materials for waste paper pulps. (1) unprinted white high quality paper (2) unprinted white coated paper (3) unprinted high quality cream paper (4) cardboard (5) unprinted medium quality paper (6) unprinted white paper black (7} woody paper without printing (8) white paper with color printing (9) white paper or art paper with color printing (10) art paper without printing (11) medium quality paper with color printing (12) paper woody with printing (13) newspaper (14) magazine
    Specific examples of residual papers include residual papers from information technology papers, such as uncoated computer papers; printer papers such as thermal papers and pressure sensitive papers; computer papers (Oft) as papers for copiers of plain paper (PPC); coated papers, such as art papers, coated papers, micro-coated papers and matted papers; c uncoated papers, such as high quality papers, note papers, letter papers, wrapping papers, cover papers, medium papers, newspapers, woody papers, imitation paper, Japanese paper, poster papers coated in machine or papers coated with polyethylene. Chemical pulp papers and high yield pulp papers prepared from one or more of these residual papers can be used for the substrate.
    Waste paper pulps are typically prepared by a method including the following four processes: 1 »Pulping process
    The waste paper is treated using a chemical product and a mechanical strength from a pulper to make fibers, while removing the printing inks from the fibers. 2. Dedusting process
    Foreign materials (for example, plastics) included in the waste paper are removed using a screen or (cleaner).
    The printing inks removed from the fibers using a tensoati.vo are removed from the pulp dispersion by a flotation method or a cleaning method. ú. Bleaching process
    The pulp dispersion is subjected to an oxidation treatment or a reduction treatment to intensify the whiteness of the pounds.
    When the waste paper pulps are mixed with new pulps, the weight ratio of the waste paper pulps is preferably not greater than 00% by weight to prevent the resulting recording medium from curling after the ink images are formed on it.
    Specific examples of the filler to be included in the recording medium substrate include white pigments such as light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthesized silica, aluminum hydroxide, alumina, lithium, zeolite, magnesium carbonate and magnesium hydroxide; and organic pigments such as plastic pigments based on polystyrene, plastic pigments based on acrylic resin, particulate polyethylene, microcapsules, particulate urea resins and particulate melamine resins. These pigments can be used alone or together.
    When the aforementioned substrate is prepared, an internal sizing agent is normally used.
    Specific examples of such internal sizing agents include neutralized rosin-based sizing agents for use in the preparation of neutralized papers, alkenyl succinic anhydride (ASA), alkyl ketene dimers (AKD) and petroleum resin-based sizing agents. Among these internal sizing agents, neutralized rosina-based sizing agents and alkylene succinic anhydride are preferable. The alkyl ketene dimers can produce good sizing effects, so the added amount can be reduced. However, through the addition of alkyl ketene dimers, the coefficient of friction on the surface of the recording medium tends to decrease. Therefore, a defective feed problem such that the recording medium is defective fed to a printer can be caused depending on the printer's feeding device.
    The thickness of the substrate is not particularly limited, but it is preferably from 50 pm to 300 pm. In addition, the weight of the substrate is practically 45 to 290 g / m 2.
    The coating layer on the substrate includes at least one pigment and a binder, and optionally includes a surfactant and other components. Materials suitable for use as a pigment include inorganic pigments and combinations of an inorganic pigment and an organic pigment.
    Specific examples of inorganic pigments include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, hydroxide magnesium, zinc hydroxide and chlorite. Among these inorganic pigments, kaolin, such as delaminated kaolin, enamelled kaolin and machined kaolin are preferable because they are capable of imparting high gloss and a similar feel to the 15 offset printing papers for the coating layer. In this regard, kaolin, including a relatively small particle beaker, which has a particle diameter distribution so that particles with a maximum diameter of 2 pm are included in an amount of at least 804 cm by weight, in a an amount of at least 504 by weight is preferable. The added amount of such kaolin is preferably not less than 50 parts by weight, based on 100 parts by weight of the binder included in the coating layer. When the amount added is less than 50 parts by weight, the gloss-enhancing effect is hardly produced. The upper limit of the amount added is not particularly determined. However, kaolin has a fluidity such that, when dispersed in water by a high shear force, the viscosity of the dispersion increases. Therefore, the amount added is preferably not more than 90 parts by weight to avoid the occurrence of defective coating.
    Specific examples of the organic pigments mentioned above include particulate resins such as styrene-acrylic copolymers, styrene-butadiene copolymers, polystyrene and polyethylene. It is preferable that these particulate resins are in an aqueous dispersion state. These organic pigments can be used alone or together.
    The amount of such organic pigment added is preferably 2 to 20 parts by weight, based on 100 parts by weight of all pigments included in the coating layer. Since organic pigments impart high gloss to the coating layer and have a relatively low specific weight compared to inorganic pigments, a bulky or glossy coating layer can form, with good coating property. When the amount added is less than 2 parts by weight, the effects are hardly produced. Conversely, when the amount added is greater than 20 parts by weight, the fluidity of the coating liquid tends to worsen, thereby deteriorating the productivity of the coating layer 5 while increasing the production costs of the coating layer,
    Organic pigments have a shape such as solid particle shapes, hollow particle shapes and screw-type particle shapes. In order to balance well the gloss-giving property, the surface-covering property and the fluidity of the coating liquid, organic pigments with a volume of the average particle diameter (i) 50 from 0.2 pm to 3.0 pin are preferable, and organic pigments with a hollow particle shape having a cavity rate of not less than 40% 15 are more preferable.
    Materials suitable for use as the binder in the coating layer include water-soluble resins and water-dispersible resins.
    The added amount of such a binder resin is preferably 2 to 100 parts by weight, and more preferably 3 to 50 parts by weight, based on 100 parts by weight of the pigment included in the coating layer. The amount added is determined so that the resulting recording medium has a liquid-absorbing property in the predetermined range mentioned above.
    Specific examples of such water-soluble resins include, but are not limited to, polyvinyl alcohol and modified polyvinyl alcohol, such as modified anionicamerite polyvinyl alcohol, modified cationicamonte polyvinyl alcohol and acetal modified polyvinyl alcohol; polyurethane; polyvinylpyrrolidone and modified polyvinylpyrrolidone, such as vinylpyrrolidone-vinyl acetate copolymers, vinylpyrrolidone-dimethylaiiiinoethyl methacrylate copolymers, quaternary vinylpyrrolidone-methylmethylaminoethylacetylmethyl acrylate; celluloses such as carboxyethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose; modified celluloses such as cationized hydroxyethylcellulose; synthetic resins such as polyesters, polyurethanes, polyacrylic acid and esters thereof, melamine resins, polyester-polyurethane copolymers and modified versions of these resins; and another 20 resins, such as poly (meth) acrylic acid, poly (meth) acrylamide, oxidized starch, phosphoric acid esters of starch, derivatives of starch, calionized ion, other modified starches, polyethylene oxide, sodium polyacrylate and d alginate sodium. These resins can be used alone or together. Among these water-soluble resins, polyvinyl alcohol, cationically modified polyvinyl alcohol, polyvinyl alcohol modified with acyl, polyesters, polyurethanes and polyester-polyurethane copolymers are preferable.
    Specific examples of such dispersive resins! » in water include, but are not limited to, polyvinyl acetate, ethylene-vinyl acetate copolymers, polystyrenes, styrene- (meth) acrylate copolymers, (meth) acrylate polymers, 10-vinyl acid (meth) acetate copolymers ) acrylic (or esters thereof), styrene-butadiene copolymers, otylene-propylene copolymers, polyvinyl ethers and silicone-acrylic copolymers.
    In addition, crosslinking agents such as methylolmclamine, methyltilance, methylhydroxypropylenourea and isocyanates can be used together with such resins. In addition, resins with a capacity for self-curing, such as copolymers with an N-methylolacrylamide group, can also be used.
    These water-soluble resins and water-dispersible resins can be used together,
    The coating layer preferably includes a cationic organic compound. Materials suitable for use as the cationic organic compound include materials, which can form a water-insoluble salt, by reacting with a sulfonic acid group, a carboxyl group and an amino group included in a dye (such as direct dyes and acid dyes) of a water-soluble paint, such as monomers, oligomers and polymers from primary to tertiary amines, and quaternary ammonium salts. These materials, oligomers or polymers of primary to tertiary amines, and quaternary ammonium salts are preferable.
    When dyes that disperse in water are used as the paint dye, such a cationic organic compound is not necessarily included in the coating layer.
    Specific examples of such a cationic organic compound include dimethylamine-cichlorohydrin polycondensates, dimethylamine-ammonia-epichlorohydrin condensates, poly (trimethylam.inoethylmethacrylatomethylsulfate), glass.l. dialylamine-acrylamide hydrochloride polymers, poly (dialylamine hydroxide hydrochloride) ), polyalylamine hydrochloride, poly (allylamine hydrochloride-diallylamine hydrochloride), acrylamide-diallylamine polymorphs, polyvinylamine copolymers, dicyandiamide, nodiatnide-ammonium-sand-formaldehyde condensates, polyalkylamine-dichloramine-dichloramine and condensate - ammonium, dimethyl chloride 1 day lilammonium, polydialyl methylethylamine hydrochloride, poly (diallyldimethylammonium) chloride, (poly) diallyldimethylammonium-sulfur dioxide, (poly) diallyldimethylammonium chloride-di-lamine hydrochloride! , copolymers of acrylamide-diallyl chloride, copolymer of acrylate-acrylamide-5 diallyl hydrochloride ina, polyethylenimine, polyethyleneimine derivatives (eg, polyethyleneimine modified with algylene oxide) and acrylamine polymers. These cationic organic compounds can be used alone or together.
    Among these compounds, combinations of a low molecular weight cationic organic compound (such as dimethylamine-opichlorohydrin polycondensates, and polyalylamine hydrochloride) and a relatively high molecular weight cationic organic compound (such as dyl (poly} diallylamide 1 ammonium chloride) are When using such a combination, image density can be improved, while reducing the chance of a diffusion problem occurring, that the outside of an image is blurred like a feather.
    The cationic organic compound included in the coating layer preferably has a cationic equivalent of 3 to θ ineq / g, which is measured by a colloidal titration method using potassium polyvinyl sulfate and toluidine blue. When the cation equivalent is in this range, a good property can be transmitted to the coating layer when the dry weight of the coating layer is in the range mentioned above. In the colloidal titration method, a sample (cationic organic compound) is dissolved in distilled water to a concentration of 0.11 by weight, and the pH of the solution is not adjusted.
    The weight of the cationic organic compound included in the coating layer is preferably 0.3 to 2.0 g / m 2 on a dry basis. When the weight is less than 0.3 g / m2, its effects to increase the image density, while reducing the chance of the diffusion problem occurring are difficult to produce.
    The optional coating layer includes a surfactant such as anionic, cationic, ampholytic and non-ionic surfactants. Among these surfactants, non-ionic surfactants are preferable. By adding a surfactant to the coating layer, water resistance, image density and image bleeding can be improved.
    Specific examples of such nonionic surfactants include ethylene oxide adducts of higher alcohols ethylene oxide adducts of alkylphenols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty acid esters of polyalcohols, polyoxide oxide adducts higher aliphatic amines ethylene, fatty acid amide otylone oxide adducts, fatty ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, glycerol fatty acid esters, pentaerythritol fatty acid esters, esters fatty acid, sorbitan and sorbitan, sucrose fatty acid esters, polyalcoholic alkyl ethers and alkanolamine fatty acid amines. These surfactants can be used alone or together.
    The polyalcohols mentioned above for use in nonionic surfactants are not particularly limited, and specific examples thereof include glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose. In addition, the ethylene oxide group of the aforementioned ethylene oxide adducts is preferably partially replaced with propylene oxide or butylene oxide, at a rate of substitution so that the resulting surfactants can maintain water solubility. The replacement rate is preferably no more than 50%.
    The HLB of such non-ionic surfactants for use in the coating layer is preferably 4 to 15, and more preferably 7 to 13.
    The amount of such surfactant added to the coating layer is preferably at most 10 parts by weight, and more preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of the cationic organic compound included in the layer. of coating.
    The coating layer can include other additives such as alumina powders, pH control agents, antiseptics and antioxidants, in amounts such that the additives do not diminish the effects of the present invention.
    The method for forming the coating layer is not particularly limited, and any known methods capable of coating or impregnating a substrate with a coating liquid can be used. The coating or impregnation can be carried out using the coatings such as conventional size press coaters, door roll size press coaters, film transfer size press coaters, blade coaters, rod coaters, jet spray coaters air and curtain liners. Among these coaters, conventional size press coaters, door roller size press coaters and film transfer size press coaters, which are attached to papermaking machines and which can coat or impregnate a substrate with a coating liquid in the machine, are preferable from the point of view of manufacturing costs The coating weight of the coating layer is not particularly limited, preferably from 0.5 to 20 g / m, and preferably from 1 to 15 g / ti , on soca base.
    After the coating or impregnation operation, the substrate can be dried, if necessary. The drying temperature is not particularly limited, but is preferably from 100 ° C to 250 VC.
    The recording medium can have a back layer on the back side thereof. In addition, an intermediate layer can be formed between the coating layer and the substrate, and between the substrate and the back layer. In addition, a protective layer can be formed on top of the coating layer. Each of the coating layer, back layer, intermediate layer or the protective layer can be made up of a single layer or of multiple layers.
    In the following, the imaging method of the present invention will be described.
    The imaging method includes a pre-treatment process for adhesion of a pre-treatment liquid to a coating layer located on at least one surface of a substrate of a recording medium; an ink adhesion imaging process including a dye, an organic solvent, a surfactant and water to the coating layer treated with the pre-treatment liquid to form an ink image; and a post-treatment process for adhesion of a post-treatment liquid to the surface containing the image of the recording medium to form a transparent protective layer on the surface of the recording medium. In the pre-treatment process, the pre-treatment liquid is applied to the engraving medium by coating or spraying (ie ink blasting).
    Suitable methods for use in the pre-treatment process include coating methods capable of uniformly coating a surface of an engraving medium (such as printing papers) with a pre-treatment liquid. Specific examples of coating methods include blade coating methods, engraving coating methods, gravure offset coating methods, bar coating methods, roll coating methods, knife coating methods, jet coating methods air, comma coating methods (roller knife coating methods), U comma coating methods, ΔKKU coating methods, smoothing coating methods, microgravure coating methods, reverse roller coating methods, four to five roll coating, dip coating methods, curtain coating methods, slip coating methods and mold coating methods.
    The pretreatment process can be carried out with a dry recording medium or a wet recording medium (i.e., a recording medium in a drying process). The pre-treated recording medium can be subjected to a drying process, if necessary. Specific examples of the drying device for use in drying the pre-treated recording medium include infrared dryers, 10 microwave dryers, roller heaters, drum heaters and hot air dryers.
    The pre-treatment liquid coating weight is preferably from 0.1 to 30.0 g / m2, and more preferably from 0.2 to 10.0 g / m2 on a wet basis. When the weight of the coating is less than 0.1 g / m 2, those chosen to improve image qualities (such as image density, saturation, pearl formation and color bleeding) are difficult to produce. In contrast, when the coating weight is greater than 30.0 g / m 2, the applied pretreatment liquid has poor drying properties, and in addition, the residual recording medium tends to curl.
    Then, the image formation process will be described.
    The imaging process is a process in which an ink image is formed on the surface of the etching medium, to which the pre-treatment liquid has adhered, by spraying (ejecting) an ink towards the surface. known inkjet engraving can be used for the image forming process. Specific examples of such inkjet recording methods include serial inkjet recording methods, in which images are formed on a sheet of recording medium by scanning an inkjet recording head in a scanning direction. main during sheet feeding of the recording medium in a sub-sweep direction, and inline inkjet recording methods, in which images are formed on a sheet of the recording medium using an inkjet recording head in line while feeding the sheet of recording medium in a sub-sweep direction.
    The driving method for driving the inkjet recording head used for the imaging process is not particularly limited. Specific examples of recording heads include on-demand recording heads, which eject inks using a driver using a piezoelectric element (such as PZ ), A driver using thermal energy, or a driver using an electrostatic force; and continuous ink jet charge control heads.
    Then, the post-treatment process will be described.
    In the post-treatment process, a post-treatment liquid, including a transparent resin, adheres to the surface that contains the image of the recording medium to form a protective layer on the surface.
    The post-treatment liquid can adhere to the entire surface that contains the image of the recording medium or to a specific part of the surface that contains the image. The method of adhering the after-treatment liquid to the recording medium is not particularly limited , and the aforementioned coating methods for use in the pretreatment or spray (ejection) liquid application methods similar to the aforementioned paint spraying (ejection) methods. Among these methods, spraying (ejection) methods similar to the aforementioned paint spraying (ejection) methods are preferable because the applicator is simple in structure, and the post-treatment liquid in the applicator is well maintained.
    The post-treatment liquid coating weight is preferably from 0.5 to 10 g / m2, and most preferably from 2 to 8 g / m2 on a dry basis. When the coating weight is less than 0.5 g / m2, the effects to improve image qualities (such as image density, saturation, pearl formation and color bleeding) are difficult to produce.
    In contrast, when the coating weight is greater than 10 g / m2, the applied after-treatment liquid has poor drying properties, and the effects of improving image quality cannot be further improved, while increasing costs operational.
    The imaging method of the present invention may further include a drying process by heating the recording medium, to which the post-treatment liquid has adhered, to punch the recording medium. Specific examples of dryers include infrared dryers, microwave dryers, roller heaters, drum heaters and hot air blowers. In addition, the imaging method of the present invention can further include a process of fixing the heating of the recording melt to a temperature of 100 to 150 ° C, after the post-treatment process to smooth the surface of the recording medium. , while fixing the images and the protective layer to the recording medium, thus improving the brightness or the ability to fix the recorded images. Specific examples of heaters include roller heaters and drum heaters, and the mirror-like (smooth surface) surface of the roller heaters or roller heaters and drum heaters comes into contact with the surface that contains the image of the recording medium. In this regard, the heating temperature is preferably not lower than the softening point of the thermoplastic resin included in the protective layer. Among these heaters, a fixing roller heated to a temperature of 100 to 150 ° C 5 is preferably used. When the temperature is greater than 150 ° C, the resin used for the protective layer tends to degrade.
    Examples of the printer for use in the imaging method of the present invention are illustrated in Figures 1-10 6.
    Figures 1-6 illustrate the entire structure of the printer.
    The printer performs a pre-treatment process in which a pre-treatment liquid adheres to a recording medium 1 by a pre-treatment device 2; an image forming process 15 in which an ink is ejected by a recording head 3 to form an image on the recording medium 1; a post-treatment process in which a post-treatment liquid adheres to the image part of the recording medium 1 by an after-treatment device 5; an optional drying process 20 cm than the recording medium .1. it is forcibly dried by a dryer; and an optional fixing process in which the recording medium 1 is subjected to a fixation treatment using a fixing device. Numbers 4, 7 and 8 denote a feeding mat respectively; a recording medium that has been subjected to the pretreatment process and in which an image is formed; and a recording medium that has been subjected to the pre-treatment process, the image formation process and the post-treatment process.
    Specifically, in Figure 1, natural drying is carried out after the post-treatment process. In Figure 2, hot air drying is performed by a dryer 6. In Figure 3, hot air drying is performed by dryer 6, and a fixation process is performed using a heat fixing roller 9. In Figure 4 , a drying / fixing process is performed using a heating roller 61. In Figure 5, a drying / fixing process is performed pox; an infrared radiator 62. In Figure 6, a drying / fixing process is performed by a microwave radiator 63.
    The pretreatment process is preferably carried out continuously at a constant linear speed of 10 to 5,000 mm / s. In these examples, a sheet of recording medium is used, and after the pretreatment process is completely carried out on the sheet of recording medium, the medium and recording begins to be subjected to the image formation process / in which the images are formed on the sheet of the engraving by an inkjet engraving method. In this method, since the speed of application of the treatment liquid is typically different from the speed of image formation, the period of time between the time of application of the pre-treatment liquid and the time of image formation 5 it is different for the purte of the front end of the image and the part of the rear end of the image on the sheet of the recording medium. Even when this time difference is considerably large, evaporation of water from the pretreatment liquid applied to the sheet of the .10 recording medium is avoided because the pretreatment liquid includes a hydrophilic solvent that has a higher boiling point and a rate of evaporation less than water in a large amount, and the pretreatment liquid is prepared to include water in an amount such as to balance the water (moisture) included in the air around the printer. Therefore, the image qualities can be controlled in such a way that there is no difference in the image qualities between the front end part and the rear end part of the image when it is visually observed.
    In the printers illustrated in Figures 1-6, after the pre-treatment liquid adheres to the recording medium sheet 1, the recording medium sheet Take to be fed towards the recording head 3 by a feeding member, such as rollers c guides, which are in contact with the recording medium sheet. In this regard, if the pretreatment liquid applied to the recording medium sheet is transferred to the feed member, problems such that the function of the feed member is diminished, and / or the feed member is contaminated, deteriorating thus, the qualities of the image tend to occur. In order to avoid the occurrence of such problems, it is preferable that the printer uses a wavy guide, a spur-shaped roller and / or a roller whose surface is made of a material repellent to the Water.
    However, it is preferable that the pre-treatment liquid adhered to the recording medium is absorbed by the recording medium as quickly as possible, and the recording medium appears to be dry. In order to reach this object, the pre-treatment liquid preferably has. a static surface tension of a maximum of 30 ml / min, so that the liquid penetrates quickly into the recording medium. In this regard, the aforementioned "apparent drying" of the pre-treatment liquid is different from the "drying / solidification" of the pre-treatment liquid, in that the liquids (such as water or organic solvents) included in the pre-treatment liquid - treatment is evaporated, and the pre-treatment liquid cannot maintain a liquid state and reaches a solid level. Therefore, using a printer with a combination of a pretreatment applicator (like the pretreatment device 2) and an image forming device (like the engraving head 3), the ink jet registration can be carried out on the recording medium sheet 1 even when the pretreatment liquid is absorbed by the recording medium sheet, and the recording medium sheet reaches the state of apparent dryness because the pretreatment liquid is not solidified. Therefore, even when the pre-treatment liquid coating weight is considerably low, the 10 qualities of the image can be markedly improved.
    Having generally described this invention, a better understanding can be obtained by reference to certain specific examples which are provided in this document for purposes of illustration only and which are not intended to be limiting.
    In the descriptions in the examples below, the numbers represent the weight ratios in parts, unless otherwise specified. EXAMPLES
    Preparation of inkjet inks
    Preparation Example 1 (Preparation of the water-soluble polymer solution A)
    The following components (1) - (3) were stirred by a stirrer during heating to dissolve the copolymer (1) - (1) α-olefin-maleic anhydride copolymer, having the formula (a) mentioned below 10.0 deliveries
    where R is an alkyl group, with 18 to 22 carbon atoms, and n is an integer from 30 to 100. (ie T-YP112 from Seiko PMC Corp., with an acid value of 190 mg KOH / g and an average molecular weight of 100,000} (2) 1 N aqueous Liou's solution, 17.34 parts (1.2 times the acid value of the copolyphlor (1)) {3} Ion exchange water, 72.66 parts
    The mixture was filtered using an open filter with an average diameter of S pm to prepare a solution of water-soluble polymer A.
    In this regard, the copolymer (1) was prepared using an olefin having 20 to 24 carbon atoms and having a structure such that the alkyl (R) groups having 18 to 22 carbon atoms (between 20 to 24 atoms of the olefin carbon, two carbon atoms linked with a double bond are incorporated into the polymer chain) are randomly connected to the polymer chain.
    Preparation Example 2 (Preparation of Black Surface Treated Pigment Dispersion)
    Ninety (90) grams of carbon black with a specific CTAB surface area of 150 m2 / g, and an IJBP oil absorption of 100 ml / 100 g was added to 3,000 ml of a 2.5 N sodium sulfate solution, and the mixture was heated to 60 ° C with stirring for 10 hours at a speed of 300 rpm to carry out an oxidation reaction. The rational product was filtered and the carbon black thus obtained was mixed with an aqueous sodium hydroxide solution to neutralize the carbon black, followed by ultrafiltration.
    After the carbon black was washed with water, the carbon black was dried, the punch carbon black was dispersed in pure water during complete agitation to prepare a dispersion of the carbon black pigment. The carbon black pigment dispersion had a mean particle diameter (1) 50 volume of 103 nm when the mean particle diameter volume was measured with a particle diameter distribution measuring instrument, NANOTRACK UPA-EX1 .50 from Nikkiso Co ,, Ltd, Preparation Example 3 (Preparation of the magenta pigment (1) Preparation of the polymer solution A After the air in URI 1 liter flask, which is equipped with a mechanical stirrer, a thermometer , a nitrogen gas supply tube, a reflux tube and a drip hopper to be replaced with a nitrogen gas, the following components were fed to this to prepare a mixture, F.stirono, 11.2 g acrylic acid 2, 8 g Lauryl methacrylate, 12.0 g Polyethylene glycol methacrylate, 4.0 g Styrene macromer, 4.0 g Mercaptoethanol, 0.4 g
    The mixture was heated to 65 ° C.
    Then, the following components were mixed and the mixture was dripped into the flask for 2.5 hours using the drip funnel, Styrene, 100.6 g Acrylic acid, 25.2 g Lauryl methacrylate, 106.0 g Polyethylene glycol methacrylate, 36.0 q Hydroxyethyl methacrylate, 60.0 g Styrene macromer, 36.0 Mercaptoethanol, 3.6 g Azobismethylvaleronitrile, 2.4 g Methylcetyl ketone, 18.0 g
    Thereafter, a mixture of 0.8 g of zobisitethyl valeronitic and 18.0 g of methyl ethyl ketone was dripped into the flask for 0.5 hour using the drip funnel.
    After the rational product in the flask was aged for 1 hour at 65 Cc, 0.8 g of azcismethylvaleronyltril was added to the flask, and the mixture was further aged for 1 hour.
    After the reaction was over, 364.0 g of methyl ethyl ketone was fed into the flask. Next, 800 g of a solution of polymer A with a solids content of 50% by weight was prepared. (2) Preparation of the polymer dispersion containing magenta pigment
    The following components were mixed by stirring.
    Polymer A solution prepared above, 28 g Red Pigment CI 122, 42 g 1 mol / L of aqueous potassium hydroxide solution, 13.6 g Methylethylene, 20.0 g Ion exchange water, 13, 6 g The mixture was kneaded using a roller mill. The paste prepared in this way was fed with 200 g of pure water and the mixture was completely stirred. Thereafter, methyl ethylene and water were distilled off the mixture using an evaporator to prepare a dispersion.
    In addition, the dispersion was subjected to pressure filtration using a polyvinylidide fluoride membrane filter with an average pore diameter of 5.0 pm to remove coarse particles. Thus, a polymer dispersion containing magenta pigment with a pigment content of 15% by weight, and a solids content of 20% by weight was prepared. The volume of the average particle diameter (D50) of the particulate polymer in the dispersion, which was measured by the method mentioned above in Preparation Example 2, was 127 nm. Preparation Example 4 (Preparation of polymer dispersion 15 containing cyan pigment)
    The procedure for preparing the polymer dispersion containing magenta pigment in Example d of Preparation 3 was repeated, except that the pigment was replaced with a phthalocyanine pigment (Pigment Blue C.I. 15: 3) to prepare a polymer dispersion containing cyan pigment.
    The volume of the average particle diameter (D50) of the particulate polymer in the dispersion, which was measured by the Sludge stone mentioned above in Preparation Example 2, was 93 nm.
    Preparation Example 5 {Preparation of polymer dispersion containing yellow pigment) The procedure for the preparation of the polymer dispersion containing magenta pigment in Preparation Example 35 was repeated, except that the pigment was replaced with a monoazo yellow pigment (CI Yellow Pigment) 74) to prepare a polymer dispersion containing yellow pigment. The volume of the average particle diameter (D50) of the particulate polymer in the dispersion, which was measured by the method mentioned above in Preparation Example 2, was 76 nm.
    Example of Preparation 6 (Preparation of polymer dispersion containing black pigment)
    The procedure for preparing the dispersion of the polymer containing magenta pigment in Example d of Preparation 3 was repeated, except that the pigment was replaced with a carbon black (ff1100 next to Degussa A.G.) to prepare a polymer dispersion containing the black pigment. The volume of the average particle diameter (D50) of the particulate polymer in the dispersion, which was measured by the method mentioned above in Preparation Example 2, was 104 nin.
    Preparation Example 7 (Preparation of the pigment dispersion
    The surfactant mentioned below (2) was dissolved in tonic exchange water (3), and then the pigment mentioned below (1) was mixed with the solution, so that the pigment was completely wet. (1) Monoazo yellow pigment, 30.0 partitions (Pigmento Amarelo CI 74, together with Dainichíseika Color & Chemicals Mfg. Co., htd.) (2) Polyoxyethylene styrenophenyl ether, 10.0 partitions {Nonionic surfactant, NOIGEN EA-177 , with Dai-ichi Kogyo Seiyaku Ltd., with an HLB dc 15.7) (3) Ion exchange water, 60, parts
    The mixture was then subjected to a dispersion treatment for 2 hours using a wet dispersion machine (DYNO MILL KDL type A, from WAS), which was filled with zirconia beads with a diameter of 0.5 mm and which spun at 2,000 rpm. Thus, a primary pigment dispersion was prepared.
    This primary pigment dispersion was mixed with 4.26 parts of an aqueous solution of a water-soluble polyurethane (TAREIAC W-5661, with Mitsui Chemicals inc., Having a solids content of 35.2%, an acid value 40 mg of KOH / g and an average molecular weight of 10,000), and the mixture was completely stirred. Thus, a dispersion of the yellow pigment containing surfactant was prepared.
    The volume of the average particle diameter (D50) of the pigment in this pigment dispersion, which was measured by the method mentioned above in Preparation Example 2, was 62 nm,
    Preparation Example 8 (Preparation of the magenta pigment dispersion containing surfactant)
    The surfactant mentioned below (2) was dissolved in ion exchange water (3), then the pigment 10 mentioned below (1) was mixed with the solution, so that the pigment was completely wet. (1} Quinacridone pigment, 30.0 parts (Red Pigment C.I. 122, by Da.ínichisoika Color and
    Chemicals Mfg. Co., Ltd.) (2) Polyoxyethylene-β-naphthyl ether, 10, 0 parts (Non-ionic surfactant, RT-100, with Takemoto Oil & Fat Co., Ltd., having an HLB of 18.5) ( 3) Ion exchange water, 60 parts
    The mix was then subjected to a dispersion treatment for 2 hours using a milled dispersion machine (DYNO MILL KDL type A, from WAB), which was filled with zirconia beads with a diameter of 0.5 mm and which spun at 2,000 rpm. Thus, a dispersion of primary pigment was
    This primary pigment dispersion was mixed with 7.14 parts of an aqueous solution of a water-soluble (meth) acrylic (meth) acrylic copolymer (JC-05 from Seiko PMC Corp., having a solids content of 21%, a an acid value of 178 mg KCH / g and a weight average molecular weight of 16,000), and the mixture was thoroughly stirred. Thus, a dispersion of magenta pigment containing surfactant was prepared.
    The volume of the average particle diameter (1150) of the pigment in this pigment dispersion, which was measured by the method mentioned above in Preparation Example 2, was 83 nm.
    Preparation Example 9 (Preparation of cyan pigment dispersion containing surfactant) The surfactant mentioned below (2) was dissolved in ion exchange water (3), and then the pigment mentioned below (1) was mixed with the solution, so that the pigment was completely wet. (1) Phthalocyanine pigment, 30.0 parles (Blue Pigment C.I. 15: 3 by Dainichiseika Color and
    Chemicals Mfq. Co., Ltd.) (2) Polyoxyethylene styrene-phenyl ether, 10.0 parts (Non-phonic surfactant, NOIGEN EA-177, with Dai-ichi
    Kogyo Sciyaku Ltd., with an HLB of 15.7). (3) Ion exchange water, 60 parts
    The mixture was then subjected to a dispersion treatment for 2 hours using a wet dispersion machine (DYNO MILL KDL type A, by W.AB), which was filled with zirconia beads with a diameter of 0.5 mm and it spun at 2,000 rpm. Thus, a dispersion of the primary pigment was prepared.
    This primary pigment dispersion was mixed with 7.51 parts of the aqueous polymer solution prepared above in Preparation Example 1, and 2.51 parts of a water-soluble polyester resin (N1CHIGO POLYESTER W-0030 with Nippon Synthetic Chemical Industry Co. Ltd., with a solids content of 29.9%, an Aoido value of 100 mg KOH / g and an average molecular weight of 7,000), and the mixture was thoroughly stirred. Thus, a dispersion of child pigment containing surfactant has been proposed,
    The volume of the mean particle diameter (D50) of the pigment in this pigment dispersion, which was measured by the method mentioned above in Preparation Example 2, was 78 nm.
    Manufacturing examples 1 to 26 (Preparation of paints 1 to 26)
    As shown in Tables .1-4 below, organic solvents (such as compounds of formulas (I) - (iV), an amide compound of formula (1-1), alkylalkanol and polyalcohols), a penetrant, a surfactant, an antiseptic and water were mixed, and the mixture was stirred for 1 hour in order to be well mixed. Under this aspect, a dispersive resin! in water it was optionally added to the mixture, and it was stirred for 1 hour. After that, a pigment dispersion, a defoaming agent and a pH control agent were added to the mixture, which was stirred for 1 hour. The dispersion was subjected to pressure filtration using a polyvinylidene fluoride membrane filter with an average pore diameter of 5.0 µm to remove coarse particles and foreign materials. Thus, the inks from Manufacturing Examples 1-26 were prepared,
    Was Tables 1-4, abbreviations and the like have the following meaning. 1. Acrylic-silicone resin emulsion: POLYSOL ROY6312, with Showa benko KK, having a solids content of 37.2% by weight and an average particle diameter volume of 171 nm, and a minimum film formation temperature (MET) of 20 ° C. 2. Polyurethane emulsion: HYDRAN APX - 101H, with DIC Corp., having a solids content of 45% by weight, an average particle diameter volume of 160 nm, and a minimum film formation temperature (MFT ) of 20 ° C. 3. KF "643: Polyether-modified silicone compound from Shi-Etsü Chemical Co., Ltd., including 100% by weight active ingredient. 4. ZONYL FS-300: Polyoxyethylenepefluoralkyl ether (from Du Pont, including the active ingredient at 40% in position} 5. SOFTAMOL EP-70251 polyoxyalkylenealkyl.tor (from Nippon Shokubai Co., Ltd., including active ingredient 40% by weight) 6. PRüXEL GXL: Antiseptic including 1 / 2 “benzotlazo.lino-3-one as a main component (with Avocia Inc., including 20% active ingredient and including dipropylene glycol) 7. KM-72F: silicone auto-emulsifying antifoaming agent (with Shin- Etsu Chemical Co ,, Ltd., including 100% active ingredient)








    The ionic properties of the inks of Manufacturing Examples 1-26 were measured by the methods mentioned below. The results are shown in Table 5 below. 1. Viscosity
    The viscosity of an ink was measured at 25 ° C using an Rfc-550 viscometer next to Toki Sarigyo Co., Ltd. 2. pH The pH of an ink was measured at 25 ° C, using an HM - 30R pop meter , with DKK-TOA Corp. 3. Static surface tension
    The static surface tension of an ink was measured at 1 ° C, using a fully automatic surface tensiometer CBVP-Z, obtained from Kyowa Interface Science Co. <Ltd. Table 5

    Preparation of liquids for treatment
    Examples of Pre-Treatment Liquid Preparation 1-9
    Each pre-treatment liquid was prepared by the following method. the components described in Table 6 below were mixed and stirred for 1 hour to prepare a mixture. The mixture was subjected to pressure filtration using a polyvinylidene f.Wore to membrane filter with an average pore diameter of 5.0 pm to remove insoluble materials, such as foreign materials. Thus, the pretreatment liquids of the Liquid Pretreatment Preparation Examples 1-9 were prepared. Table 6

    Abbreviations and the like in Tabelíi 6 mean the
    Following. ZONYL FS-300, KE-643 and PROXEL GXL are described above in Tables 1-4. 1. L-lactic acid (having a carboxyl}: L-lactic acid obtained from Tokyo Kasoi Chemical Industry Co., Ltd., with a purity of 85% or more including 3 carbon atoms. 2. Acid L - (-) - tartaric (having two carboxyl groups}: L- (+) - larLic acid, obtained from Kanto Chemical Cu., Inc., with a degree of purity equal to or greater than 99.5% and including 4 carbon atoms 3. DL-malic acid (having two carboxyl groups): DL-malic acid, obtained from Kanto Chemical Co., Inc., with a degree of purity equal to or greater than 99% and including 5 atoms carbon 4. FUTARGENT 251: Fluorine-containing surfactant containing the branched perfluoralkynyl group obtained from Moos Co., Ltd., including the 100% active ingredient.
    The physical properties of the pretreatment liquids in Manufacturing Examples 1-9 were measured by the methods mentioned below. 1. pB The pH of a pre-treatment liquid was measured at 25 ° C, using a pH meter, HM-30R, obtained from DKK-TQA Corp. 2. Static surface tension
    The static surface tension of a pre-treatment liquid was measured at 25 "C, using a fully automatic surface tensiometer CBVP-Z, obtained from Kyowa
    Interface Science Co., Ltd.
    In addition, the ratio (AM / AC) of an organic amine to an organic acid was calculated using the following equation;
    AM / AC - (number of water-soluble organic monoamine IROIS) / ((number of moles of water-soluble aliphatic organic acid) x (number of acid groups included in a molecule of water-soluble aliphatic organic acid)) 0 $ results are shown in Table 7 below. Table 7

    Examples of Pre-treatment Liquid Preparation 10-20 The procedure for preparing the pre-treatment liquids in Pre-treatment Liquid Preparation Examples 1-9 was repeated, except that the components were replaced with the components described in Tables 0-1 and 8-2 below. Thus, pre-treatment liquids from
    Examples of Liquid Pre-Treatment Preparation 10-20 were prepared. In this regard, the water-soluble cationic polymers A-1 to A-5 were prepared as follows.
    Preparation Example A-1 (Preparation of the cationic polymer) The cationic polymer is a copolymer of N, N-dimethylalylamine hydrochloride and N-methylhydrylamine hydrochloride (in a molar ratio of 0.7: 0.3 in formula).
    Initially, 237.58 g (1.4 mol) of a 71.66% aqueous solution of N, N-dimethylalylamine hydrochloride, and 147.23 g (0.6 mol) of a 60.17% aqueous solution of N-methylhydrylamine hydrochloride were fed to a separate 1-10 liter flask equipped with a stirrer, a thermometer and a reflux condenser to prepare an aqueous solution with a monomer concentration of 67.27%. After the aqueous solution was heated to 60 ° C and the temperature remained constant, 4.56 g (1.0 mol% based on monomers) of ammonium porsulfate serving as a radical polymerization initiator was added to this, to carry out this polymerization, In addition, 4.56 g (1.01 mol, based on monomers) of ammonium persulfate was added to this within 2 hours and 4 hours after the start of polymerization. In addition, 20 9.13 (2.0 mol%, based on monomers) of ammonium persulfate was added to this within 23 hours, 24 hours, 25 hours, 26 hours, 27 hours and 29 hours after beginning of polymerization. After that, the polymerization reaction was continued for 3 hours. Thus, a brown solution of a copolymer of N, N-dimethylalylamine hydrochloride and N-methyldiallylamine hydrochloride (in a 0.7: 0.3 molar ratio in formula) (i.e., cationic polymer solution of Example dc Preparation Al) was prepared.
    The average molecular weight of this copolymer, which was determined by a chromatographic gel permeation method, was 1,800.
    Preparation Example A-2 (Preparation of the cationic polymer)
    The cationic polymer is a copolymer of N, N-dimethylalamine hydrochloride and N-methyldiallylamine hydrochloride (in a 0.9: 0.1 molar ratio in formula).
    Initially, 533.56 g (2.7 moles) of a 61.54% aqueous solution of N, N-dimethylalylamine, and 73.62 g (0.3 mol) of a 60.17% aqueous solution of N hydrochloride - metildia.li lamina were fed to a 1 liter separable flask equipped with a stirrer, a thermometer and a reflux condenser to prepare an aqueous solution with a monomer concentration of 61.37%, After the aqueous solution was heated to 60 C and the temperature remains constant, 6.85 q (1.0 mol% based on monomers) of ammonium persuliate serving as a radical polymerization initiator was added to this to carry out the polymerization. In addition, 6.85 g (1.0 mol%, based on monomorphs) of ammonium persulfate was added to this at 7. hours and 4 hours after the start of polymerization. In addition, 13.69 g (2.0 mol%, based on monomers) of ammonium persulfate was added to this at 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 47 hours and 40 hours after polymerization starts. After that, the polymerization reaction was added continuously for 2 hours. Thus, a brown solution of a copolymer of N, N-dimethylalylamine hydrochloride and N-methylhydrylamine hydrochloride (in 10 a molar ratio of 0.9: 0.1 in formula) (ie, cationic polymer solution of the Example of Preparation A-2) was prepared.
    The average molecular weight of this copolymer, which was determined by a gel permeation chromatography method, was 700.
    Example d Preparation A-3 (Preparation of the cationic polymer) The cationic polymer is a copolymer of monolylamine dehydrochloride and N, N-dimethylalylamine hydrochloride (in nina 20 molar ratio of 0.5: 1), 5 cm formula). Initially, 64.87 g (0.50 mol) of a 72.11% aqueous solution of monoalylamine hydrochloride, 100.99 g (0.50 mol) of a 60.21% aqueous solution of N hydrochloride, N-dimethylalylamine and 13.45 g of water were added to a flask with three 300 ml necks equipped with a stirrer, a thermometer and a reflux condenser to prepare an aqueous solution with a monomer concentration of 60%. After the aqueous solution is heated to 60 ° C and the temperature remains constant, 8.63 g (3.2% by mol based on the monomers} of 2,2'-azobis dihydrochloride (2-aminodipropane) serving as an initiator of Radical polymerization was added to this to carry out the polymerization. In addition, 8.68 g of 2,2 * -azobis dihydrochloride (2-aminodipropane) was added 10 to this, in the times of 24 hours, 48 hours and 72 hours after the start of the polymerization. After that, the polymerization reaction continued for 24 hours. The pale yellow rational solution thus prepared was added in 3 liters of a solution of acetone-isopropane. (with a weight ratio of 1: 1 ) to precipitate the copolymer.After the copolymer is filtered using a glass filter, the copolymer was washed well and then dried for 48 hours at 60 ° C. Thus, a brown solution of a monoaliamine hydrochloride copolymer and N, N-dimothylalylamine hydrochloride (in a 0.5: 0.5 molar ratio in formula) (ie, solution d and cattonic polymer from Preparation Example A-3) was prepared.
    The average molecular weight of this copolymer, which was determined by a permeation chromatography method was qcl, was 800.
    Preparation Example A-4 (Preparation of the cationic polymer) The cationic polymer is a copolymer of diallyldimethylamine hydrochloride and sulfur dioxide.
    Initially, 100 inU of a solution of dimethyl sulfoxide 1 mol / h of diallyldimethylamine hydrochloride and 100 ml of a solution of dimethyl sulfoxide 1 mol / L of sulfur dioxide were added to a flask with four necks of 300 ml equipped with a stirrer, a thermometer and a reflux condenser. After 0.82 g of azobisisobutyronitrile serving as a polymerization initiator was added to this, the polymerization was carried out for 24 hours at 40 ° C. The reaction solution thus prepared was dripped in methanol to precipitate the copolymer. After the copolymer was filtered through a glass filter, the copolymer was subjected to drying under reduced pressure. In this way, 18 g of a copolymer (i.e., the cationic polymer of Preparation Example A-4) was prepared.
    The average molecular weight of this copolymer, which was determined by a goal permeation chromatography method using polyethylene glycol as the standard material, was about 3,000.
    The copolymer has a repeat unit with the following formula {19}.

    Preparation Example A "5 (Preparation of the cationic polymer) The cationic polymer is a copolymer of diallyldimethylammonium chloride and acrylamide.
    Initially, 134.7 g (0.5 mol) of a 60S aqueous solution of diallyldimethylammonium chloride and 176 g of distilled water were fed to a 500 ml four-necked flask equipped with a stirrer, a thermometer and a condenser. reflux, and the pH of the mixture was controlled to be in a range of 3 to 4 using hydrochloric acid. Then, 18.3 g (0.25 mol) of acrylamide and 3.9 g of sodium hypophosphite were added thereto, and the mixture was stirred at 50 ”C to dissolve acrylamide and sodium hypophosphite. heated to 60 ° C, 1.7 g of a 28.5% aqueous solution of ammonium persulfate was added thereto. After the reaction was carried out for 4 hours with the concomitant temperature control in a range of 60 ° C to 65 "C, 3.5 g of a 28.5% aqueous solution of ammonium persulfate was additionally added to this. The mixture was subjected to a reaction for 20 hours at 60 ° C. Thus, a copolymer of dialyldimethylammonium-acrylamide chloride (i.e., the cationic polymer of Preparation Example A-5) was prepared. The average molecular weight of this copolymer , which was determined by a ÇJGJL permeation chromatography method, was 3,000.
    Table 8-2

    THERE bare abbreviations and the like Tables 8-1 and 8-2 mean the following. SOFTANOL EP-7025 and PROXKL GXL are described above in Tables 1-4. 1. Ammonium lactate: ammonium lactate obtained from Kanto Chemical Co., Inc., with a pore size of 73 to 77%. 2. Ammonium acetate: ammonium acetate obtained from Kanto 3. WS-4Q20: Polyamide ^ epichlorohydrin copolymer obtained from Seiko PMC Corp ,, including the 25-% active ingredient. 4. SHALLOL DM-283P: Quaternary ammonium-type cationic polymer compound with the formula mentioned below (20) 'obtained from Dai-ichi Kogyo Seiyaku Co ,, Ltd., including 50% active ingredient and having a molecular weight of about 28,000.
    where X represents a halogen atom and n is an integer. 5. KM-72F: Antoomulsifying silicone antifoaming agent obtained from Shin-Etsu Chemical Co., Ltd., including the 100% active ingredient, 6. Composed with the formula (Fl) -c Cíf'9-CMaCH ( OH) CH2O- {CHzCHjO) as-CuHas 7. Compound with the formula (F-2) CFjCF '(CF2CFÍ) 3-CHaCH2O- (CH2CIL2O) fcH where j is 0 or an integer from 1 to 10, and k is 0 or an integer from 1 to ^ 0, 8, Compound with the formula (F-3—1)
    where Rf represents ~ CF3f or -CF2CF3 / n is an integer from 1 to 4, m is an integer from 6 to 25 and p is an integer from 1 to 4. 9. Composed with the formula (F 4-1 )
    where Rf stands for "CF3 or -CF2CF3, eq is an integer from 1 to 6, £ 0 The pH and static surface tension of pretreatment liquids 10-20 were measured by the methods used to measure the properties of the liquids in pretreatment pretreatment 1 to 9. The $ 0 results are shown in Table 9 below.


    Preparation examples 21-30 (Preparation of post-treatment liquids)
    Each post-treatment liquid was prepared by the following method,
    The components described in Tables 10-1 and 10-2 below were mixed and stirred for 1 hour to prepare a mixture. The mixture was subjected to filtration under pressure using a polyvinylidene fluoride membrane filter with an average pore diameter of 5 d .00 pm to remove coarse particles and foreign materials. Thus, post-treatment liquids of Preparation Examples 21-30 were prepared. Table 10-1

    Table 10-2

    In 10-1 and 10-2, the abbreviations and the like mean the following. ZONYL FS-300, Kfc '300 or PROXEL GXL are described above in Tables .1-4. 1. LOMIFLON FE — 4500F: Fluorine-containing resin emulsion obtained from Asahi Glass Co., Ltd., with a solids content of 52%, a minimum film formation temperature (MITT) of 28 ° C and a dc temperature glass transition (Tg) from 18 to 23 ° C. 2. POLYSOL ROY6312: Emulsion of silicone acrylic resin obtained from Showa Penko KK, having a solids content of 40%, a minimum film formation temperature (MET) of 20 ° C and a glass transition temperature (Tg ) of 8 ° C, 3. HYíJRAN HW-930: Polyester urethane resin emulsion obtained from DIC Corp, with a 50% solids content, a minimum film formation temperature (MKT) of a maximum of 0 ° C and a softening temperature of 115 ° C to 120 ° C. 4. VONCOAT 9455: Emulsion of styrene-acrylic resin obtained from PIC Corp., having a solids content of 40%, a minimum film formation temperature (MFT) of 38 ° C to 46 ° C and a temperature of glass transition (Tg) of 29 ° C. 5. VONCOAT HC-280: Emulsion of acrylic resin obtained from DIC Corp., having a solids content of 50%, a minimum film formation temperature (MFT) of 0 * C to 3 "'C and a temperature of glass transition (Tg) of 2 ° C. 6. VINYBI.AN 2580: Emulsion of acrylic resin obtained from the
    Nissin Chemical Co., Ltd ,, with a solids content of 45%, a minimum film-forming temperature (MET) of at least 100 ° C and a glass transition temperature (Tg) of 100 ° C. 6. VINYBLAN 2586; Emulsion of csLirene-acrylic resin obtained from Nissin Chemical Co-Ltd., with a content of 5 solids of 45%, a minimum film formation temperature (MET) of at most 0 σC and a glass transition temperature (Tg ) -33 ° C. 7. Compound with the formula (Fl) -and C ^ -CHaCH (OH) CH20- {CH2CH2O) 2s-Ci2II25 When using pre-treatment liquids, paints and post-treatment liquids, images were formed in several recording media. 1. Pre-treatment process As described above in Tables 11 below, the pre-treatment liquids of Preparation Examples 1-20 were applied by a roller coating method to the coating layer surfaces of the recording medium, followed by by natural drying. In this respect, the coating weights (on a soca basis) of the coated pretreatment liquids are described in Table 11, and the pretreatment process was not carried out in Comparative Examples 1 and 3-5. image As described in Table 11 below, the inks in Manufacturing Examples 1-26 were ejected by an inkjet recording device (IPS10 GXK-5500, obtained from Ricoh Co., Ltd.) under environmental conditions of 23 ± 0.5 ° C and 50-r5% RH to perform an image formation process. Under this aspect, the conduction voltage of the piezoelectric element was altered so that the quantities of the ejected inks were equal and, therefore, the inks adhere to the recording medium in the same quantities. In addition, the printing mode of the inkjet engraving machine has been defined as a "plain paper - clear image" mode. 3. Post-treatment process The post-treatment liquids from Preparation Examples 1-20 were applied over the imagom portions by a roller coating method or a spray (ejection) method using an inkjet head under the conditions described in Table 12. In the roller coating method, the post-treatment liquid was applied to the entire surface of the recording medium with the images on it, and the weight of the soca post-treatment layer was measured. In the spray method, the post-treatment liquid was applied only over the image potion, and the weight of the dry post-treatment layer per 1 m2 was determined based on the amount of the ejected paint and the resin content in the powder liquid. -treatment. The results are shown in Table 12. In addition, there were some examples, a heat fixation roller came into contact with the post-treatment layer (protective layer) to effect fixation and smoothing. In Comparative Examples 1, 2 and 4, the post-treatment process was not carried out. Table 11

    Table 12


    The abbreviations and the like in Table 11 szcjná ti have the following. 1. OK TOP COAT: Offset printing paper obtained from Oji Paper Co./ Ltd., grade A2. 2. OK KINFUJI +: Offset printing paper obtained from Oji Paper Co., Ltd., grade Al. 3. SA KINFUJH: Offset printing paper obtained from Oji Paper Co., Ltd., grade AO. 4. AURORA COAT: Offset printing paper obtained from Nippon Paper Industries Co., Ltd., grade A2. 5. SUPER MI DAL: Paper for offset printing obtained from Nippon Paper Industries Co., Ltd., grade A2. 6. RICOH BUSINESS COAT GLOSS 100: Goal jet printing paper obtained from Ricoh Co., Ltd., grade A2. 7. SPACE DX; Gravure printing paper obtained from Nippon Paper Industries Co., Ltd. 8. MIRROR COAT PLATINUM: Molded offset paper for offset printing obtained from Oji Paper Co., Ltd. 9. SUPER FINE PAPER: Paper for printing on jet jet obtained from Seiko Epson Corp. 10. TYPE 6200: Plain paper copier paper (PPC) obtained from Ricoh Co., Ltd.
    The images recorded by the methods of Examples 1-23 and Comparative Examples 1-12 were evaluated for image density, saturation, pearl formation, wrinkling (rippling), blurring and brightness. The results are shown in Table 13 below.
    Evaluations were performed on each of the various color images, based on predetermined evaluation criteria. In a case where the evaluation results for the various color images varied, the fashion (that is, the most popular evaluation result) is described in Table 13. When there were two or more fashions, the best fashion is described in Table 13. One Since the ink was not ejected in Comparative Example 7, the evaluation was not carried out.
    The mark in Table 13 means that the assessment (measurement) could not be performed. In addition, since the cause of color bleeding is the same as that of pearl formation, the results of color bleeding assessment are the same as those of pearl formation, the results of color bleeding assessment are not described in Table 13. 1, Image Density
    After performing a pretreatment process on a recording medium, as described in Table 11, a color image of a graph including a 64-point solid square image, which was prepared using Microsoft Word 2000, was recorded in the middle of pre-treated recording. In this regard, the printer's printing mode has been set to a mode that is a "glossy, glossy white paper" mode modified so as not to be color compensated using a conductor attached to the printer. After that, the post-treatment process was performed on that, as described in Table 12.
    The image density of the black square image was measured with an X-RJTK 939 espoetrodensitometer obtained from X-Rito Corp. The image density was classified as follows. @ (Excellent): Not less than 2.0 for black image
    Not less than 1.25 for yellow image
    Not less than 2.0 for magenta image
    Not less than 2.0 for cyan image o (Sun): Not less than 1.9 and less than 2.0 for black image Not less than 1.2 c less than 1.25 for image I will love
    Not less than 1.9 and less than 2.0 for magenta image
    Not less than 1.9 and less than 2.0 for cyan A image (Acceptable): not less than 1, 8 and less than 1.9 for black image
    Not less than 1.15 and less than 1.2 for yellow image
    Not less than 1.8 and less than 1.9 for magenta image
    Not less than 1.8 and less than 1.9 for cyan image x (Bad): Less than 1.8 for black image
    Less than 3.15 for .yellow image
    Less than 1.8 for magenta image Less than 1.8 for cyan image 2. Image saturation A color image of the graph was formed by the method used to evaluate the image density, and then the post-treatment process was accomplished in that. The print mode of the printer has been set to a mode which is a "glossy-light paper" mode modified to not be subjected to color compensation using a conductor attached to the printer. The solid square image was subjected to colorimetric measurement using the X-RITE 939 spectrodensitometer obtained from X-Rite Corp. The ratio (M / S) of the measured value (M) of the saturation to the value (S) of the saturation of the standard color image (Japan color Ver. 2) was calculated. In this respect, the saturation of the colored images of yellow, magenta and cyan patterns are 91.34, 74.55 and 62.82, respectively.
    Saturation was classified as follows. (Ω) (Excellent): The ratio is not less than 1.0. o (Good): The ratio is not less than 0, 9 and less than 1.0. x (Bad): The ratio is monor than 0, 9. 3. Pearl formation
    After performing a pretreatment process on a recording medium, as described in Table 11, a solid color image was recorded on the recording medium.
    The solid color image was visually observed for 10 and the images are determined to be images of uneven density (that is, images with pearl formation). Pearl formation was classified as follows. @ (Excellent): The images showed no pearl formation. o (Good): The images showed a slight pearl formation. Δ (Acceptable): The images showed pearl formation, but this occurred at an acceptable level, * (Bad): The images showed severe pearl formation. 4. Knrugaraento 20 After carrying out a pre-treatment process with a recording medium, as described in Table 11, a solid image with a size of 3 cm x 15 cm (where three solid square images are arranged in an arrangement), whose The image was prepared using the Microsoft Word 2.000 program, registered in the pre-treated recording machine. In this regard, the printer's printing mode has been set to a mode that is a modified "glossy-light paper" mode not subjected to color compensation using a conductor attached to the printer.
    The wrinkle was classified as follows. © (Excellent): the images showed no wrinkles, and the recording medium was fed without problem. o (Good): The images caused a slight wrinkling, but the recording medium was fed without problem. A (Acceptable): The images caused wrinkling, but the recording medium was fed without a problem. x (Bad): The images caused serious wrinkling, and the recording medium was fed with a problem. 5. Blurring of the image
    A color image of the graph was formed by the method used to assess the image density, and then the post-treatment process was performed on that. In this regard, the printing mode was the "glossy-light paper" mode.
    After the image was dried for 24 hours under environmental conditions of 23 + 2 CU and 50 ± 15% RH, the solid square image was rubbed back and forth with ten voices with a No. 3 cotton cloth, which is defined in JIS L0003 and which is connected to a CM ~ 1 stopwatch meter using a double-sided tape. The optical density of the cotton cloth was measured with the X-RITE 939 spectrodensitometer obtained from the X-Rite Corp, before and after the friction test to determine the difference between the optical density of the portion of the cotton cloth used for rubbing and the optical density of the cotton cloth prior to the friction test (ie the background density of the cotton cloth). The haze was classified as follows. ® (Excellent): The difference in optical density was less than 0.05. o (Good): Δ difference in optical density was not less than 0.05 and less than 0.1.
    A (Acceptable): The difference in optical density was not less than 0.1 c was less than 0.15. x (Bad): The difference in optical density was not less than 0.15. 6. Image brightness
    A color image of the graph was formed by the same method used to assess the image density, and then the post-processing process was performed on that.
    In this regard, the printer's printing mode has been set to a mode which is a 'glossy-light paper' mode modified so as not to be color compensated using a conductor attached to the printer. The brightness at 60 ”of the solid square image was measured with a gloss meter. The brightness was classified as follows. © (Excellent): The brightness was not less than 50%. o (Good): The brightness is not less than 30% and less than 50%. Δ (Acceptable): The brightness is not less than 15% and less than 30%. * (Bad); The brightness is less than 15%. Table 13


    Modifications or additional variations of the present invention are possible in light of the above teachings. It should, therefore, be understood that within the scope of the 5 appended claims the invention may be practiced in a manner different from that specifically described in this document.
    权利要求:
    Claims (7)
    [0001]
    1. Image formation method characterized by the fact that it comprises: adhering a pre-treatment liquid to a surface of a recording medium having a coating layer on it, in which the recording medium includes a support, and the coating layer coating is located on at least one surface of the support and where the pre-treatment liquid includes at least water and at least one of: i) a water-soluble aliphatic organic acid; ii) an ammonium salt of organic acid; or iii) a water-soluble cationic polymer; adhering an inkjet ink, including a dye, an organic solvent, a surfactant and water to the surface of the recording medium, to which the pre-treatment liquid has adhered, to form an image of the ink; and adhering a post-treatment liquid to the surface of the recording medium, on which the image was formed, wherein the after-treatment liquid includes a component capable of forming a transparent protective layer on the surface having an image of the recording medium, to form a protective layer at least on the ink image in the recording medium, in which the organic solvent of the ink includes: a polyalcohol with an equilibrium moisture content of at least 30% by weight at 23 ° C and 80% RH ; an amide compound having the formula mentioned below
    [0002]
    2. Imaging method according to claim 1, characterized by the fact that the amide compound has the following formula (1-1):
    [0003]
    3. Imaging method according to claim 1 or 2, characterized by the fact that the pre-treatment liquid includes a water-soluble aliphatic organic acid, having the following formula (V):
    [0004]
    4. Image-forming method according to claim 3, characterized by the fact that the pre-treatment liquid also includes a water-soluble organic monoamine compound.
    [0005]
    5. Image-forming method according to claim 4, characterized by the fact that the water-soluble organic monoamine compound has one of the following formulas (VI) and (VII):
    [0006]
    6. Imaging method according to claim 1 or 2, characterized in that the pre-treatment liquid includes at least one of ammonium lactate, ammonium acetate and a water-soluble cationic polymer.
    [0007]
    7. Image formation method according to any one of claims 1 to 6, characterized by the fact that the post-treatment liquid includes at least one water-dispersible resin selected from the group consisting of acrylic resins, styrene resins acrylics, urethane resins, silicone-acrylic resins and fluorine-containing resins
    类似技术:
    公开号 | 公开日 | 专利标题
    BR102013000712B1|2020-11-17|image formation method
    JP6292330B2|2018-03-14|Ink, inkjet recording apparatus, inkjet recording method, and recording set
    EP2686393B1|2018-02-07|Inkjet ink, inkjet recording method, and inkjet recording device
    EP2467262B1|2015-09-30|Image forming method, and image formed matter
    EP2766439B1|2016-05-11|Inkjet ink, inkjet recording method, and inkjet recording apparatus
    US8927623B2|2015-01-06|Recording ink, ink/media set, ink cartridge, inkjet recording method and inkjet recording apparatus
    US20140204156A1|2014-07-24|Inkjet recording method and inkjet recording device
    EP2774771B1|2019-09-04|Pre-treatment liquid and image forming method
    BR112013021183B1|2020-08-11|LIQUID TREATMENT LIQUID AND IMAGE FORMATION METHOD USING TREATMENT LIQUID
    EP2234814A1|2010-10-06|Image forming method and image formed record
    WO2007072951A1|2007-06-28|Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus
    JP2009113499A|2009-05-28|Composition and process
    JP5779865B2|2015-09-16|Inkjet recording method
    EP3015517B1|2018-01-03|Ink set, inkjet recording method, and colored body
    JP2005144905A|2005-06-09|Ink medium set and ink jet recording method using the same
    JP2009096054A|2009-05-07|Image recording method, image recording apparatus, and image recorded article
    JP2010188605A|2010-09-02|Ink liquid media set for inkjet recording and inkjet recording method
    JP2006273893A|2006-10-12|Ink set, and recording method and recorded material using the same
    JP6303271B2|2018-04-04|Image forming method
    JP2008239705A|2008-10-09|Ink set, recording method using this, and recorded matter
    JP5967496B2|2016-08-10|Ink composition for inkjet recording
    JP2004330696A|2004-11-25|Recording medium, ink jet recording method and recording image
    同族专利:
    公开号 | 公开日
    CN103192620A|2013-07-10|
    JP2013163370A|2013-08-22|
    JP6064602B2|2017-01-25|
    CN103192620B|2015-01-21|
    US20130176369A1|2013-07-11|
    EP2614964B1|2017-01-04|
    US9068090B2|2015-06-30|
    EP2614964A2|2013-07-17|
    BR102013000712A2|2017-10-10|
    EP2614964A3|2014-04-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPH06105429B2|1988-08-15|1994-12-21|日本電気株式会社|Micro program controller|
    JP2860123B2|1989-11-30|1999-02-24|株式会社リコー|inkjet printer|
    US5224987A|1991-11-12|1993-07-06|E. I. Du Pont De Nemours And Company|Penetrants for aqueous ink jet inks|
    JPH0671882A|1992-06-05|1994-03-15|Seiko Epson Corp|Ink jet head and production thereof|
    JPH06159911A|1992-11-27|1994-06-07|Hitachi Ltd|Combination refrigerators|
    JP2000053997A|1998-08-04|2000-02-22|Nof Corp|Detergent composition|
    US6232361B1|1998-12-11|2001-05-15|Sun Chemical Corporation|Radiation curable water based cationic inks and coatings|
    JP4138219B2|1999-08-30|2008-08-27|花王株式会社|Water-based ink|
    JP2004330568A|2003-05-06|2004-11-25|Seiko Epson Corp|Ink jet type printing machine and printing method|
    JP2007144975A|2005-10-26|2007-06-14|Ricoh Co Ltd|Inkjet recording medium and recording method|
    KR100980746B1|2005-12-22|2010-09-07|가부시키가이샤 리코|Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus|
    US20070197685A1|2006-01-18|2007-08-23|Tamotsu Aruga|Recording ink as well as ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus and inkjet recording method|
    EP1994102B1|2006-03-10|2011-12-28|Ricoh Company, Ltd.|Recording ink, ink cartridge, inkjet recording method, and inkjet recording apparatus|
    JP5118832B2|2006-08-22|2013-01-16|株式会社リコー|Ink for recording and ink media set, ink cartridge, ink jet recording method and ink jet recording apparatus|
    US7919544B2|2006-12-27|2011-04-05|Ricoh Company, Ltd.|Ink-media set, ink composition, ink cartridge, inkjet recording method, inkjet recording apparatus, and ink recorded matter|
    JP5097395B2|2006-12-28|2012-12-12|株式会社リコー|Ink for recording, ink media set, ink cartridge, ink jet recording method, ink jet recording apparatus, and ink recorded matter|
    JP5240501B2|2007-03-19|2013-07-17|株式会社リコー|Ink set, ink cartridge, ink jet recording method, and ink jet recording apparatus|
    US7828887B2|2007-04-23|2010-11-09|Hewlett-Packard Development Company, L.P.|Dye-based ink formulations|
    JP5263584B2|2007-06-12|2013-08-14|株式会社リコー|Ink jet recording ink, ink media set, ink cartridge, ink jet recording apparatus, and ink jet recording method|
    JP2009166387A|2008-01-17|2009-07-30|Ricoh Co Ltd|Image formation method and image formation recorded matter|
    JP5621192B2|2008-09-05|2014-11-05|株式会社リコー|Ink jet ink, ink cartridge, ink jet recording apparatus, ink jet recording method, image forming method, and ink recorded matter|
    JP5776141B2|2009-06-23|2015-09-09|株式会社リコー|Ink jet recording ink, ink jet recording method using the ink, cartridge containing the ink, and recorded matter|
    US8814340B2|2009-08-21|2014-08-26|Ricoh Company, Ltd.|Image forming method, and image formed matter|
    JP5558053B2|2009-09-04|2014-07-23|富士フイルム株式会社|Ink composition, ink set, and image forming method|
    JP5499344B2|2009-09-28|2014-05-21|大日本塗料株式会社|Water-based ink composition|
    JP5574099B2|2010-05-26|2014-08-20|セイコーエプソン株式会社|Ink composition for inkjet printing and inkjet printing method|
    JP2012000893A|2010-06-17|2012-01-05|Ricoh Co Ltd|Inkjet recording treatment liquid, inkjet cartridge, inkjet recording ink set, and inkjet recording method|
    JP5811759B2|2010-10-18|2015-11-11|株式会社リコー|Ink for recording, ink cartridge, ink jet recording method, ink jet recording apparatus, and ink recorded matter|
    JP5768394B2|2011-02-10|2015-08-26|株式会社リコー|Ink set for ink jet recording, ink jet recording method using the ink set, and recorded matter|
    JP5810883B2|2011-12-14|2015-11-11|株式会社リコー|Image forming method|
    JP2014094998A|2012-11-07|2014-05-22|Ricoh Co Ltd|Inkjet recording method|US6932124B2|2003-11-19|2005-08-23|Ice House America Llc|Automated ice bagging apparatus and methods|
    US7735527B2|2006-04-27|2010-06-15|Ice House America Llc|Automated ice delivery apparatus and methods|
    JP5601075B2|2010-08-04|2014-10-08|株式会社リコー|Ink jet ink, ink cartridge, ink jet recording method, ink jet recording apparatus, and ink recorded matter|
    JP5655618B2|2011-02-18|2015-01-21|株式会社リコー|Inkjet treatment liquid and image forming method using the treatment liquid|
    JP5825126B2|2011-03-14|2015-12-02|株式会社リコー|Ink jet ink, ink jet recording method, and ink jet recording apparatus|
    JP5810883B2|2011-12-14|2015-11-11|株式会社リコー|Image forming method|
    JP5957915B2|2012-02-01|2016-07-27|株式会社リコー|Cleaning liquid / filling liquid, cartridge containing the cleaning liquid / filling liquid, and method for cleaning, filling, and storing an inkjet recording apparatus using the cleaning liquid / filling liquid|
    JP6065607B2|2012-02-03|2017-01-25|株式会社リコー|Inkjet ink|
    US9056993B2|2012-07-10|2015-06-16|Ricoh Company, Ltd.|Ink composition, inkjet recording method, and printed matter|
    JP5910372B2|2012-07-11|2016-04-27|株式会社リコー|Image forming method|
    JP2014051625A|2012-09-07|2014-03-20|Ricoh Co Ltd|Ink for ink jet, ink cartridge, ink jet recording apparatus, and recorded matter|
    JP2014065890A|2012-09-10|2014-04-17|Ricoh Co Ltd|Ink for inkjet recording, ink cartridge, inkjet recording apparatus and recorded matter|
    CN104981351B|2012-12-20|2017-02-22|惠普发展公司，有限责任合伙企业|Post-printing treatment|
    JP6075075B2|2013-01-23|2017-02-08|株式会社リコー|Inkjet recording method and set of recording ink and recording medium|
    JP6269145B2|2013-03-13|2018-01-31|株式会社リコー|Ink jet ink, ink cartridge using the ink, ink jet recording apparatus, and ink recorded matter|
    CN105579232B|2013-07-31|2018-06-12|惠普发展公司，有限责任合伙企业|Thermal energy applied to dry printing fluids|
    JP2015044405A|2013-08-02|2015-03-12|株式会社リコー|Inkjet recording method and inkjet recording device|
    JP6287608B2|2013-09-02|2018-03-07|株式会社リコー|Ink composition for ink jet recording, recording apparatus and recorded matter|
    JP2015054421A|2013-09-11|2015-03-23|キヤノン株式会社|Image recording method and ink set|
    JP2016020469A|2013-09-13|2016-02-04|株式会社リコー|Ink for inkjet, ink set, ink cartridge, inkjet recording device, inkjet recording method and ink recorded article|
    JP6164033B2|2013-10-10|2017-07-19|株式会社リコー|Image forming method and image forming apparatus|
    JP6452317B2|2014-05-19|2019-01-16|キヤノン株式会社|Resin fine particle dispersion, ink for ink jet recording, ink jet recording method, ink cartridge, and ink jet recording apparatus|
    US9616694B2|2014-05-30|2017-04-11|Canon Kabushiki Kaisha|Image recording method|
    US10160248B2|2014-06-19|2018-12-25|Ricoh Company, Ltd.|Processing fluid, image forming method, recorded matter, and inkjet recording device|
    JP6390414B2|2014-12-22|2018-09-19|株式会社リコー|Inkjet recording method and ink set|
    US10280321B2|2015-01-29|2019-05-07|Ricoh Company, Ltd.|Ink, ink container, inkjet recording device, and recorded matter|
    CN105922778B|2015-02-27|2021-02-09|精工爱普生株式会社|Ink jet recording method and ink jet recording apparatus|
    JP6589340B2|2015-02-27|2019-10-16|セイコーエプソン株式会社|Inkjet recording method|
    CN105922777B|2015-02-27|2019-05-07|精工爱普生株式会社|Ink jet recording method and ink group|
    JP6714810B2|2015-04-14|2020-07-01|セイコーエプソン株式会社|Recording method and recording apparatus|
    EP3253574B1|2015-04-30|2018-09-26|Koenig & Bauer AG|Process and machine assemblies of printing presses for sequentially machining sheet-type stock|
    JP6494454B2|2015-07-10|2019-04-03|キヤノン株式会社|Inkjet recording method and inkjet recording apparatus|
    US9938421B2|2015-07-24|2018-04-10|Ricoh Company, Ltd.|Set of ink and print medium, inkjet printing method, inkjet printing apparatus, printed matter, ink, and ink stored container|
    EP3334790B1|2015-09-23|2021-07-14|Sun Chemical Corporation|Waterbased uv inkjet ink containing synthetic thickener|
    CN108472974B|2016-01-15|2020-04-07|东洋油墨Sc控股株式会社|Ink set and method for producing printed matter|
    WO2017140713A1|2016-02-19|2017-08-24|OCE Holding B.V.|Pre-treatment composition|
    JP6711146B2|2016-06-02|2020-06-17|株式会社リコー|Image forming set, image forming apparatus, and image forming method|
    US10150881B2|2016-07-29|2018-12-11|Riso Kagaku Corporation|Aqueous inkjet ink set for textile printing and method for producing printed textile item|
    JP6969191B2|2017-07-26|2021-11-24|セイコーエプソン株式会社|Inkjet ink composition for sublimation transfer and sublimation transfer inkjet recording method|
    KR102178853B1|2017-08-18|2020-11-13|주식회사 엘지화학|Infrared ray transmittance ink composition for inkjet, method for preparing a bezel pattern using the same, the bezel pattern using the same method and display panel comprising the bezel pattern|
    WO2019044673A1|2017-08-29|2019-03-07|コニカミノルタ株式会社|Inkjet image formation method|
    EP3622111B1|2017-10-18|2021-05-26|Hewlett-Packard Development Company, L.P.|Printing on a textile|
    WO2019084382A1|2017-10-27|2019-05-02|Nike Innovate C.V.|Articles comprising coated fibers and methods of making coated fibers and articles|
    EP3495154A1|2017-12-06|2019-06-12|Ricoh Company, Ltd.|Image forming method, image forming device, and method of manufacturing printed matter|
    CN110317491A|2018-03-30|2019-10-11|兄弟工业株式会社|Pretreating agent, pretreating agent bringing device, image forming method|
    US20220061464A1|2019-02-27|2022-03-03|Nike, Inc.|Articles, bladders and methods of making articles and bladders|
    JP2020199717A|2019-06-11|2020-12-17|株式会社リコー|Printing method and printing device|
    DE102020120411A1|2020-08-03|2022-02-03|Canon Production Printing Holding B.V.|Device and method for printing a recording medium with a printing device|
    法律状态:
    2017-10-10| B03A| Publication of an application: publication of a patent application or of a certificate of addition of invention|
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-08-04| B09A| Decision: intention to grant|
    2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-002423|2012-01-10|
    JP2012002423|2012-01-10|
    [返回顶部]