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    • 专利摘要:
    POST-TREATMENT LIQUID FOR INK JET ENGRAVING, IMAGE FORMATION METHOD, CARTRIDGE AND IMAGE FORMATION EQUIPMENT. A post-treatment liquid for inkjet engraving including a urethane resin, a fluorotensive, an organic solvent soluble in water and water.
    公开号:BR102013002698B1
    申请号:R102013002698-0
    申请日:2013-02-04
    公开日:2020-11-17
    发明作者:Michihiko Namba
    申请人:Ricoh Company, Ltd.；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
    The present invention relates to an after-treatment liquid for inkjet engraving, an imaging method, a cartridge and an imaging apparatus. DESCRIPTION OF RELATED TECHNIQUE
    An inkjet engraving method has been expanding rapidly in recent years as it makes it possible to engrave a color image on flat paper and at low operating costs. However, this method has problems that image defects typified by letter drop (smoothing) are likely to occur depending on combinations of an ink and a recording medium and also that the image quality degrades greatly as well as degradation of the image quality. folding on offset printing paper combined with water-based ink as long as it has extremely low absorbency of water-based ink. inkjet engraving method, colored inks that have different colors are superimposed one after the other. This causes the colored inks to blur or mix with a color boundary part (hereinafter referred to as 5 color drip), which is a problem of greatly diminished image quality.
    Thus, in order to increase the image quality by solving these problems, methods of image formation using a treatment liquid and an ink are proposed. For example, a method of discharging a treatment liquid from a head for uniform application of the treatment liquid, a method of pneumatically spraying and a method of uniform coating by controlling the pressures of one coating cylinder and one opposite cylinder are applied. considered.
    In addition, with respect to a treatment liquid used in a post-process after printing with an ink, a method including the processes of a pre-treatment process, a printing process and an after-treatment process, wherein a UV varnish is sprayed particularly in the post-treatment process (for example, see JP Patent Application Open to the Public (JP-A) No. 2004- 330568), and a method of conferring scratch resistance to coating liquid including a resin after printing are considered (for example, see JP-A No. 2010-105187 and JP-A No. 2010-115854).
    The method described in JP-A No. 2004-330568 above has problems with increased device size, increased costs, and material safety. Also, the methods described in JP-A No. 2010-105187 and JP-A No. 2010-115854 have problems in ensuring the discharge stability of the masking liquid including a resin from the head and increased costs of materials such as resins and, especially, the scratch resistance of the printed materials of the offset printing paper using a water based ink is not enough. An oil-based ink is generally used on offset printing paper, but its use is restricted in view of resource conservation in recent years as well as security. Also, in view of energy conservation, printing is more favored with water-based ink, and especially when printing batches with a small number of pages, there is a trend that the market is shifting to printing on demand using a inkjet process. Generic offset printing paper is made for an oil-based ink specification, and its absorbance for a water-based ink is extremely low. Thus, the ink does not wet and diffuses evenly and bleeds severely, and there are major degradation problems, especially in the folding quality and drying properties of the image and in the fixation capacity immediately after printing in a fast pass print.
    Consequently, an inkjet recording on a recording medium, still on the recording on offset printing paper using a water-based ink, a post-treatment liquid for inkjet recording that allows an image that has folding quality superior and scratch resistance even in fast pass printing has now been sought. SUMMARY OF THE INVENTION
    The present invention aims to solve the above problems in conventional technologies and in obtaining the following object. That is, the present invention aims to provide a post-treatment liquid for inkjet engraving that allows an image having superior folding quality and resistance to engraving even in printing of a quick pass in inkjet engraving and a means of embossing and printing an inkjet printing paper using water-based ink.
    The means to solve the problems are as follows.
    That is, an after-treatment liquid for inkjet etching of the present invention is an after-treatment liquid for ink-jet etching including a urethane resin, a fluorotensive, an organic solvent soluble in water and water.
    The present invention can solve conventional problems and provide an after-treatment liquid for inkjet engraving that allows an image having superior folding quality and resistance to engraving 10 even when printing a quick pass in inkjet engraving in one recording medium, as well as the recording of an offset printing paper using water-based ink. BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1 is a schematic diagram illustrating an example of a general configuration of an imaging method of the present invention (natural drying).
    Figure 2 is a schematic diagram illustrating an example of a general configuration of an imaging method 20 of the present invention (drying with hot air.
    Figure 3 is a schematic diagram illustrating an example of a general configuration of an imaging method of the present invention (hot air drying + hot fixing roller).
    Figure 4 is a schematic diagram illustrating an example of a general configuration of an imaging method of the present invention (heat roller drying). Figure 5 is a schematic diagram illustrating an example of a general configuration of an imaging method of the present invention (drying with infrared radiation).
    Figure 6 is a schematic diagram illustrating an example of a general configuration of an imaging method of the present invention (microwave drying).
    Figure 7 is a perspective view illustrating an ink cartridge loading section of an inkjet recording device (image forming apparatus) with its cover open.
    Figure 8 is a schematic configuration diagram explaining an overall configuration of an inkjet recording device.
    Figure 9 is a schematic diagram illustrating a post-treatment liquid bag as an example of a cartridge of the present invention.
    Figure 10 is a schematic diagram illustrating a cartridge in which the post-treatment liquid bag of Figure 9 is still contained in a cartridge box. DETAILED DESCRIPTION OF THE INVENTION Post-Treatment Liquid for Inkjet Engraving
    A post-treatment liquid for inkjet engraving of the present invention (hereinafter may be abbreviated as a post-treatment liquid) includes a urethane resin, a fluorotensive, an organic solvent soluble in water and water, and includes other components as needed. Urethane Resin
    Urethane resin is an essential component to provide image scratch resistance to an imaging section. A mixing ratio is preferably 10 wt% to 90 wt% of the total post-treatment liquid. Sufficient image scratch resistance can be provided when it is within this range. Also, the brightness of the image can be controlled by controlling the particle diameter and smoothing during film formation of the urethane resin.
    The urethane resin is not particularly restricted and can be appropriately selected according to the purpose. However, an emulsifying urethane resin that has superior dispersion stability is preferable, and an emulsifying ether-based urethane resin is more preferable in view of the film forming and bending properties of imparting the post-treatment liquid to the section image formation.
    An average particle diameter of the ether-based urethane resin 5 is not particularly restricted and can be selected appropriately according to the purpose. However, it is preferably 10 nm to 300 nm, more preferably 10 nm to 100 nm, and particularly preferably 10 nm to 80 nm. When the average 10-particle diameter is less than 10 nm, the viscosity of the resin may be too high to discharge into an inkjet printer. Also, when the average particle diameter exceeds 300 nm, particles can clog in a nozzle of an inkjet printer, causing 15 discharge failure.
    Also, an ether-based glass transition temperature of the urethane resin is not particularly restricted and can be selected appropriately according to the purpose. However, it is preferably -50 ° C to 150 ° C, and 20 more particularly -10 ° C to 30 ° C. When it is 150 ° C or less, sufficient scratch resistance can be achieved. However, a glass transition temperature of less than -50 ° C is not preferable since the film is very soft, decreasing the scratch resistance. In this document, the glass transition temperature can be measured by DSC (differential scanning calorimetry) or TMA (thermomechanical analysis).
    A minimum film-forming temperature (MET) of the ether-based urethane resin is not particularly restricted and can be appropriately selected according to the purpose. However, it is preferably 25 ° C or less. With the minimum film-forming temperature of the ether-based urethane resin of 25 ° C or less, film formation can be carried out at 25 ° C or less, and bonding to the paper fiber proceeds automatically without heating or drying. a recording medium with image formation. In this document, the "minimum film-forming temperature" above means a minimum temperature at which a continuous, transparent film is formed when aqueous emulsion particles obtained by dispersing the ether-based urethane resin particles in water are flowing finely over a metal plate such as aluminum and its temperature is increased.
    Like the ether-based urethane resin, the 20 properly synthesized can be used, or commercially available products can be used. These can be used alone or in combination of two or more. Examples of ether-based urethane resin include those described in JP-A No. 2009-67907, JP-A No. 2009-173805 and JP-A No. 2009-161726. Also, examples of commercially available products include: W5661, XW-75-W932, manufactured by
    Mitsui Chemicals Inc. and SF460S, manufactured by Nippon Unicar Co., Ltd. 5 Fluorotensoativo Fluorotensoativo is added by applying the after-treatment liquid evenly over the imaging section. With the presence of fluorosurfactant, the wetting and diffusion of post-treatment liquid points after 10 release improves, and uniformity improves. Fluorotensive is not particularly restricted and can be appropriately selected according to the purpose. However, those having 2 to 16 fluorine-substituted carbon atoms are preferable, and those having 4 to 16 fluorine-substituted carbon atoms are more preferable. A fluorine effect cannot be obtained with those that have less than two fluorine-substituted carbon atoms, and ink storage stability problems can occur with those that have excess fluorine-carbon atoms. These can be used alone or in combination of two or more.
    Examples of fluorotensive agents include: a perfluoroalkyl phosphate ester compound; a perfluoroalkyl ethylene oxide adduct; and a polyoxyalkylene ether polymeric compound having a perfluoroalkyl ether group on a side chain.
    Among these, the polyoxyalkylene ether polymeric compound that has a perfluoroalkyl ether group 5 in a side chain is particularly preferable since it has less foaming properties. A fluorotensive agent represented by the general formula (1) below is still preferable. CF3CF2 (CF2CF2) m- CF2CF2O (CF2CF2O) nH 10 General formula (1) where, in the general formula (1), m represents an integer from 1 to 10, and n represents an integer from 1 to 40. Examples of compound of perfluoroalkyl phosphate ester 15 include a perfluoroalkyl phosphate ester and a perfluoroalkyl phosphate ester salt. Examples of polymeric polyoxyalkylene ether compounds that have a perfluoroalkyl ether group 20 in a side chain include: a polyoxyalkylene ether polymer that has a perfluoroalkyl ether group in a side chain; a sulfate salt of a polyoxyalkylene ether polymer that has a perfluoroalkyl ether group on a side chain; and a salt of a perfluoroalkyl ether polymer having an ether group on a side chain. 5 10 A counterion in the salts of these fluorotensive agents is not particularly restricted and can be selected appropriately according to the purpose. However, examples thereof include Li, Na, K, NH4, NH3CH2CH2OH, NH2CH2CH2OH) 2, and NH (CH2CH2OH) 3.
    As specific examples of fluorotensive, the compounds represented by the general formula (2) to (1) are favorably used. (1) Anionic fluoride surfactant
    General Formula (2) where, in the general formula (2) Rf 'represents a mixture of hydrophobic groups containing fluorine represented by the following structural formulas; A represents -SO2X, -COOX, or -PO3 [where X is a counterion, specifically representing H, Li, Na, K, NH4, NH3CH2CH2OH, NH2 (CH2CH2OH) 2 OR NH (CH2CH2OH) 3] •
    where, in the general formula (3), Rf 'represents a group containing fluorine represented by the following general structure: X represents the same as X in the general formula (2); n 5 represents an integer of 1 or 2, and m represents 2-n.
    where, in the formula, n represents an integer from 3 to 10.
    * • General formula (4) where in general formula (4), Rf 'represents the same as 10 Rf' in general formula (3) and X represents the same as X in general formula (2). Rf'-SO3-X General formula (5) where, in the general formula (5) Rf 'represents the same as Rf' in the general formula (3), and X represents the same as X in the general formula (2). (2) Non-ionic fluorotensive
    General formula (6) where, in general formula (6), Rf represents the same as Rf in general formula (2), and n represents an integer 5 from 5 to 20.
    where, in the general formula () Rf 'represents the same as Rf in the general formula (3) and n represents an integer from 1 to 40. ^ amphoteric affective (3) Fluorotensoativo
    General formula (8) (8), Rf represents the same as where, in formula 0e • vThe oligomer type
    (4) Fluorotension General formula (9) CH2 where, in general formula (9), Rf "represents a group containing fluorine represented by the structural formula below; n represents an integer from 1 to 10; and X represents the same as X in the general formula (2).
    where, in the formula, n represents an integer from 1 to 4.
    General formula (10) where, in general formula (10), Rf "represents the same as Rf" in general formula (9); and 1 represents an integer from 0 to 10, m represents an integer from 0 to 10 10 and n represents an integer from 0 to 10 (where 1 + n is an integer from 1 or greater).
    Like fluorosurfactants, those properly synthesized can be used, or commercially available products can be used. Examples of commercially available products include: SURFLON (registered trademark) S-lll, S-112, S-113, S-121, S-131, S-132, S- 141, S-145 (all manufactured by Asahi Glass Co ., Ltd.); FLUORAD FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Ltd.); MEGAFACE (registered trademark) F-470, F-1405, F-474 (all manufactured by DIC Corporation); ZONYL (registered trademark) TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300 (all manufactured by DuPont Co.); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Company Ltd.); and POLYFOX (registered trademark) PF-136A, PF-156A, PF-151N, PF-154, PF-159 (all manufactured by OMNOVA Solutions Inc.). Among them, FS-300 manufactured by DuPont Co., FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Company Ltd., and POLYFOX PF-151N manufactured by OMNOVA Solutions Inc. are particularly preferable in view of the favorable print quality, especially in view of the significant improvement in color development and tinting level for the paper.
    A fluorotensive content in the post-treatment liquid is preferably 0.001 wt% to 5 wt%, and more preferably 0.05 wt% to 1 wt%. When the content is less than 0.001% by weight, an effect of adding a surfactant can decrease. When it exceeds 5% by mass, no difference in effect can be seen despite the increased amount of the addition. Water-soluble organic solvent
    The water-soluble organic solvent is not particularly restricted and can be selected appropriately according to the purpose. For example, those described below for a post-treatment liquid can also be used. The water-soluble organic solvent can be used alone or in combination of two or more. A mixing ratio of the water-soluble organic solvent in the post-treatment liquid is, similar to the post-treatment liquid described below, preferably 10% by mass to 80% by mass, and more preferably 15% by mass at 60%. % in large scale. 15 Water
    Water is not particularly restricted and can be selected appropriately according to the purpose. For example, pure water such as ion exchange water, ultrafiltered water, reverse osmosis water and distilled water, or ultrapure water can be used. These can be used alone or in combination of two or more. Other components
    The other components are not particularly restricted and can be selected appropriately according to the purpose. Examples of these include a penetrating agent, surfactant, water-dispersible resin particles, a water-soluble polymer, a defoamer, an antiseptic and fungicide, a rust inhibitor, a pH adjuster, a resistivity modifier, an antioxidant, an ultraviolet absorber, an oxygen absorber, a light stabilizer, and a viscosity modifier. These can be used alone or in combination of two or more. Image formation method
    One imaging method of the present invention is an inkjet imaging method, including an imaging process that forms an image on a recording medium using an ink and an after-treatment coating process. an image-forming section formed by the image-forming process by discharging the post-treatment ink recording liquid of the present invention, and further includes a pre-treatment process that subjects the recording medium to a pre-treatment with a pre-treatment liquid before the imaging process according to need. Recording medium
    The recording medium is not particularly restricted and can be selected appropriately according to purpose. Examples of the same include flat paper having a size degree of 10 s or greater and air permeability of 5 s to 50 s, which do not include a coating layer and is generally used as copy paper. However, the post-treatment liquid of the present invention is particularly effective for inkjet engraving on offset printing paper using water-based ink.
    Offset printing paper
    Offset printing paper is coated paper that is used in commercial printing such as so-called air paper (AO, Al), coated paper A2, coated paper A3, coated paper B2, coated paper with light weight, and lightly coated paper , indicating a paper used for offset printing and engraving printing.
    Art paper is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include: OK Kanefuji N, Satin Kanefuji R40N, Ultrasatin Kanefuji N, Ultra OK Kanefuji N, Kanefuji One Side (all manufactured by Oji Paper Co., Ltd.); NPi Special Art, NPi Super Art, NPi Super Dull, NPi Dull Art (all manufactured by Nippon Paper Industries Co., Ltd.); UUtrillo Super Art, Ultrillo Super Dull, Ultrillo Premium (all manufactured by Daio Paper Corporation); High-Quality Art, Tokuhishi Art, Super Mat Art A, High-Quality Dull Art
    A (all manufactured by Mitsubishi Paper Mills Ltd.); Raicho Super Art N, Raicho Super Art MN, Raicho Super Art, Raicho Dull Art N (all manufactured by Chuetsu Pulp & Paper Co., Ltd.).
    A2 coated paper is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include OK Top Coatt (plus), OK Top Coat S, OK Casablanca, OK Casablanca V, OK Trinity, OK Trinity NaVi, New Age, New Age W. OK Top Coat Mat N, OK Royal Coat, OK Top Coat Dull, Z Coat, OK Kasahime, OK Kasao, OK Kasao Satin, OK Top Coat +, OK Non-wrinkle, OK Coat V, OK Coat N Green 100, OK Mat Coat Green 100, New Age Green 100, Z Coat Green 100 ( all manufactured by Oji Paper Co., Ltd.); Aurora Coat, Shiraoi Mat, Imperial Mat, Silver Diamond, Recycle Coat 100, Cycle Mat 100 (all manufactured by Nippon Paper Industries Co., Ltd.); Mu Coat, Mu White, Mu Mat, White Mu Mat (all manufactured by Hokuetsu Paper Mills Ltd.); Raicho Coat N, Regina Raicho Coat 100, Raicho Mat Coat N, Regina Mat 100 (all manufactured by Chuetsu Pulp & Paper Co., Ltd.); Pearl Coat, White Pearl Coat N, New V Mat, White New V Mat, Pearl Coat REW, White Pearl Coat NREW, New V Mat REW, White New V Mat REW (all manufactured by Mitsubishi Paper Mills Ltd.).
    A3 coated paper (coated with light weight) is not particularly restricted and can be selected appropriately according to the purpose. Examples of it include: OK Coat L, Royal Coat L, OK Coat LR, OK White L, OK Royal Coat LR, OK Coat L Green 100, OK Mat Coat L Green 100 (all manufactured by Oji Paper Co., Ltd.) ; Easter DX, Recycle Coat L100, Aurora L, Recycle Mat L100, <SSS> Energy White (all manufactured by Nippon Paper Industries Co., Ltd.); Utrillo Coat L, Matisse Coat (all manufactured by Daio Paper Corporation); Hi Alpha Mat, (N) Kinmari L, Kinmari HiL (all manufactured by Hokuetsu Paper Mills Ltd.); N Pearl Coar L, N Pearl Coat LREW, Swing Mat REW (all manufactured by Mitsubishi Paper Mills Ltd.); Super Emine, Emine, Chaton (all manufactured by Chuetsu Pulp & Paper Co., Ltd.).
    B2 coated paper (coated with medium quality) is not particularly restricted and can be selected appropriately according to the purpose. Examples of it include OK Medium Quality Coat, (F) MCOP, OK Astro Gloss, OK Astro Dull, OK Astro Mat (all manufactured by Oji Paper Co., Ltd.); King O (manufactured by Nippon Paper Industries Co., Ltd.).
    Lightly coated paper is not particularly restricted and can be selected appropriately according to the purpose. Examples of this include: OK Royal Light
    S Green 100, OK Ever Light Coat, OK Ever Light R, OK Ever Green, Clean Hit MG, OK Microcoated Super Eco G, Eco Green Dull, OK Microcoated Mat Eco G100, OK Star Light Coat, OK Soft Royal, OK Bright, Clean Hit G, Yamayuri Bright, Yamayuri Bright G, OK Aqua Light Coat, OK Royal Light S Green 100, OK Bright (rough, shine), Snow Mat, Snow Mat DX, OK Kasahime, OK Kasayuri (all manufactured by Oji Paper Co ., Ltd.); Pyrene DX, Pegasus Hyper 8, Aurora S, Andes DX, Super Andes DX, Space DX, Seine DX, Special Gravure DX, Pegasus, Silver Pegasus, Pegasus Harmony, Greenland DX100, Super Greeland DX100, <SSS> Energy Soft, <SSS > Energy Light, EEHenry (all manufactured by Nippon Paper Industries Co., Ltd.); Kant Excel, Excel Super B, Excel Super C, Kant Excel Bal, Utrillo Excel, Heine Excel, Dante Excel (all manufactured by Daio Paper Corporation); Cosmo Ace (manufactured by Nippon Daishowa Paperboard Co., Ltd.); Semi-Jo L, Hi Beta, Hi Gamma, Shiromari L, Hamming, White Hamming, Semi-Jo HiL, Shiromari HiL (all manufactured by Hokuetsu Paper Mills Ltd.); Ruby Light HREW, Pearl Soft, Ruby Light H (all manufactured by Mitsubishi Paper Mills Ltd.); Chaton, Ariso, Smash (all manufactured by Chuetsu Pulp & Paper Co., Ltd.); Star Cherry, Cherry Super (all manufactured by Marusumi Paper Co., Ltd.). Pre-treatment liquid
    The pretreatment liquid includes a water-soluble organic solvent, water, and any of an aliphatic organic acid salt and an inorganic metal salt, and further includes other components as needed. Aliphatic organic acid salt
    The aliphatic organic acid salt is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include sodium L-aspartate, magnesium L-aspartic acid, calcium ascorbate, sodium L-ascorbate, sodium succinate, disodium succinate, diamonium succinate, aluminum citrate, potassium citrate, calcium citrate, triamonium citrate, tripotassium citrate, trisodium citrate, diamonium citrate, disodium citrate, zinc lactate, aluminum lactate, ammonium lactate, potassium lactate, calcium lactate, sodium lactate, magnesium lactate, potassium tartrate, calcium tartar, DL sodium tartrate, and sodium potassium tartrate. These can be used alone or in combination of two or more.
    Inorganic metal salt
    The inorganic metal salt is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include magnesium sulphate, aluminum sulphate, magnesium sulphate, nickel sulphate, iron (II) sulphate, copper (II) sulphate, zinc sulphate, iron (II) nitrate, iron nitrate (III) ), cobalt nitrate, strontium nitrate, copper (II) nitrate, nickel (II) nitrate, lead (II) nitrate, magnesium (II) nitrate, nickel (II) chloride, calcium (II) chloride ), strontium chloride, barium chloride, magnesium chloride, sodium sulfate, potassium sulfate, lithium sulfate, sodium hydrogen sulfate, potassium bisulfate, sodium nitrate, potassium nitrate, sodium carbonate, potassium carbonate , sodium hydrogen carbonate, potassium bicarbonate, sodium chloride, potassium chloride. These can be used alone or in combination of two or more.
    An added amount of aliphatic organic acid salt or the inorganic metal salt is not particularly restricted and can be selected appropriately according to the purpose. However, it is preferably 0.1 wt% to 30 wt%, and more preferably 1 wt% to 20 wt% of the total pre-treatment liquid. When it exceeds 30% by mass, the aliphatic organic acid salt cannot dissolve sufficiently, resulting in precipitation. When it is less than 0.1% by mass, an effect of increased image density may decrease. Water-soluble organic solvent
    The water-soluble organic solvent is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include polyhydric alcohols having an equilibrium moisture content of 30% by weight or greater in an environment with a temperature of 23 ° C and a humidity of 80%.
    Specific examples of such a water-soluble organic solvent include 1,2,3-butanotriol (boiling point: 175 ° C / 33hPa, 38% by mass), 1,2,4-butanotriol (boiling point: 190 ° C at 191 ° C / 24hPa, 41% by weight), glycerin (boiling point: 290 ° C, 49% by weight), diglycerin (boiling point: 270 ° C / 20hPa, 38% by weight), triethylene glycol (point boiling point: 285 ° C, 39% by weight), tetraethylene glycol (boiling point: 324 ° C to 330 ° C, 37% by weight), diethylene glycol (boiling point: 245 ° C, 43% by weight) , 1,3-butanediol (boiling point: 203 ° C to 204 ° C, 35% by mass). These can be used alone or in combination of two or more. Among the water-soluble organic solvents, glycerin and 1,3-butanediol are preferable since they become less viscous when including moisture. Also, the use of at least one of glycerin and 1,3-butanediol in 50% by weight or more of the total water-soluble organic solvent is more preferable as long as it is superior in terms of ensuring discharge stability or preventing the fixation of a waste ink 5 in a support device of an ink discharge device. The water-soluble organic solvent can also serve as a wetting agent.
    Also, examples of a water-soluble organic solvent or a wetting agent other than the above, which can be used in combination as needed include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, heterocyclic compounds containing nitrogen, amides, amines, sulfur-containing compounds, propylene carbonate, and 15 ethylene carbonate.
    Polyhydric alcohols are not particularly restricted and can be selected appropriately according to the purpose. Examples of these include dipropylene glycol (boiling point: 232 ° C), 1.5-20 pentanediol (boiling point: 242 ° C), 3-methyl-1,3, butanediol (boiling point: 203 ° C) , propylene glycol (boiling point: 187 ° C), 2-methyl-2,4-pentanediol (boiling point: 197 ° C), ethylene glycol (boiling point: 196 ° C to 198 ° C), tripropylene glycol (boiling point: 267 ° C), hexylene glycol (boiling point: 197 ° C), polyethylene glycol (viscous solid liquid), polypropylene glycol (boiling point: 187 ° C), 1,6-hexanediol (point boiling point: 253 ° C to 260 ° C), 1,2,6-hexanotriol (boiling point: 178 ° C), trimethylethane (solid; melting point: 199 ° C to 201 ° C) and trimethylolpropane (solid; melting point 61 ° C).
    The alkyl ethers of polyhydric alcohol are not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include ethylene glycol monoethyl ether (boiling point: 135 ° C), ethylene glycol monobutyl ether (boiling point: 171 ° C), diethylene glycol monomethyl ether (boiling point: 194 ° C), ether diethylene glycol monoethyl (boiling point: 197 ° C), diethylene glycol monobutyl ether (boiling point: 231 ° C), ethylene glycol mono-2-ethylhexyl ether (boiling point: 229 ° C) and monoethyl ether propylene glycol (boiling point: 132 ° C).
    Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether (boiling point: 237 ° C), and ethylene glycol monobenzyl ether.
    Heterocyclic compounds containing nitrogen are not particularly restricted and can be selected appropriately according to the purpose. Examples of these include 2-pyrrolidone (boiling point: 250 ° C, melting point: 25.5 ° C), N-methyl-2-pyrrolidone (boiling point: 202 ° C), 1,3-dimethyl- 2-imidazolidinone (5-boiling point: 226 ° C), ε-caprolactam (boiling point: 270 ° C) and y-butyrolactone (boiling point: 204 ° C to 205 ° C).
    Amides are not particularly restricted and can be selected appropriately according to the purpose. Examples of these include formamide (boiling point: 10 210 ° C), N-methylformamide (boiling point: 199 ° C to 201 ° C), N, N-dimethylformamide (boiling point: 153 ° C) and N, N-diethylformamide (boiling point: 176 ° C to 177 ° C).
    Amines are particularly restricted and can be selected appropriately according to the purpose. Examples of these include monoethanolamine (boiling point: 170 ° C), diethanolamine (boiling point: 268 ° C), triethanolamine (boiling point: 360 ° C), N, N-dimethylaminoethanolamine (boiling point: 139 ° C), N-methyldiethanolamine (boiling point: 243 ° C), N-20 methylethylamine (boiling point: 159 ° C), N-phenylethanolamine (boiling point: 282 ° C to 287 ° C), and 3- aminopropylethylamine (boiling point: 169 ° C). Sulfur-containing compounds are not particularly restricted and can be selected appropriately according to the purpose. Examples of these include dimethyl sulfoxide (boiling point: 139 ° C), sulfolane (boiling point: 285 ° C), and thiodiglycol (boiling point: 282 ° C). Water
    Water is not particularly restricted and can be selected appropriately according to the purpose. For example, pure water such as ion exchange water, ultraviolet water, reverse osmosis water and distilled water, or ultrapure water can be used. These can be used alone or in combination of two or more. Other components
    The other components are not particularly restricted and can be selected appropriately according to the purpose. Examples of these include a wetting agent, a penetrating agent, and an antiseptic and a rust inhibitor that are also used in a paint described below. In the present document, there are cases where the water-soluble organic solvent serves as a wetting agent, but a separate wetting agent can be added. Also, as a wetting agent, a solid wetting agent can be used. These can be used alone or in combination of two or more. Solid wetting agent
    The solid wetting agent is not particularly restricted and can be selected appropriately according to the purpose. However, sugars are preferred.
    Sugars are not particularly restricted and can be selected appropriately according to the purpose. Examples thereof include monosaccharides, disaccharides, oligosaccharides (including trisaccharides, tetrasaccharides), and polysaccharides. Specific examples thereof include glucose, mannose fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose and maltotriose. In this document, the term "polysaccharides" refers to sugars in a broad sense of the term, and is used to mean substances that are extensively present in nature, including a-cyclodextrin, cellulose. Also, examples of derivatives of these sugars include sugar-lowering sugars (for example, sugar alcohols (General formula: HOCH2 (CHOH) nCH2θH (where n represents an integer from 2 to 5), and oxidized sugar (for example, acid aldonic, uronic acid)}, amino acids and thioacids Among these, sugar alcohols are preferable, and specific examples of them include maltitol and sorbitol, which can be used alone or in combination of two or more.
    A content of the water-soluble organic solvent or a content of the water-soluble organic solvent and the wetting agent in the pre-treatment liquid are not particularly restricted and can be selected appropriately according to the purpose. However, it is preferably 10% by mass to 80% by mass, and still preferably 15% by mass to 60% by mass. When it exceeds 80% by mass, drying defects may occur in the recording medium depending on the types of water-soluble organic solvent or wetting agent. When it is less than 10% by mass, a composition of the pre-treatment liquid can change greatly due to the evaporation of moisture in the pre-treatment process. Penetrating Agent
    The penetrating agent is not particularly restricted and can be selected appropriately according to the purpose. However, a non-wetting glycol or polyol ether having 8 to 11 carbon atoms is preferable. It most preferably has a solubility of 0.2 wt% to 5.0 wt% in water at 25 ° C, and 2-ethyl-1,3-hexanediol [solubility: 4.2% (25 ° C)] , 2,2,6-trimethyl-1,3-pentanediol [solubility: 2.0% (25 ° C)] are particularly preferable. These can be used alone or in combination of two or more.
    The non-wetting polyol is not particularly restricted and can be selected appropriately according to the purpose. However, examples of the same include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2- propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol and 5-hexane-1,2-diol.
    The penetrating agent other than the above that can be used in combination is not particularly restricted as long as it is dissolved in the pretreatment liquid to adjust the desired physical properties, and it can be selected appropriately according to the purpose. Examples of the same include: alkyl and aryl ethers of a polyhydric alcohol such as diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoalkyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether ; and tetraethylene glycol chlorophenyl ether; and lower alcohols such as ethanol.
    A content of penetrating agent in the pre-treatment liquid is not particularly restricted and can be selected appropriately according to the purpose.
    However, it is preferably 0.1% by mass to 5.0% by mass. When the content is less than 0.1 mass%, the penetrating agent cannot have an effect for the pretreatment liquid to penetrate. When the content exceeds 5.0% by mass, the penetrating agent separates from the solvent due to its low solubility for the solvent, which can result in an improved penetration effect being saturated. Ink
    The ink is not particularly restricted as long as it can be used for inkjet engraving, and can be selected appropriately according to the purpose. However, a water-based paint is preferable in view of the remarkable effect of the after-treatment liquid. Water-based ink
    The water-based ink includes a water-dispersible dye, a water-soluble organic solvent, a surfactant, a penetrating agent and water, and, in addition, includes other components as needed. Color dispersible in water
    The water-dispersible dye is not particularly restricted and can be selected appropriately according to the purpose. A pigment is preferable in view of water resistance, but a dye can be used in combination to adjust color within a range that does not degrade weather resistance. The pigment is not particularly restricted and can be selected appropriately according to the purpose. 5 Examples of this include black or colored inorganic pigments and organic pigments. These can be used alone or in combination of two or more.
    Inorganic pigments are not particularly restricted and can be selected appropriately and according to the purpose. Examples of these include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow and carbon black manufactured by a method hitherto known as the method of contact, 15 oven method and thermal method. These can be used alone or in combination of two or more.
    Organic pigments are not particularly restricted and can be selected appropriately according to the purpose. Examples of these include 20 azo pigments (including azo lake, insoluble azo pigments, condensed azo pigments, azo chelate pigments, etc.), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments , quinacridone pigments, dioxazin pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), dye-type chelate (eg, basic dye chelate, acid dye chelate, 5 etc.), pigments nitro, nitrous pigments and aniline black. These can be used alone or in combination of two or more.
    Among these pigments, those that have a high affinity for water are preferable. Specific examples of preferable black pigments include carbon blacks such as furnace carbon black, lamp carbon black and channel carbon black (C.I. Pigment Black 7); metals such as copper and iron (C.I. Pigment Black 11); metal oxides such as titanium oxide; organic pigments such as aniline black (C.I. Pigment Black 1).
    Also, specific examples of preferable color pigments include: CI Yellow pigment 1, 3, 12, 13, 14, 7, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 20 74, 81, 83, 95, 97, 98, 100, 101, 104, 408, 109, 110, 117, 120, 128, 138, 150, 151, 153, 183; C.I. Orange pigment 5, 13, 16, 17, 36, 43, 51; CI Red Pigment 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53 : 1, 57: 1 (Bright Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 82, 83, 88, 101 (red iron oxide), 104, 105, 106, 108 ( cadmium red), 112, 114 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219; C.I. Pigment 5 violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38; C.I.
    Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3 (Phthalocyanine Blue), 16, 17: 1, 56, 60, 63; and C.I.Green pigment 1, 4, 7, 8, 10, 17, 18, 36.
    When the water-dispersible dye is a pigment-based dye 10, preferred embodiments thereof include the following first and second embodiments. In particular, a water dispersible dye of the first embodiment is preferably used.
    The first embodiment includes a polymeric emulsion in which a water-insoluble or weakly-soluble pigment is included in the polymeric particles (aqueous dispersion of the polymeric particles including a pigment).
    The second embodiment includes a pigment that includes at least one type of a hydrophilic group on a surface of the same and demonstrates water dispersibility in the absence of a dispersant (which can also be referred to as a "self-dispersing pigment" hereinafter) .
    In the present document, in the second embodiment, it is preferable to include a water-dispersible resin described hereinafter.
    As the water-dispersible dye of the first embodiment it is preferable to use, in addition to the pigment, a polymeric emulsion in which a pigment is included in the polymeric particles. The polymeric emulsion in which a pigment is included in polymeric particles is that in which a pigment is encapsulated in the polymeric particles or in which a pigment is adsorbed on a surface of the polymeric particles. In this case, it is not necessary for the entire pigment to be encapsulated or adsorbed and a part of the pigment can be dispersed in the emulsion.
    Examples of a polymer that forms the polymeric emulsion include a vinyl polymer, a polyester polymer and a polyurethane polymer, and vinyl polymer and polyester polymer are preferable. For example, the polymers described in JP-A No. 2000-53897 and JP-A No. 2001-139849 can be used.
    Like the water-dispersible dye of the second modality, those subjected to surface modification in such a way that at least one type of a hydrophilic group is attached to a pigment surface directly or through other atomic groups. Like surface modification, a method in which a specific functional group (functional groups such as sulfonic group and carboxyl group) is chemically attached to a pigment surface or a wet oxidation treatment is carried out using at least any of the hypohalous acid and a salt is used. Among these, a modality in which the pigment having a carboxyl group attached to a surface of the same is dispersed in water is particularly preferable. Since the pigment is modified on the surface in this way to have a carboxyl group attached to it, the stability of the dispersion improves and, in addition, the high print quality can be obtained as well as the water resistance of the recording medium after printing still gets better.
    Also, a water based ink including this self-dispersing pigment of the second modality has superior redispersibility after drying and, thus, favorable printing can be easily performed by a simple cleaning operation without the occurrence of clogging even though the humidity of the ink near a inkjet nozzle has evaporated after a long period of printing pause.
    A volume-average particle diameter (D50) of the self-dispersing pigment in the paint is preferably 0.01 pm to 0.16 pm. The self-dispersing pigment is preferably ionic, and a pigment charged anionically by an anionic hydrophilic group, etc. it is more preferable. The anionic hydrophilic group is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include -COOM, -SO3M, -5 PO3M2, -SO2NH2, -SO2NHCOR (where M represents an alkali metal, an ammonium or an inorganic ammonium; and R represents an alkyl group having 1 to 12 carbon atoms, a group phenyl which may have a substituent or a naphthyl group which may have a substituent). Among these, colored pigments having -COOM, -SO3M attached to a surface of the same are preferable.
    Also, the alkali metal "M" in the hydrophilic group is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include lithium, sodium and potassium. The organic ammonium "M" in the hydrophilic group is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include mono- to trimethylammonium, mono- to trimethyl ammonium and mono- to 20 trimethanolammonium.
    A method for obtaining anionically charged colored pigment is not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include a method of introducing -COONa to a color pigment surface. Examples of the method for introducing -COONa to a colored pigment surface include: a method of oxidizing the colored pigment with sodium hypochlorite; a sulfonation method; and a reaction method with a diazonium salt.
    The anionic hydrophilic group can be attached to a pigment surface through other atomic groups. The other atomic groups are not particularly restricted and can be selected appropriately according to the purpose. Examples of the same include an alkyl group having 1 to 12 carbon atoms, a phenyl group that may have a substituent and a naphthyl group that may have a substituent.
    Specific examples of the case where the anionic hydrophilic group is attached to a carbon black surface through other atomic groups include: -C2H4COOM (where M represents an alkali metal or a quaternary ammonium) and - PhSOβM (where pH represents a phenyl group; M represents an alkali metal or a quaternary ammonium).
    A colorant content in water-based ink is not particularly restricted and can be selected appropriately according to the purpose. However, as a solid content, 2 wt% to 15 wt% is preferable, and more preferably 3 wt% to 12 wt%. A content of less than 2% by mass or exceeding 15% by mass is not preferable since the paint with the former may have decreased the color-developing property and image density and with the latter having poor discharge properties due to increased viscosity. Water-soluble organic solvent
    The water-soluble organic solvent is not particularly restricted and can be selected appropriately according to the purpose. However, the same water-soluble organic solvent as for the pre-treatment liquid is used favorably. Similar to the pretreatment liquid, there are cases where the water-soluble organic solvent serves as a wetting agent, but it is also possible to add a separate wetting agent. Also, it is possible to use a solid wetting agent as the wetting agent.
    A mass ratio of the water-dispersible dye to the water-soluble organic solvent affects the stability of ink discharge from a head. For example, when a solid content of water-dispersible dye is large despite a small amount of water-soluble organic solvent, evaporation of water near a nozzle of the ink in the nozzle may proceed, resulting in poor discharge.
    A water-soluble organic solvent content in water-based ink is not particularly restricted and can be selected appropriately according to the purpose. However, 20% by mass is preferred to 50% by mass, and more preferable 20% by mass to 45% by mass. When the content is less than 20% by mass, the stability of the discharge may decrease, or the waste ink may be attached to a support device of an ink recording device. Also, when the content exceeds 50% by mass, the drying properties on paper may be less, and, in addition, the quality of the letter on flat paper may decrease.
    Examples of preferred water-soluble organic solvent include glycerin, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, a, 2-butanediol, 1,3-butanediol, 2,3-butanediol, 1 , 4-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-methyl-2,4-hexanediol, 1 , 2-octanodiol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, tetramethyl urea and urea. Surfactant
    The surfactant is not particularly restricted and can be selected appropriately according to the purpose. However, those with non-sacrificed dispersion stability, a low surface tension, and high penetration property and leveling property with respect to the types of water-dispersible dye and a combination with the water-soluble organic solvent are preferable. For example, an anionic surfactant, a nonionic surfactant, silicone surfactant and a fluorotensive are preferable. Among these, the silicone surfactant and the fluorotensive are particularly preferable. These surfactants can be used alone or in combination of two or more.
    A surfactant content in water-based paint is not particularly restricted and can be selected appropriately according to the purpose. However, it is preferable 0.01 wt% to 3.0 wt%, and more preferably 0.5 wt% to 2 wt%. When the content is less than 0.01% by weight, an effect of adding a surfactant may not be obtained. When it exceeds 3.0% by mass, the penetration into the recording medium increases more than necessary, and decreased image density and line crossing may occur, especially with flat paper. Penetrating agent
    The penetrating agent is not particularly restricted and can be selected appropriately according to the purpose. However, the same penetrating agent as for the pre-treatment liquid can preferably be used.
    A water-based ink penetrating agent content is not particularly restricted and can be selected appropriately according to the purpose. However, 0.1% by mass is preferable to 4.0% by mass. When the content is less than 0.1% by mass, fast drying properties cannot be obtained, resulting in a blurred image. When it exceeds 4.0% by mass, the dispersion stability of the colorant is impaired, and decreased image density and cross line, for example, easily clogged nozzle and excessive increase in penetration to a recording medium. Water
    Water is not particularly restricted and can be selected appropriately according to the purpose. Examples of this include: pure water such as ion exchange water, ultrafiltered water, reverse osmosis water and distilled water; and ultrapure water. These can be used alone or in combination of two or more. Other components
    The other components are not particularly restricted and can be selected appropriately according to need. Examples of these include a pH adjuster, an antiseptic and fungicide, a chelate reagent, a rust inhibitor; an antioxidant, an ultraviolet absorber, an oxygen absorber, and a light stabilizer. These can be used alone or in combination with two or more. The pH adjuster is not particularly restricted as long as it can adjust a pH of water-based ink prepared in 7 to 11 without adversely affecting the ink. It can be selected appropriately according to the need.
    Examples of pH adjuster include amine alcohols, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, and alkali metal carbonates. 15 When the pH of water-based ink is less than 7 or exceeds 11, a dissolved amount of an ink head and ink supply unit increases, which can cause defects such as ink change or leakage and flushing. Examples of amino alcohols include diethanolamine, triethanolamine, and 2-amino-2-ethyl-1,3-propanediol.
    Examples of hydroxides of an alkali metal element include lithium hydroxide, sodium hydroxide and potassium hydroxide.
    Examples of ammonium hydroxides include ammonium hydroxide and quaternary ammonium hydroxide.
    Examples of phosphonium hydroxides include quaternary phosphonium hydroxide.
    Examples of alkali metal carbonates include lithium carbonate, sodium carbonate and potassium carbonate.
    The antiseptic and fungicide is not particularly restricted and can be selected appropriately according to need. Examples of the same include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate and sodium pentachlorophenol.
    The chelate reagent is not particularly restricted and can be selected appropriately as needed. Examples of the same include sodium ethylenediaminetetraacetate, sodium nitritotriacetate, sodium hydroxyethylethylenediamine triacetate, sodium diethylene triamine pentaacetate and sodium uramyldiacetate.
    The rust inhibitor is not particularly restricted and can be selected appropriately according to need. Examples of the same include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaetritol tetranitrate and dicylexylammonium nitrite.
    The antioxidant is not particularly restricted and can be selected appropriately according to need. Examples of the same include a phenol-based antioxidant (including a hindered phenol-based antioxidant), an amine-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
    The ultraviolet absorber is not particularly restricted and can be selected appropriately according to need. Examples of the same include a benzophenone based ultraviolet absorber, a benzotriazole based ultraviolet absorber; a salicylate based ultraviolet absorber, a cyanoacrylate based ultraviolet absorber, and a nickel complex salt based ultraviolet absorber. Physical properties of water-based paint
    The physical properties of water-based paint are not particularly restricted and can be selected appropriately according to the purpose.
    A water-based ink viscosity at 25 ° C is preferably 5 mPa.s to 20 mPa.s. An effect of the desired print density and letter quality can be obtained with the viscosity being 5 mPa.s or greater. At the same time, the discharge property can be ensured with the viscosity suppressed at 20 mPa.s or less. In this document, viscosity can be measured at 25 ° C, for example, using a viscosity meter (RE-550L, manufactured by Toki Sangyo Co., Ltd.).
    Also, the water-based ink static surface tension at 25 ° C is preferably 20 mN / m to 35 mN / m, and more preferably 20 mN / m to 30 mN / m. When the static surface tension is within the range of 20 mN / m to 35 mN / m, the ink increases penetration, which is effective in reducing runoff and resulting in favorable drying properties when printing on flat paper, and the ink is more easily placed in a pre-treatment layer, resulting in improved color development and white dots. However, when the static surface tension exceeds 35 mN / m, ink leveling in a recording medium is less likely to occur, and the drying time may be longer. Water-based ink coloring
    An ink and water based color is not particularly restricted and can be selected appropriately according to the purpose, and examples of it include yellow, magenta, cyan and black. A multicolored image can be formed by engraving using an ink set as a combination of two or more colors, and a complete color image can be formed by engraving using an ink set as a combination of all colors. Water-based paint production
    Water-based ink is manufactured by dispensing or dissolving the water-dispersible dye, the water-soluble organic solvent, the surfactant, the penetrating agent and the water, and, furthermore, the other components as needed, in an aqueous medium, and still stirring and mixing as needed. A method for stirring and mixing is not particularly restricted and can be selected appropriately according to the need, using a sand mill, a homogenizer, a ball mill, a paint stirrer, an ultrasonic disperser, a stirrer using propellers of common stirrers, a magnetic stirrer, and a high speed disperser, for example. The image formation method applies a stimulus not only to the ink, but also to the pre-treatment liquid and to the after-treatment liquid liquid to release them (ink discharge), in this way an image can be recorded in the middle recording, or a pre-treatment liquid or a post-treatment liquid can be applied over the image forming section. A method for peeling is not particularly restricted, however, several nozzles for discharging ink can be used.
    An ink head includes a liquid chamber, a fluid resistance unit, a diaphragm and a nozzle member, at least part of which is preferably formed of a material including silicon or nickel. Also, the inkjet nozzle has a nozzle diameter, preferably 30 pm or less, and more preferably 1 pm to 20 pm.
    The stimulus is not particularly restricted as long as it can be generated by several stimulus generating units and can be selected appropriately according to the purpose. Examples of it include heat, pressure, vibration and light. These can be used alone or in combination of two or more. Among these, heat and pressure are favorable.
    In the present document, examples of stimulus generating units include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, and a light, and specific examples thereof include: an actuator piezo such as a piezoelectric element; a thermal actuator that makes use of a phase exchange by boiling a liquid film using an electrothermal conversion element such as a heating resistor; an alloy actuator with shape memory that uses a metal phase shift due to a temperature shift; and an electrostatic actuator that uses an electrostatic force. Pre-treatment process
    A method for depositing a pre-treatment liquid to the recording medium in the pre-treatment process is not particularly restricted and can be selected appropriately as needed. Examples of the same include a coating method and a method for using the peel (ink discharge) unit. However, the coating method that applies the pre-treatment liquid evenly to a surface of the printing paper is preferable. Examples of the coating method include a blade coating method, an engraving coating method, an offset engraving coating method, a bar coating method, a roll coating method, a knife coating method, a air knife coating method, comma coating method, U comma coating method, AKKU coating method, smoothing coating method, microgravure coating, inverted roller coating method, four-roller or five-roller coating method, a dip coating method, a curtain coating method, a slip coating method and a dye coating method.
    The pre-treatment process is effective for the recording medium when the process is carried out on a surface of the same that is sufficiently dry or being dried. In this document, a drying step can be allocated to dry the pre-treated recording medium as needed. For example, the drying step includes printing paper using an infrared drying apparatus, a microwave drying apparatus, a roller heater or a drum heater, or with hot air.
    An amount of pre-treatment liquid deposition on the recording medium is preferably in the range of 0.1 g / m2 to 30.0 g / m2, and more preferably in the range of 0.2 g / m2 to 10 , 0 g / m2. When the amount of deposition is less than 0.1 g / m2, the image quality (image density, color saturation, folding and color flow) is unlikely to improve. When it exceeds 30.0 g / m2, the drying properties of the pre-treatment liquid degrade, and ripple can still occur. Image formation process
    The imaging process is a process for forming an image on the recording medium by applying a stimulus (energy) to an ink to release the ink onto the recording medium on which a pre-treatment liquid has been coated according to need. Various methods known so far can be used for this process, examples of which include an inkjet engraving method by head scanning and an inkjet engraving method of recording an image on a specific sheet using inline heads.
    A method for driving a recording head as an ink stripping unit in the imaging process is not particularly restricted and can be selected appropriately as needed. For example, an on-demand head using a piezoelectric element actuator using a PZT, a thermal power scheme, or an actuator using an electrostatic force can be performed with a head of a controlled head with a continuous jet charge. Post-treatment process
    The post-treatment process is a process of forming a protective layer by depositing the post-treatment liquid including a transparent resin on a surface of an imaging section formed in the imaging process.
    The post-treatment liquid can be deposited on the entire surface of the recording medium, on the entire surface of the imaging section, or only on a specific area of the imaging section. One method for depositing the after-treatment liquid is not particularly restricted and several methods can be selected appropriately depending on the types of after-treatment liquid. However, a method similar to the pre-treatment liquid coating method or a method similar to the paint stripping method is preferable. Among these, in view of the configuration of the apparatus and the stability in storage of the post-treatment liquid, the method similar to the paint release method is particularly preferable.
    A dry amount of deposition of the post-treatment liquid on the recording medium is preferably 0.5 g / m2 to 10 g / m2, and more preferably 2 g / m2 to 8 g / m2. When the amount of deposition is less than 0.5 g / m2, image quality (image density, color saturation, brightness and fixability) hardly improves. When it exceeds 10 g / m2, the drying properties of the protective layer decrease and the effects of improving image quality are saturated, which are economically disadvantageous.
    In the imaging method of the present invention, a step to heat dry the recording medium in which the post-treatment liquid has been deposited can be allocated as needed. Heat drying can be carried out, for example, by an infrared drying apparatus, a microwave drying apparatus, a roller heater, a drum heater or hot air. Also, for softening and fixing the image on a surface of the image forming section, a fixation step can be allocated for fixing heat by heating to 100 ° C to 150 ° C by a heat fixing unit. In this way, the brightness and the ability to fix a recorded material improve. The heat clamping unit is not particularly restricted and can be selected appropriately according to the need. However, a roller heater and a drum heater having a heated mirror surface are favorably used. A mirror surface portion (smooth portion) of the roller heater and drum heater can be contacted to a surface of an imaging section. A heat setting temperature is not particularly restricted and can be selected appropriately according to need.
    However, it is preferably at a softening point of a thermoplastic resin used for the protective layer or greater. However, in view of image quality, safety and economy, a fixing cylinder heated to 100 ° C to 150 ° C is preferable. When it is heated to above 150 ° C, a resin used in the post-treatment can degrade.
    Examples of the imaging method of the present invention are illustrated in figures 1 to 6.
    These are schematic diagrams, each illustrating a total configuration of the imaging method, where a pre-treatment liquid is deposited on a recording medium in a pre-treatment process, and the ink is discharged to form an image in an image-forming process, and a post-treatment liquid is deposited on an image-forming section in a post-treatment process, and drying and fixation processes are still allocated.
    Specifically, figure 1 illustrates a case of natural drying; figure 2 shows a case of drying with hot air; figure 3 illustrates a case of using a heat fixing cylinder in addition to drying with hot air; figure 4 shows a case of drying with a heat cylinder; figure 5 illustrates a drying case with infrared irradiation; Figure 6 illustrates cases of microwave drying. It is preferable to carry out the pretreatment process continuously at a constant linear speed of 20 mm / s 5 to 5,000 mm / s. Thus, in these examples, using a sheet recording medium, after completing a step of depositing the pre-treatment liquid on the recording medium, the image formation process is started, and an image is formed by a recording method with inkjet. In this method, a pre-treatment liquid deposition speed and an image recording speed do not coincide in most cases, and thus, in a recording start portion and a recording end portion of the recording medium. recording of this sheet, there is a 15 time discrepancy from the pre-treatment liquid being applied for an image to be recorded. Even if this discrepancy increases, the evaporation of moisture from the liquid is significantly suppressed for the adjusted pretreatment liquid to have a higher boiling point than water, to have a large amount of an aqueous solvent that has a velocity small evaporation rate, and have a moisture ratio close to an amount in equilibrium with an amount of moisture in the air in an environment where the printer is used. Consequently, a difference in image quality between the recording start portion and the recording end portion on the sheet recording medium can be reduced to below a level that can be visually observed. As in the case of the methods of figures 1 to 6, after depositing the pre-treatment liquid, in order to form an image, it is generally necessary to transport the recording medium on which the pre-treatment liquid has been deposited is transported by a unit that contacts the recording medium such as cylinder and guide. In this case, if the pre-treatment liquid deposited on the recording medium is transferred to a recording medium transport member, the transport function is compromised or the accumulated contamination, which can result in decreased image quality. To prevent this problem, measurements such as using a corrugated plate as a guide, forming the roller into a toothed crown shape or using a water spill material onto a surface of the roller can be taken for the apparatus, and trouble occurrences can be reduced.
    However, it is desirable that the pre-treatment liquid deposited on the recording medium be absorbed by the recording medium as quickly as possible so that the recording medium is apparently dry. To achieve this goal, it is effective to have a static surface tension of the pre-treatment liquid at 30 mN / m or less so that the liquid penetrates quickly into the recording medium. "Drying and solidification" after deposition of the pre-treatment liquid does not mean that the pre-treatment liquid is absorbed by the recording medium and appears to be apparently dried as described above, but it does mean that the pre-treatment liquid cannot maintain a liquid state and solidifies due to the evaporation of liquid compounds such as moisture. Thus, by selecting a favorable pre-treatment liquid and using an image forming apparatus as a combination of a pre-treatment liquid application apparatus and an image forming apparatus, the pre-treatment liquid is absorbed into the medium of engraving, and the inkjet engraving can be carried out with the pre-treatment liquid not solidified even though it is apparently dry. Consequently, the image quality can be significantly improved with an extremely small amount of pre-treatment liquid deposition. Cartridge
    A cartridge of the present invention includes the post-treatment inkjet engraving liquid of the present invention contained in a container, and further includes other members selected appropriately according to need. The container is not particularly restricted and its shape, structure, composition and materials can be selected appropriately according to the purpose. Examples of the same include a plastic container and those that include a pouch formed from an aluminum laminate film or a resin film.
    Specific examples thereof include a treatment liquid cartridge illustrated in figure 9 and figure 10 described below. Image forming apparatus
    An imaging apparatus of the present invention is an apparatus equipped with a cartridge of the present invention, in addition to several units relating to imaging, and further includes other units as needed.
    As an example, the imaging apparatus of the present invention includes an imaging unit that forms an image by an inkjet method on a surface of a recording medium; a storage unit that stores a first treatment liquid (pre-treatment liquid), a storage unit
    storage (a cartridge of the present invention) that stores a second treatment liquid (post-treatment liquid), and a storage unit (ink cartridge) that stores an ink; a processing unit that processes the surface of the recording medium prior to imaging by the imaging unit of the first treatment liquid; and a processing unit that processes with the treatment liquid after imaging by the imaging unit, and further includes other units selected appropriately according to need. The imaging unit includes at least one ink release unit, and further includes other units such as stimulus generation unit and control unit as needed.
    Figure 7 and Figure 8 are schematic diagrams (explanatory diagrams) illustrating an example of the imaging apparatus of the present invention. The image forming apparatus shown in Figure 7 (hereinafter referred to as inkjet engraving apparatus) includes: an apparatus body (101); a paper feed tray (102) mounted on the body of the apparatus (101) for loading sheets; a discharge tray (103) mounted on the body of the apparatus (101) to store the sheets on which an image is recorded (formed); and an ink cartridge loading section (104). On an upper surface of the ink cartridge loading section (104), an operating unit (105) including operating codes and indicators is arranged. The ink cartridge loading section (104) includes an open and closed front cover (115) for attaching and detaching the ink cartridges (200). Reference numbers (111) and (112) indicate a top cover and a front side of a front cover, respectively. A post-treatment liquid can be discharged if a cartridge containing the after-treatment liquid is mounted in place of these ink cartridges (200) or in addition to them.
    In the body of the apparatus (101), as shown in figure 8, a cartridge (133) is held slidably by a guide rod (131) and a tie rod (132) as guide members stretched horizontally by the left and right side plates (not shown) in a main scan direction, and the scan movement is performed by a main scan engine (not shown).
    In the cartridge (133), a plurality of ink discharge openings from a recording head (134) composed of four (4) ink jet recording heads that discharge ink drops of the respective colors, namely yellow (Y ), cyan (C), magenta (M), black (Bk) is arranged in one direction intersecting a main scan direction and is installed so that the ink droplet discharge direction is directed upwards.
    Like an inkjet recording head that constitutes the recording head (134), a head equipped with a piezo actuator such as a piezoelectric element, a thermal actuator that makes use of a phase exchange by boiling a film of a liquid using an electrothermal conversion element such as a heating resistor or a memory alloy actuator that uses a metal phase shift due to a temperature shift as a power generation unit to discharge the paints can be used.
    Also, sub-tanks (135) of the respective colors are installed in the carriage (133) to supply inks of the respective colors to the recording head (134). The sub-tanks (135) are refilled with the inks supplied from the ink cartridges (200) mounted on the ink cartridge loading section (104) through an ink supply tube (not shown).
    However, as a paper feed unit for feeding sheets (142) loaded on a sheet stacking unit (pressure plate) (141) of the paper feed tray (102), there is a half-moon roll [roll paper feeder (143)] which feeds one sheet at a time from the sheets (142) in the sheet stacking unit (141) and a separation pad (144) composed of a material having a high friction coefficient facing the paper feed roller (143). This separation pad (144) is angled towards the paper feed roller (143). As a transport unit for transporting the sheet (142) fed from this paper feed unit on one side downstream of the recording head (134), the apparatus includes: a conveyor belt (151) for transporting the sheet ( 142) by 15 electrostatic absorption; a counter roller (152) for transporting the sheet (142) sent from the paper feed unit through a guide (145) interspersed between the conveyor belt (151); a transport guide (153) for having the sheet (142) sent in a substantially vertical direction 20 and upwards after the conveyor belt (151) deflects it approximately by 90 °; and a front pressure cylinder (155) inclined to the conveyor belt (151) by a compression member (154), and also includes a loading roller (156) as a loading unit for loading a surface of the conveyor belt (151 ).
    The conveyor belt (151) is an endless belt stretched between a conveyor roller (157) and a tension roller (158), and can circulate in a conveyor direction of the belt. This conveyor belt (151) includes, for example, a surface layer as a sheet adsorption surface formed of a resin material having a thickness of 40 pm without resistivity control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE ); and a back layer (a medium resistance layer, a soil layer) made of this surface layer, but with carbon resistivity control. Behind the conveyor belt (151), a guide member (161) is arranged, corresponding to an image forming region by the recording head (134). In the present document, as a paper unloading unit for unloading the sheet (142) on which the engraving was carried out with the recording head (134), there is a separating claw (171) to separate the sheet (142) from of the conveyor belt (151), an unloading roller (172) and an unloading roller (173), and the unloading tray (103) is arranged downstream of the unloading roller (172).
    At the rear of the device body (101), a two-sided paper feed unit (181) is detachably mounted. The double-sided paper feed unit (181) captures and inverts the sheet (142) 5 returned by the conveyor belt (151) by turning in a reverse direction to feed it back to the counter roller (152) and the conveyor belt (151 ). In the present document, on a top surface of the double-sided feed unit (181), a manual sheet feed unit 10 (182) is arranged.
    In the inkjet recording apparatus, the sheet (142) is separated one by one and fed from the paper feed unit, and the sheet (142) fed in a substantially vertical direction and upwards is guided by the guide (145) and transported while sandwiched between the conveyor belt (151) and the counter cylinder (152). In addition, one end of it is guided by the transport guide (153) and pressed against the conveyor belt (151) by the front pressure cylinder 20 (155), and its transport direction is offset by approximately 90 °.
    At this time, the conveyor belt (157) is loaded by the loading cylinder (156) and the sheet (142) is electrostatically adsorbed and transported by the conveyor belt (151). In the present document, by activating the recording head (134) moving the carriage (133) according to an image signal, drops of ink are discharged onto the sheet (142) being interrupted to record a line. After the sheet (142) is transported by a predetermined quantity, the recording of a next line is carried out. Upon receiving an end of recording signal or a signal that a rear end of the sheet (142) has reached the recording area, the recording operation is completed, and the sheet (142) is unloaded into the discharge tray (103).
    Then, the ink remaining in the subtank (135) is detected to be almost empty, a required amount of ink is supplied from the ink cartridge (200) to the subtank (135).
    In this inkjet recording device, when the ink in the ink cartridge (200) is running out, it is possible to replace only the internal ink bag by decomposing an ink cartridge housing (200). Also, the ink cartridge (200) can supply the ink in a stable manner even when it is arranged vertically in a front loading configuration. Thus, in a case where a top of the device body (101) is blocked, for example, the device is arranged on a shelf or an object is placed on a top surface of the device body (101), the ink cartridge (200) can be easily changed.
    In this document, the example of a series-type inkjet recording device (alternative type) in which a car scan is explained above, but it is similarly applied to an inkjet-type recording device in series line equipped with an in-line head.
    Also, although not shown, in a case where a pre-treatment liquid or after-treatment liquid is coated with a roller, a control of actuation of the cylinders to coat such as a coating cylinder is required. Thus, a motor control unit for coating, a motor to be controlled and a control sensor are arranged.
    In addition, when the pre-treatment liquid or after-treatment liquid is discharged by inkjet, there is a risk of nozzle clogging caused by mixing colors unless a maintenance operation is carried out separately from the inks. . Thus, it is desirable that an engine moving the maintenance unit be arranged for each treatment liquid separately from these for the paints.
    Then, the cartridge containing the pre-treatment liquid or the post-treatment liquid (hereinafter referred to as a treatment liquid) is explained with reference to figure 9 and figure 10. In the present document, figure 9 is a diagram illustrating an example of the cartridge of the present invention, and figure 10 is a diagram including a case of the cartridge of figure 9 (external).
    As illustrated in figure 9, a treatment liquid is filled into a treatment liquid bag 241 from a treatment liquid inlet 242, and the remaining air in the treatment liquid bag is evacuated. Then, the treatment liquid inlet 242 is sealed. When in use, the treatment liquid is supplied to the device by inserting a needle from the device body into an outlet of treatment liquid 243 made of a rubber material. The treatment liquid pouch 241 is formed of a packaging material having no air permeability such as laminated aluminum film. Also, as illustrated in figure 10, it is generally contained in a cartridge wrapper 244 made of plastic and used as a cartridge 200 being detachably mounted on various imaging devices.
    Also, if the cartridge 240 is used as an ink cartridge by filling it with ink instead of treatment liquid, similarly to the treatment liquid cartridge, it can be used to detachably mount on various imaging devices .
    In addition, the ink, the pre-treatment liquid and the post-treatment liquid can be stored together in a cartridge with a large capacity (for example, rectene). EXAMPLES
    Hereinafter, the present invention is explained in more detail with reference to examples and comparative examples 10, but the present invention is not to be interpreted by these examples. PRODUCTION EXAMPLE 1
    A homogeneous mixture was prepared by mixing and stirring the materials of a formulation shown below 15 as a post-treatment liquid for inkjet recording for 1 hour. It was then subjected to pressure filtration through a polyvinylidene fluoride membrane filter that has an average pore diameter of 5.0 pm to remove coarse particles and dust, and a post-treatment liquid for etching. inkjet of production example 1 was obtained. LIQUID POST-TREATMENT FOR ENGRAVING WITH INK JET 1
    Urethane resin WLS-210 based on anionic self-emulsifying ether (manufactured by DIC Corporation: Active ingredient: 35% by weight) 28.6% by weight • 1,3-Butanediol 15% by weight • Glycerin 15% by weight • ZONYL FS-300 (fluorotensive, manufactured by DuPont Co .; ingredient: 1% by weight) 1% by weight • Pure water 40.4% by weight PRE-TREATMENT NET
    Uniform mixtures were prepared by mixing and stirring the formulation materials shown below as pretreatment liquids 1 and 2 respectively for 1 hour. Then they were subjected to a polyvinylidene fluoride membrane filter that has an average pore diameter of 5.0 pm to remove coarse particles and dust, and pre-treatment liquids were obtained respectively. PRE-TREATMENT LIQUID 1 • Lactic acid 10% by weight • 1,3-Butanediol 10% by weight • Glycerin 10% by weight • 2-ethyl-1,3-hexanediol 1% by weight • Pure water 69% by weight PRE-TREATMENT LIQUID 2 • Magnesium sulphate • 1,3-Butanediol • Glycerin • 2-ethyl-1,3-hexanediol • Pure water 10% by mass 10% by mass 10% by mass 1% by mass 69% by weight pasta PREPARATION OF DISPERSION OF POLYMERIC PARTICLES CONTAINING PIGMENT Preparation of polymeric solution A
    After a 1 liter bottle equipped with a mechanical stirrer; a thermometer; a nitrogen gas inlet tube, a reflux tube and a drip funnel be sufficiently purged with nitrogen gas, 11.2 g styrene, 2.8 g acrylic acid, 12.0 g lauryl methacrylate, 4.0 g of polyethylene glycol methacrylate, 4.0 g of a styrene macromer and 0.4 g of mercaptoethanol were mixed and heated to 65 ° C.
    Then, a mixed solution of 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxyethyl methacrylate, 36.0 g of styrene macromer, 3.6 g of mercaptoethanol, 2.4 g of azobismethylvaleronitrile and 18.0 g of methyl ethyl ketone were added dropwise to the flask over 2.5 h. After the drop addition, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was added dropwise to the flask over 0.5 h. After being aged at 65 ° C for 1 h, 0.8 g of 5 azobismethylvaleronitrile was added, and it was further aged for 1 h. After the completion of the reaction, 364.0 g of methyl ethyl ketone were added to the fraction, and 800 g of polymeric solution A having a concentration of 50% by mass were obtained. 10 Preparation of the dispersion of polymeric particles containing the magenta pigment Preparation Example a
    After sufficient stirring of 28 g of polymeric solution A, 42 g of CI Pigment red 122, 13.6 g of a 1 mol / 1 aqueous solution of potassium hydroxide, 20.0 g of methyl ethyl ketone and 13.6 g of ion exchange water, the mixture was kneaded using a roller mill.
    After a obtained paste was sufficiently stirred with an addition of 200 g of pure water, methyl ethyl ketone and water 20 were distilled using an evaporator, and it was further subjected to pressure filtration through a polyvinylidene fluoride membrane having a diameter of average pore of 5.0 µm in order to remove coarse particles. In this way, a dispersion of polymeric particles containing the magenta pigment having a pigment content of 15% by weight and a solid content of 20% by weight was obtained.
    An average pore diameter (D50) of the polymeric particles in this dispersion was measured, and was 82.7 nm. In this document, the measurement of an average particle diameter (D50) was performed using a particle size distribution measuring device (NANOTRAC UPA-EX150, manufactured by Nikkiso Co., Ltd.).
    Preparation of the dispersion of polymeric particles containing the cyan pigment Preparation Example b
    A dispersion of polymeric particles containing the cyan pigment which has a pigment content of 15% by weight and a solids content of 20% by weight was obtained in the same way as in the preparation example a except that CI Pigmento red 122 in the example of preparation a was exchanged for a phthalocyanine pigment (CI Pigment blue 15: 3).
    An average particle diameter (D50) of polymeric particles in this dispersion was measured similarly to preparation example a and was 110.6 nm.
    Preparation of the dispersion of polymeric particles containing the yellow pigment Preparation Example c
    A dispersion of polymeric particles containing the yellow pigment which has a pigment content of 15% by weight and a solids content of 20% by weight was obtained in the same way as in the preparation example a except that CI Pigmento red 122 in the example of preparation a was exchanged for a monoazo yellow pigment (CI Pigment Yellow 74).
    An average particle diameter (D50) of polymeric particles in this dispersion was measured similarly to preparation example a and was 105.4 nm.
    Preparation of the dispersion of polymeric particles containing the carbon black pigment Preparation Example d
    A dispersion of polymeric particles containing the carbon black pigment which has a pigment content of 15% by weight and a solids content of 20% by weight was obtained in the same way as in the preparation example except CI CI Pigment Red 122 in preparation example a was changed to a carbon black (FW100, manufactured by Degussa).
    A mean particle diameter (D50) of polymeric particles in this dispersion was measured similarly to preparation example a and was 75.2 nm.
    Preparation Examples 1 to 8 of water-based inks for inkjet engraving
    A homogeneous mixed solution was prepared by mixing and stirring a water-soluble organic solvent, a penetrating agent, a surfactant, a fungicide, water and a water-dispersible resin depending on the preparation examples shown in the respective preparation example columns in the table 1-1 and table 2 below for 1 h. Then, a pigment dispersion, defoamer and pH adjuster were added, which were mixed and stirred for 1 hour, and a dispersion was obtained. This dispersion was subjected to pressure filtration through a polyvinylidene fluoride membrane filter having an average pore diameter of 5.0 pm to remove coarse particles and dust, and the water-based inks for inkjet engraving of the examples Preparation 1 to 8 15 were obtained, respectively. TABLE 1-1
    TABLE 1-2

    The meanings of the abbreviations, etc., in table 1-1 and table 1-2 are as follows: - CAB-0-JET260: a self-dispersing magenta pigment dispersion manufactured by Cabot Inc. having a content of 5 solids in 11% pigment - CAB-O-JET250: a self-dispersing cyan pigment dispersion manufactured by Cabot, Inc. having a solids content in the 11% pigment CAB-0-JET270: a self-dispersing yellow pigment dispersion manufactured by Cabot, Inc. having an 11% pigment solids content - CAB-O-JET300: a self-dispersing black pigment dispersion manufactured by Cabot, Inc. having a 15% pigment solids content resin resin emulsion fluorine: LUMIFLON FE4500 manufactured by Asahi Glass Co., Ltd. Having a solids content of 52% by weight, an average particle diameter of 1.36 nm and a minimum film formation temperature (MFT) = 28 ° C - KF-640: a polyether modified silicone surfactant (manufactured by Shin-Etsu Chemical Co., Ltd .; ingredient: 100% by mass) - Proxel GXL: a fungicide having 1,2-benzisothiazolin-3-one as a major component (manufactured by Avecia Biotechnology Inc .; ingredient: 20% by weight; including dipropylene glycol) KM-72F: a self-emulsifying silicone defoamer (manufactured by Shin-Etsu Chemical Co., Ltd .; ingredient: 100% by mass) Examples 1-1 to 2-4, Comparative Examples 1-1 to 2-4
    Using the pre-treatment liquids, the inks and the after-treatment liquid in combination as shown in the columns of examples 1-1 to 2-4 of table 2 and in the columns of comparative examples 1-1 to 2-4 of the table 3, an image was formed on the offset printing paper (OK Top Coat, manufactured by Oji Paper Co., Ltd .: Type A2) with an IPSIO GXE-5500 inkjet printer manufactured by Ricoh Company Ltd., and then the post-treatment liquid was discharged over an imaging section. The printing was done by printing a pass at a resolution of 1,200 dpi. In the examples and the comparative examples, a recording medium treated with the pre-treatment liquid was used.
    The images formed in the respective examples and comparative examples were evaluated for their resistance to image scratching (dirt holding capacity) and folding as follows. The results are summarized and shown in table 2 and table 3. Dirt holding capacity
    An image formed was a graphic including a 64-point "black square" character created with Microsoft Word 2000, and the post-treatment liquid was discharged over the image formation section.
    Then, the formed image was dried at a temperature of 23 ± 2 ° C and a humidity of 50 ± 15% relative humidity for 24 h, and the portion of the "black square" on the printing surface was rubbed back and forward 10 times with JIS L0803 Cotton, n2 3 attached to a CM-1 watch gauge with double-sided tape. Then, a reflection density of the ink adhered to the cotton was measured with X-Rite 939 (manufactured by X-Rite, Inc.), and subtracting the texture from the cotton color, the reflection density of the dirt portion was determined according to following evaluation criteria. In this document, "black square" is a solid black square character (code) and is inevitably expressed as "black square" since it cannot be used in this document.
    Evaluation Criteria A: less than 0.07 B: 0.07 or more, less than 0.1 C: 0.1 or more Folding The pretreatment process was carried out on the sheets, and then solid cyan images , magenta and green were printed, followed by drying with hot air. Then, the solid images were observed for uneven density (folding) and evaluated according to the following evaluation criteria. Assessment Criteria A: none B: mild C: present TABLE 2
    5 TABLE 3
    As can be understood from examples 1-1 to 2-4 and comparative examples 1-1 to 2-4, in an inkjet engraving method it is possible to obtain an image that has folding quality and 10 superior smudge-fixing ability (scratch resistance) can be obtained using a post-treatment liquid including a urethane resin, a fluorotensive, a water-soluble organic solvent in a post-processing of a forming section Image. The aspects of the present invention are as follows: <1> A post-treatment liquid for inkjet engraving, including a urethane resin, a fluorotensive, an organic solvent soluble in water and water. <2> The post-treatment liquid for inkjet engraving according to <1>, wherein the urethane resin is a urethane resin based on self-emulsifying ether 5. <3> An ink-jet imaging method, including: an imaging process, in which an image is formed on a recording medium using an ink; and 10 an aftertreatment process, in which the aftertreatment liquid for inkjet engraving according to any one of <1> to <2> is discharged to cover an image forming section formed in the process of image formation, and the image formation section comprises the image. <4> The imaging method according to <3>, in which the ink is a water-based ink, and the recording medium is offset printing paper. <5> The imaging method according to any one of <3> to <4>, wherein the imaging method includes a pre-treatment process prior to the imaging process; and wherein in the pre-treatment process, the recording medium is treated with a pre-treatment liquid, including: a water-soluble organic solvent, water, and an aliphatic organic acid salt or an inorganic metal salt, or both. <6> A cartridge, including the post-treatment liquid for inkjet engraving according to any of <1> to <2>. <7> An imaging device, including a cartridge according to <6> loaded in it.
    权利要求:
    Claims (6)
    [0001]
    1. Post-treatment liquid for inkjet engraving comprising: a urethane resin; a fluortensoativo; a water-soluble organic solvent; and water; characterized by the fact that the urethane resin is a urethane resin based on anionic self-emulsifying ether.
    [0002]
    2. Inkjet engraving image method characterized by the fact that it comprises: forming an image on a recording medium using an ink; and post-treating an image-forming section formed in forming an image by discharging an after-treatment liquid for inkjet engraving to coat the image-forming section; wherein the imaging section comprises the image, and wherein the after-treatment liquid for inkjet engraving is the after-treatment liquid for inkjet engraving as defined in claim 1.
    [0003]
    3. An image-forming method according to claim 2, characterized by the fact that the ink is a water-based ink, and the recording medium is an offset printing paper.
    [0004]
    An image-forming method according to any one of claims 2 to 3, characterized in that it further comprises pre-treatment before forming an image: in which the recording medium is treated with a pre-treatment liquid pre-treatment; and wherein the pre-treatment liquid comprises: a water-soluble organic solvent; Water; and an aliphatic organic acid salt or an inorganic metal salt, or both.
    [0005]
    5. Cartridge characterized by the fact that it comprises the post-treatment liquid for inkjet engraving as defined in claim 1.
    [0006]
    6. Imaging apparatus characterized by the fact that it comprises a cartridge as defined in claim 5.
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    同族专利:
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    法律状态:
    2015-06-30| 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 04/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012020660|2012-02-02|
    JP2012-020660|2012-02-02|
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