WO2023105737A1 - Jeu d'encre pour impression à jet d'encre, procédé d'impression à jet d'encre et dispositif d'impression à jet d'encre - Google Patents

Jeu d'encre pour impression à jet d'encre, procédé d'impression à jet d'encre et dispositif d'impression à jet d'encre Download PDF

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Publication number
WO2023105737A1
WO2023105737A1 PCT/JP2021/045458 JP2021045458W WO2023105737A1 WO 2023105737 A1 WO2023105737 A1 WO 2023105737A1 JP 2021045458 W JP2021045458 W JP 2021045458W WO 2023105737 A1 WO2023105737 A1 WO 2023105737A1
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Prior art keywords
ink
inkjet recording
treatment liquid
inkjet
ink set
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PCT/JP2021/045458
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English (en)
Japanese (ja)
Inventor
歩 上井
正幸 牛久
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コニカミノルタ株式会社
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Priority to PCT/JP2021/045458 priority Critical patent/WO2023105737A1/fr
Priority to JP2023565826A priority patent/JPWO2023105737A1/ja
Publication of WO2023105737A1 publication Critical patent/WO2023105737A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/17—Ink jet characterised by ink handling
    • B41J2/18—Ink recirculation systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink

Definitions

  • the present invention relates to an ink set for inkjet recording, an inkjet recording method, and an inkjet recording apparatus. More specifically, the present invention relates to an ink set for ink jet recording, which has good ink ejection stability and improved image quality of recorded matter.
  • the inkjet recording (also called “printing”) method is a recording method in which small droplets of ink are ejected from an inkjet head and landed on the surface of a recording medium such as paper. With this method, it is possible to print high-resolution and high-quality images at high speed with a relatively inexpensive device.
  • inkjet printing especially when water-based ink is used, when a character or image pattern is printed on the surface of a recording medium, the liquid component permeates the recording medium and then dries, fixing the ink.
  • plain paper, special paper, high-quality paper, or recycled paper with high ink absorption as the recording medium, the ink can be easily fixed and a high-quality image can be provided.
  • a recording medium with low or no absorbency such as , art paper, lightly coated paper, or film
  • the ink droplets do not easily penetrate into the recording medium, so drying does not occur due to penetration. Bleeding occurred between the droplets, and the image quality was impaired.
  • the ink In order to improve the image quality of the recorded matter (printed matter), it is preferable that the ink has high viscosity on the surface of the recording medium and is quickly fixed. On the other hand, when the ink is ejected from the inkjet head, if the viscosity of the ink is too high, it becomes difficult to stably eject the required amount to the required location. Therefore, it is preferable that the ink has good ejection stability and is quickly fixed on the surface of the recording medium.
  • Patent Literature 1 discloses a technique for an aqueous inkjet ink in which the ratio of the viscosity when the shearing force is strongly controlled and the viscosity when the shearing force is weakly controlled is a certain value or more. Since the ink has relatively high so-called thixotropic properties, the viscosity decreases when subjected to a shearing force, but the viscosity is relatively high when the ink remains stationary without being subjected to a shearing force.
  • the ink can be fixed immediately on the surface of the recording medium, but when it is ejected from the inkjet head, it is necessary to adjust the viscosity to the optimum level by applying a shearing force, etc., and precise control of the circulation flow rate, etc. is required. was necessary.
  • the treatment liquid includes one that forms a layer (ink-receiving layer) that absorbs the liquid components of the ink and improves drying properties, and one that aggregates the solid components to intentionally increase the viscosity of the ink.
  • a layer ink aggregation layer
  • two types are known that form a layer (ink aggregation layer) that prevents ink bleeding and color unevenness between ink droplets.
  • a treatment liquid containing an aggregating agent is applied to the surface of the recording medium, and then the ink is applied, and the treatment liquid and the ink are combined (mixed) in a liquid state to obtain the ink.
  • a method (hereinafter, also referred to as “wet-on-wet method”) is known for quickly aggregating a coloring material inside and quickly fixing a mixture of a treatment liquid and an ink.
  • the treatment liquid is preferably applied using a blade-like member or a sponge-like member while rotating the roller.
  • the application amount can be adjusted by controlling, the treatment liquid is applied uniformly over a certain range. Therefore, it is difficult to finely control the application amount of the treatment liquid in correspondence with the application amount of the ink. Further, no study has been made on a method of applying the treatment liquid by an inkjet method.
  • the processing liquid contains resin particles and a thickener (hydrophobic-modified water-soluble urethane resin) to increase the viscosity of the processing liquid, thereby improving the recording properties with low or no absorbency.
  • a thickener hydrophobic-modified water-soluble urethane resin
  • the treatment liquid has a relatively high viscosity, when applied by an inkjet method, good ejection stability cannot be obtained. It was found to be defective.
  • Cited Document 4 discloses a technique for improving optical density and marker resistance by including an associative thickener in the treatment liquid (reaction liquid).
  • the present invention has been made in view of the above-mentioned problems and circumstances, and the problem to be solved is an ink set for inkjet recording, an inkjet recording method, and an inkjet recording method, in which the ejection stability of the ink is good and the image quality of the recorded matter is improved. It is to provide a recording device.
  • the present inventors have investigated the causes of the above problems and found that, in an inkjet recording ink set containing an ink and a treatment liquid, the thickener contained in the ink causes excessive aggregation of the coloring material.
  • the present inventors have found that the presence of the inhibiting function provides good ejection stability of the ink and improves the image quality of the recorded matter, leading to the present invention. That is, the above problems related to the present invention are solved by the following means.
  • An inkjet recording ink set comprising an ink and a treatment liquid,
  • the ink contains a thickener, a coloring material, water and an organic solvent
  • the treatment liquid contains a flocculant, water and an organic solvent
  • the ink is composition A
  • a composition B is obtained by removing the thickening agent from the ink
  • a composition C is obtained by mixing the composition A and the treatment liquid
  • the composition D is obtained by mixing the composition B and the treatment liquid
  • V C and V D satisfy the following relational expressions (1) and (2): Formula (1): V A >V B
  • Items 1 to 10 wherein the composition obtained by mixing the ink and the treatment liquid has a viscosity VC of 15 mPa ⁇ s or more at a shear rate of 2 [1/s] at 25°C.
  • An inkjet recording method using an inkjet recording ink set Using the inkjet recording ink set according to any one of items 1 to 11, An inkjet recording method, wherein the ink and the treatment liquid are combined with each other on the surface of a recording medium.
  • Item 15 The inkjet recording method according to any one of Items 12 to 14, wherein the ink set for inkjet recording is discharged from an inkjet recording apparatus having a circulation mechanism.
  • Item 16 The inkjet recording method of Item 15, wherein the circulation mechanism is bidirectional circulation.
  • An inkjet recording apparatus using an inkjet recording ink set Using the inkjet recording ink set according to any one of items 1 to 11,
  • the inkjet recording device has the inkjet head for the ink and the inkjet head for the treatment liquid, The inkjet head for ink and the inkjet head for treatment liquid are mounted on the same carriage, or An inkjet recording apparatus, wherein the inkjet head for ink and the inkjet head for treatment liquid are mounted on separate carriages, and the carriages are adjacent to each other without a drying mechanism interposed therebetween.
  • a wet-on-wet method in order to sufficiently agglomerate the coloring material in the ink.
  • the coalescence (mixing) of the liquid ink and the treatment liquid on the surface of the recording medium increases the chances of contact between the coloring material in the ink and the aggregating agent in the treatment liquid, so that aggregation proceeds sufficiently.
  • the particle size of aggregates composed of a flocculant and a coloring material becomes too large, i.e., over-aggregation tends to occur, and smoothness is reduced, resulting in a decrease in glossiness.
  • the problem was the deterioration of image quality. Therefore, in the wet-on-wet method, it is necessary to adjust the progress of aggregation to the extent that image quality does not deteriorate.
  • the present inventors conducted extensive studies and found that there exists a compound that has a function of inhibiting excessive aggregation of the coloring material. was found to improve.
  • a compound (thickener) that has the property of increasing the viscosity of the ink when contained in the ink, it is possible to adjust the viscosity of the ink to a viscosity that provides good ejection stability. have understood.
  • Schematic diagram showing an inkjet recording device Carriage bottom view
  • the ink set for inkjet recording of the present invention is an ink set for inkjet recording containing an ink and a treatment liquid, wherein the ink contains a thickener, a coloring material, water and an organic solvent, and the treatment liquid aggregates agent, water and an organic solvent, and the thickener has a function of inhibiting overaggregation of the colorant.
  • This feature is a technical feature common to or corresponding to the following embodiments.
  • the ink is a composition A
  • the ink excluding the thickener is a composition B
  • the viscosities V C and V D at a shear rate of 2 [1/s] at 25 ° C. of the compositions C and D are expressed by the following relational expression (1 ) and (2) are preferably satisfied.
  • Formula (2) V C ⁇ V D
  • the composition A has a viscosity VA of 15 mPa ⁇ s or less at a shear rate of 1000 [1/s] at 25°C.
  • the ratios R C and R D of the number of coarse particles of 5 ⁇ m or more in the compositions C and D satisfy the following relational expression (3).
  • the content of the thickening agent is within the range of 5 to 100% by mass with respect to the total mass of the coloring material.
  • the thixotropic index at 25°C of the ink is preferably in the range of 0.85 to 1.0.
  • the thickener has at least a hydrophilic portion and a hydrophobic portion in the same particle.
  • the content of the organic solvent in the ink is in the range of 5 to 25% by mass with respect to the total mass of the ink.
  • the aggregating agent is preferably a polyvalent metal salt, a cationic polymer or an organic acid, and more preferably the polyvalent metal salt contains at least calcium salt or magnesium salt.
  • the composition obtained by mixing the ink and the treatment liquid has a viscosity V C at a shear rate of 2 [1/s] at 25° C. of 15 mPa ⁇ s or more.
  • the ink jet recording method of the present invention is characterized in that the ink set for ink jet recording of the present invention is used, and the ink and the treatment liquid are united with each other on the surface of the recording medium.
  • the ink set is ejected from the staggered inkjet heads.
  • the ink set for inkjet recording is preferably ejected from an inkjet recording apparatus having a circulation mechanism, and more preferably, the circulation mechanism is bidirectional circulation.
  • the inkjet recording apparatus of the present invention uses the inkjet recording ink set of the present invention, the inkjet recording apparatus has the inkjet head for the ink and the inkjet head for the treatment liquid, and the inkjet head for the ink and the treatment liquid.
  • the inkjet head for the treatment liquid is mounted on the same carriage, or the inkjet head for the ink and the inkjet head for the treatment liquid are mounted on separate carriages, and the carriages are adjacent to each other without a drying mechanism interposed therebetween. It is characterized by
  • the ink set for inkjet recording of the present invention is an ink set for inkjet recording containing an ink and a treatment liquid, wherein the ink contains a thickener, a coloring material, water and an organic solvent, and the treatment liquid aggregates agent, water and an organic solvent, and the thickener has a function of inhibiting overaggregation of the colorant.
  • the ink according to the present invention is a water-based ink containing water.
  • Water-based inks can have a relatively low VOC (volatile organic compound) content compared to solvent inks, and are therefore preferable because they can reduce the burden on the environment.
  • VOC volatile organic compound
  • the treatment liquid Due to the reaction with the aggregating agent in the ink, the coloring material in the ink agglomerates and the viscosity of the mixture of the ink and treatment liquid increases. It is possible to suppress bleeding and color unevenness between ink droplets.
  • overaggregation Excessive aggregation of the coloring material in the ink is called "overaggregation", and by suppressing overaggregation, good image quality can be obtained in the printed matter.
  • the thickener contained for the purpose of obtaining good ejection stability further has a function of inhibiting overaggregation of the coloring material, thereby suppressing overaggregation of the coloring material and improving image quality.
  • the effect is remarkable in the wet-on-wet method in which overaggregation tends to occur.
  • the presence or absence of excessive aggregation can be determined by viscosity.
  • the viscosity of the mixture of the ink according to the present invention (including the thickener) and the treatment liquid (mixed liquid) is such that the ink excluding the thickener is mixed with the treatment liquid. If the viscosity is lower than or equal to that of the other (mixed liquid), it can be determined that excessive aggregation is suppressed. A method for measuring the viscosity will be described later.
  • the ink according to the present invention contains a thickener, a coloring material, water and an organic solvent, and is characterized in that the thickening agent has a function of inhibiting excessive aggregation of the coloring material.
  • the ink according to the present invention can adjust the viscosity of the ink and obtain good ejection stability. Also, the organic solvent content in the ink can be reduced. Furthermore, since the thickener has a function of inhibiting overaggregation of the coloring material, overaggregation of the coloring material is suppressed, and image quality can be improved.
  • Thickening agent refers to a substance that increases the viscosity of a liquid when added, and in the present invention, further refers to a substance that has the function of inhibiting overaggregation of a coloring material.
  • the method and conditions for measuring viscosity are not particularly limited.
  • Whether or not the thickener has a function of inhibiting overaggregation of the coloring material is determined, for example, by comparing the ink (including the thickener) according to the present invention and the ink excluding the thickener. are mixed with the treatment liquid, and the viscosity of the mixture and the ratio of the number of coarse particles are compared. A method for comparing the viscosity and the ratio of the number of coarse particles will be described later in detail.
  • the ink according to the present invention behaves as if it were a physically cross-linked macromolecule due to intermolecular interactions caused by containing the thickening agent. It is thought that the viscosity of the system increases due to Since the coloring material is retained in the macromolecules, excessive aggregation of the coloring material can be suppressed even when mixed with a treatment liquid containing an aggregating agent. However, since the physical cross-linked structure of macromolecules is formed by intermolecular interactions, the coloring material is not completely retained, and some coloring materials can move freely, and the flocculant and It is possible to aggregate by reaction. Therefore, the coloring material can be appropriately aggregated.
  • any compound that has the function of increasing the viscosity of the liquid and inhibiting overaggregation of the coloring material is particularly limited. can be used without
  • the thickening agent according to the present invention may be an inorganic compound or an organic compound. From the viewpoint of interaction with the coloring material, the thickening agent is preferably an organic compound, and at least It is more preferable to have a hydrophilic part and a hydrophobic part in the same particle.
  • Particles here refer to aggregates formed by aggregation of molecules, and the types of molecules may all be the same or different. In addition, in the assembly, the molecules may form chemical bonds with each other. Further, “having at least a hydrophilic part and a hydrophobic part in the same particle” means that at least the same aggregate has a hydrophilic part and a hydrophobic part, and is composed only of a hydrophobic part without a hydrophilic part. molecules may be present in the aggregate.
  • an emulsifier surfactant
  • an aggregate may be formed only by molecules having a hydrophilic portion and a hydrophobic portion in the same molecule.
  • water-insoluble resin fine particles or water-soluble resins described below are preferable.
  • the content of the thickening agent is preferably in the range of 0.1 to 5% by weight with respect to the total weight of the ink. By being within the above range, good ejection stability of the ink can be obtained. Also, the content of the thickening agent is preferably in the range of 5 to 100% by mass with respect to the coloring material. By being within the above range, excessive aggregation can be sufficiently suppressed.
  • inorganic compounds include inorganic compounds such as silica (SiO 2 ), alumina, and titania, and clay minerals such as bentonite and montmorillonite, among which silica powder, hydrophobically treated silica powder, or a mixture thereof. is preferred.
  • fine silica powder pulverized by a dry method for example, Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.
  • fine powder obtained by modifying the above fine silica powder with trimethyldisilazane for example, Aerosil RX300, manufactured by Nippon Aerosil Co., Ltd.
  • a fine powder obtained by modifying the silica fine powder with polydimethylsiloxane for example, Aerosil RY300, manufactured by Nippon Aerosil Co., Ltd.
  • Laponite manufactured by BYK-Chemie
  • silicate a synthetic layered silicate made from naturally occurring inorganic mineral sources
  • the average particle size of the inorganic compound is preferably within the range of 5-50 ⁇ m, more preferably within the range of 5-12 ⁇ m.
  • Water-insoluble resin microparticles As the organic compound, the following water-insoluble resin fine particles can be used.
  • the water-insoluble resin fine particles can be dispersed in an aqueous medium by having at least a hydrophilic portion and a hydrophobic portion in the same particle.
  • resin fine particle dispersion The resin fine particles described below are water-insoluble resin fine particles, and a water-insoluble resin fine particle dispersion containing the water-insoluble resin fine particles exhibits solubility or affinity for ink.
  • the "water-insoluble resin fine particles” are originally water-insoluble, but have a form in which the resin is dispersed in an aqueous medium as micro fine particles.
  • hydrophilic portion into a water-insoluble resin (hydrophobic portion) (forced emulsification using an emulsifier or the like, or introducing a hydrophilic functional group into the molecule), the hydrophilic portion and the hydrophobic and can be dispersed in an aqueous medium.
  • a structure having a hydrophilic portion and a hydrophobic portion in the same molecule, that is, a hydrophilic functional group is introduced into the molecule to form a stable aqueous dispersion by itself without using an emulsifier or a dispersion stabilizer. It is preferably a water-insoluble resin that can self-emulsify to form.
  • the term “water-insoluble” means that when the resin is dried at 105° C. for 2 hours and then dissolved in 100 g of water at 25° C., the dissolved amount is 10 g or less, preferably 5 g or less, and further Preferably, it refers to a resin weighing 1 g or less.
  • the dissolved amount is the dissolved amount when the salt-forming group of the resin is 100% neutralized with acetic acid or sodium hydroxide, depending on the type.
  • the fine resin particles are preferably acrylic resin fine particles, urethane resin fine particles, polyester resin fine particles, or composite resin fine particles of urethane resin and acrylic resin.
  • the dispersion becomes unstable and the fine particles are adsorbed and aggregated to each other, resulting in an increase in the particle size of the fine particles.
  • the average particle size (Z average particle size) of the fine resin particles is preferably 1000 nm or more.
  • the average particle size (Z-average particle size) of fine particles can be measured by the following procedure using a particle size measuring device and a dynamic light scattering method.
  • a slurry containing resin fine particles is diluted with ion-exchanged water so that the resin fine particles are 0.1% by mass, the diluted slurry is irradiated with a laser beam, and the scattered light intensity scattered from the resin fine particles changes over time in microseconds.
  • Measure in The Z-average particle size of the resin fine particles is obtained by applying the scattering intensity distribution caused by the detected resin fine particles to a normal distribution and using the cumulant analysis method.
  • the particle size measuring device include Zetasizer Nano ZS manufactured by Spectris.
  • the particle size measuring device is equipped with data analysis software, and the Z-average particle size can be calculated by automatically analyzing the measurement data with the data analysis software.
  • a resin may be added in addition to the thickener from the viewpoint of improving fixability to the recording medium.
  • the fixing resin it is preferable to use fine resin particles having an average particle size (Z-average particle size) of less than 1000 nm at the time of aggregation.
  • polyester resin, urethane resin, acrylic resin, or composite resin particles of urethane resin and acrylic resin are preferably anionic or nonionic.
  • the resin fine particles preferably contain an acid structure (hydrophilic portion).
  • an acid structure hydrophilic portion
  • the acid structure may be present in the side chain of the resin, or may be present at the end.
  • the acid structure is not necessarily required, and the acid structure may or may not be present. good too.
  • a part or all of the acid structure is preferably neutralized.
  • the neutralizing agent that neutralizes the acid structure are preferably organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, and triethanolamine.
  • the glass transition point (Tg) of the fine resin particles is preferably in the range of -30 to 100°C.
  • the glass transition point (Tg) is determined from the endothermic peak when the temperature is raised in the temperature range of ⁇ 30 to 200° C. at a temperature elevation rate of 10° C./min using a DSC (differential scanning calorimeter). It can be identified by reading the transition temperature Tg.
  • polyester resin A polyester resin having a polyester skeleton as water-insoluble resin fine particles can be obtained by using a polyhydric alcohol component and a polycarboxylic acid component such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic acid ester. can.
  • a dihydric alcohol specifically an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1, 4-butylene glycol, 1,6-hexanediol, etc.), alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.), carbon Alicyclic diols having numbers 6 to 36 (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene oxides having 2 to 4 carbon atoms in the alicyclic diols (ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO)) adduct (addition mole number range of 1
  • polycarboxylic acid components include divalent carboxylic acids (dicarboxylic acids), specifically alkanedicarboxylic acids having 4 to 36 carbon atoms (succinic acid, apidic acid, sebacic acid, etc.), alkenylsuccinic acids ( dodecenyl succinic acid, etc.), alicyclic dicarboxylic acids having 4 to 36 carbon atoms (dimer acid (dimerized linoleic acid), etc.), alkenedicarboxylic acids having 4 to 36 carbon atoms (maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.), aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid or derivatives thereof, naphthalenedicarboxylic acid, etc.). These may be used alone or in combination of two or more.
  • the number average molecular weight of the polyester resin is preferably within the range of 1,000 to 50,000, more preferably within the range of 2,000 to 20,000.
  • polyester resin commercially available products may be used.
  • urethane resin A urethane resin having a hydrophilic group can be used as the water-insoluble resin fine particles.
  • Urethane resin is an aqueous dispersion of self-emulsifying urethane that has a water-soluble functional group in its molecule, or a forced emulsifying urethane water that is emulsified under strong mechanical shearing force using a surfactant in combination.
  • a dispersion is preferred.
  • the urethane resin in the aqueous dispersion can be obtained by reacting a polyol with an organic polyisocyanate and a hydrophilic group-containing compound.
  • polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propylene glycol, neopentyl glycol, 1,3- and 1,4-butanediol, 3-methylpentanediol, Low-molecular-weight polyols such as hexamethylene glycol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, cyclohexanedimethanol; succinic acid, glutaric acid, adipine acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrofuranic acid, endomethinetetrahydrofuranic acid, condensates with polyvalent carboxylic acids such as hexahydrophthalic acid, and the like.
  • Low-molecular-weight polyols such as
  • polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene polytetramethylene glycol, polypropylene polytetramethylene glycol, and polytetramethylene glycol.
  • polycarbonate polyols can be obtained by reacting carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene with diols.
  • diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propylene glycol, neopentyl glycol, 1,3- and 1,4-butanediol, 3-methylpentanediol, hexamethylene glycol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, cyclohexanedimethanol and the like.
  • organic polyisocyanates examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate.
  • aromatic isocyanates such as (TMXDI); aliphatic isocyanates such as hexamethylene diisocyanate (HMDI); be done. These may be used alone or in combination of two or more.
  • a urethane resin can be obtained by a known method.
  • a urethane prepolymer can be obtained by mixing the polyol, organic polyisocyanate, and hydrophilic group-containing compound and reacting them at 30 to 130° C. for 30 minutes to 50 hours.
  • the urethane prepolymer becomes a urethane resin with hydrophilic groups by extending it with a chain extender and polymerizing it.
  • the chain extender is preferably water and/or an amine compound. By using water or an amine compound as a chain extender, the isocyanate-terminated prepolymer can be efficiently extended by reacting with free isocyanate in a short period of time.
  • amine compounds include aliphatic polyamines such as ethylenediamine and triethylenediamine; aromatic polyamines such as metaxylenediamine and toluylenediamine; and polyhydrazino compounds such as hydrazine and adipic acid dihydrazide.
  • the amine compound may contain, together with the polyamine, a monovalent amine such as dibutylamine, methyl ethyl ketoxime, or the like as a reaction terminator, to the extent that polymerization is not greatly hindered.
  • a solvent that is inert with isocyanate and capable of dissolving the urethane prepolymer may be used.
  • these solvents include dioxane, methyl ethyl ketone, dimethylformamide, tetrahydrofuran, N-methyl-2-pyrrolidone, toluene, propylene glycol monomethyl ether acetate, and the like.
  • These hydrophilic organic solvents used in the reaction step are preferably finally removed.
  • amine catalysts e.g., triethylamine, N-ethylmorpholine, triethyldiamine, etc.
  • tin-based catalysts e.g., dibutyltin dilaurate, dioctyltin dilaurate, octylic acid
  • Tin, etc. titanium-based catalysts (eg, tetrabutyl titanate, etc.) may be added.
  • the number average molecular weight of the urethane resin is preferably increased as much as possible by introducing a branched structure or an internal crosslinked structure, and is preferably from 50,000 to 1,000,000. Within the above range, the urethane resin becomes difficult to dissolve in a solvent, and a coating film excellent in weather resistance and water resistance can be obtained.
  • the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC). Solvent: tetrahydrofuran (THF), column temperature: 40° C.) can be determined from a calibration curve prepared from polystyrene standard samples.
  • urethane resins such as WBR-016U (manufactured by Taisei Fine Chemical Co., Ltd.), Superflex (registered trademark) 620, 650, 500M, E-2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). , Permaline (registered trademark) UC-20 (manufactured by Sanyo Chemical Industries, Ltd.), Parasurf UP-22 (manufactured by Ohara Palladium Chemical Co., Ltd.), and the like.
  • WBR-016U manufactured by Taisei Fine Chemical Co., Ltd.
  • Superflex registered trademark
  • E-2000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Permaline registered trademark
  • UC-20 manufactured by Sanyo Chemical Industries, Ltd.
  • Parasurf UP-22 manufactured by Ohara Palladium Chemical Co., Ltd.
  • the acrylic resin can be obtained by using a copolymer with an acrylic acid ester component, a methacrylic acid ester component, a styrene component, or the like.
  • acrylic acid ester components and methacrylic acid ester components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, blue (meth) acrylate, and (meth) acrylic acid-2- Hydroxyethyl, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate ) benzyl acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid,
  • styrene components include styrene, 4-methylstyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-acetylstyrene and styrenesulfonic acid. These components may be used alone or in combination of two or more.
  • the number average molecular weight (Mn) of the acrylic resin is preferably 1,000 to 50,000, more preferably 2,000 to 20,000.
  • Mn number average molecular weight
  • the number average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC).
  • Solvent: tetrahydrofuran (THF), column temperature: 40° C.) can be determined from a calibration curve prepared from polystyrene standard samples.
  • acrylic resin a commercially available product may be used. Fine Chemical Co., Ltd.), 2682, 2680, 2684, 2685, 2687 (manufactured by Nissin Kagaku Kogyo Co., Ltd.).
  • the fine resin particles may be fine composite resin particles, and are preferably fine composite resin particles obtained by emulsifying an acrylic resin with a urethane resin. That is, it is preferable that the fine composite resin particles have an inner layer made of an acrylic resin and a surface layer made of a urethane resin.
  • the urethane resin exists at the interface between the acrylic resin as the water-insoluble resin fine particles and the water as the continuous phase, and functions as a water-insoluble resin fine particle layer different from the resin that protects the water-insoluble resin fine particles.
  • composite resin fine particles obtained by emulsifying acrylic resin with urethane resin in this way, unlike using acrylic resin alone, it is possible to suppress deterioration in compatibility with urethane resin and pigment flocculant.
  • the physical properties of the image (coating film) can be improved, and the stability of the ink can also be improved, compared to emulsifying and mixing the acrylic resin and the urethane resin respectively.
  • the mass ratio (U/A) between the urethane resin (U) and the acrylic resin (A) is in the range of 40/60 to 95/5.
  • the mass ratio (U/A) between the urethane resin (U) and the acrylic resin (A) is preferably in the range of 40/60 to 80/20.
  • the total resin content of the acrylic resin and the urethane resin in the composite resin fine particles is not particularly limited, but is preferably 5.0% by mass or more relative to the total mass of the composite resin fine particles. It is more preferably within the range of 0.0 to 70.0% by mass. Within the above range, good fixability between the recording medium and the ink can be obtained.
  • a surfactant that acts as an emulsifier can be used together with the urethane resin.
  • an emulsifier By adding an emulsifier, the storage stability of the fine composite resin particles can be improved.
  • An anionic surfactant or a nonionic surfactant can be used as an emulsifier, and both are more preferably used in the present invention.
  • the content of the emulsifier (surfactant) is preferably in the range of 1.0 to 20.0% by mass with respect to the total mass of the total resin including the acrylic resin and the urethane resin. By being within the above range, water resistance and solvent resistance can be improved.
  • the content mass ratio (X/Y) between the anionic surfactant (X) and the nonionic surfactant (Y) is preferably within the range of 100/0 to 50/50. By being within the above range, the emulsifiability and the storage stability of the ink can be further improved.
  • anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, sulfosuccinates, alpha olefin sulfonates, N-acyl amino acid salts, carboxylates, phosphate esters, and the like. Among them, sulfosuccinate or alpha olefin sulfonate is preferred.
  • the salt type include, but are not particularly limited to, metal salts such as sodium salts, potassium salts and magnesium salts, and triethanolamine salts.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamine ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and the like. . Among them, polyoxyethylene alkyl ethers or polyoxyethylene alkylphenyl ethers are preferable.
  • the average particle size of the fine resin particles is preferably 1000 nm or more when used as a thickening agent. Further, from the viewpoint of improving the fixability to the recording medium, when the fine resin particles are used as a fixing resin separately from the thickening agent, the average particle size is preferably in the range of 10 to 500 nm, more preferably 10 to 300 nm. more preferably within the range of 10 to 200 nm. As described above, the average particle size can be measured by a commercially available particle size measuring instrument using a dynamic light scattering method, an electrophoresis method, or the like. The particle size range can be measured with high accuracy. When the fine resin particles are used from the viewpoint of improving fixability, the acid structure is not necessarily required, and the acid structure may or may not be present.
  • polyester resin Pesresin A-110F, A-520, A-613D, A-615GE, A-640, A-645GH, A-647GEX (manufactured by Takamatsu Oil Co., Ltd.), Vylonal (registered trademark) MD-1200, 1480, 2000 ( Above, manufactured by Toyobo), Elitel (registered trademark) KA-5034, KA-5071S, KA-1449, KA-0134, KA-3556, KA-6137, KZA-6034, KT-8803, KT-8701, KT- 9204, KT-8904, KT-0507, KT-9511 (manufactured by Unitika Ltd.)
  • NeoRez registered trademark
  • R-967 R-600, R-9671
  • W-6061 W-5661
  • WS-4000 manufactured by Mitsui Chemicals, Inc.
  • Evafanol registered trademark
  • HA-560 manufactured by Nicca Chemical Co., Ltd.
  • Water-soluble resin As the organic compound, the following water-soluble resins can be used.
  • a water-soluble resin can be dispersed in an aqueous medium by having a hydrophilic portion and a hydrophobic portion in the same molecule.
  • water-soluble resins examples include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, sodium polyacrylate, hydroxycellulose, carboxymethylcellulose, and polyethylene glycol. These may be used alone or in combination of two or more.
  • water-soluble resin such as Joncryl (registered trademark) JDX-6500 (manufactured by BASF). Copolymer resins described in JP-A-2011-94082 may also be used.
  • thickener As the thickener according to the present invention, commonly used thickeners other than those mentioned above can be used, and examples thereof include associative thickeners. Commercially available products such as BYK (registered trademark)-425 (manufactured by BYK-Chemie) can be used as the associative thickener.
  • resins that are generally used as pigment dispersants can also be used as the thickener according to the present invention.
  • a commercial product may be used as the pigment dispersant, and examples thereof include Disperbyk 190 and 193 (manufactured by BYK-Chemie).
  • the ink according to the present invention can form an image on the surface of a recording medium by containing a coloring material.
  • the coloring material is not particularly limited as long as it can be colored, and includes dyes and pigments. Pigments are preferred from the viewpoint of forming images on recording media with low or no absorption.
  • pigments include anionic dispersed pigments, such as self-dispersing pigments having anionic groups on the surface, pigments dispersed with an anionic polymer dispersant, and pigments dispersed by coating the surface with an anionic resin. It is preferable to use a pigment or the like.
  • the anionic dispersed pigment is not particularly limited, and known ones can be used. Examples thereof include inorganic pigments such as titanium oxide, and organic pigments such as insoluble pigments and lake pigments.
  • the term "lake pigment” refers to a pigment that is made insoluble by precipitating a water-soluble dye with a lake agent (precipitant).
  • Titanium oxide has three crystal forms: anatase, rutile, and brookite.
  • General-purpose forms can be roughly divided into anatase and rutile. Although it is not particularly limited, it is preferably a rutile type having a high refractive index and high hiding power.
  • titanium oxide commercially available products can be used, such as TR series (trade name, manufactured by Fuji Titanium Industry Co., Ltd.), JR series (trade name, manufactured by Tayca), and Typaque (registered trademark) (trade name, manufactured by Ishihara Sangyo Co., Ltd.). ) and the like.
  • insoluble pigments include, but are not limited to, azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, thiazine, dioxazine, and thiazole. , phthalocyanines, diketopyrrolopyrroles and the like.
  • organic pigments preferably used in the present invention include the following.
  • pigments for magenta or red for example, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 53:1, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I.
  • Pigment Red 166 C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 202, C.I. I. Pigment Red 222, C.I. I. Pigment Violet 19 and the like.
  • pigments for orange or yellow for example, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 15:3, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 155 and the like. In particular, C.I. I. Pigment Yellow 155 is preferred.
  • pigments for green or cyan for example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.
  • black pigments for example, C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7 and the like.
  • the pigment dispersant used to disperse the pigment is not particularly limited, but is preferably a polymeric dispersant having an anionic group, and further preferably has a molecular weight within the range of 5000 to 200000.
  • polymeric dispersants examples include 2 selected from styrene, styrene derivatives, vinylnaphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, and fumaric acid derivatives.
  • Block copolymers, random copolymers and salts thereof, polyoxyalkylenes, polyoxyalkylene alkyl ethers, etc., having structures derived from more than one kind of monomers are included.
  • the polymer dispersant preferably has an acryloyl group and is preferably added after being neutralized with a neutralizing base.
  • the neutralizing base is not particularly limited, but is preferably an organic base such as ammonia, monoethanolamine, diethanolamine, triethanolamine, morpholine and the like.
  • titanium oxide when used as the pigment, it is preferable to disperse the titanium oxide with a polymer dispersant having an acryloyl group.
  • the content of the polymeric dispersant in the ink is preferably in the range of 10 to 100% by mass, more preferably in the range of 10 to 40% by mass, relative to the total mass of the pigment.
  • a so-called capsule pigment in which the pigment is coated with the polymer dispersant may be used.
  • a method for coating the pigment with the polymer dispersant known methods can be used. and a method of coating while polymerizing.
  • Particularly preferred methods include the following methods.
  • a water-insoluble resin is dissolved in an organic solvent such as methyl ethyl ketone, and the acidic groups in the resin are partially or completely neutralized with a base.
  • a pigment and deionized water are added to disperse the pigment.
  • the organic solvent is removed, water is added as necessary, and a pigment dispersion is prepared.
  • the average particle size of the pigment in the dispersed state in the ink is preferably 50 nm or more and less than 300 nm. Within the above range, the dispersion stability of the pigment can be improved, and the storage stability of the ink can be improved.
  • the particle size of the pigment can be determined by a commercially available particle size measuring instrument using a dynamic light scattering method, an electrophoresis method, etc., but the measurement by the dynamic light scattering method is simple and can be measured with high accuracy.
  • the pigment can be dispersed with a dispersing machine together with a dispersant and other additives required according to the purpose.
  • the disperser a known one can be used, and examples include ball mills, sand mills, line mills, high-pressure homogenizers, and the like. Among them, it is preferable to disperse the pigment by a sand mill because the particle size distribution becomes sharp.
  • the material of the beads used for sand mill dispersion is not particularly limited, but zirconia or zircon is preferable from the viewpoint of preventing the generation of bead fragments and contamination with ionic components. Also, the bead diameter is preferably within the range of 0.3 to 3 mm.
  • the content of the pigment in the ink is not particularly limited, but it is preferably in the range of 7 to 18% by mass for titanium oxide and 0.5 to 7% by mass for the organic pigment relative to the total mass of the ink. % is preferred.
  • the ink according to the invention contains water.
  • water-based ink By using water-based ink, the content of organic solvents such as VOCs (volatile organic compounds) can be reduced compared to solvent ink.
  • Water is not particularly limited, and may be ion-exchanged water, distilled water, or pure water.
  • the water content in the ink is preferably in the range of 40 to 90% by weight with respect to the total weight of the ink.
  • the ink according to the present invention can improve the wettability of the ink and the moisture retaining property of the ink on the recording medium.
  • an organic solvent is used also for the purpose of thickening, but it is desirable to suppress the VOC content to 30% by mass or less from the viewpoint of reducing the burden on the environment and drying property.
  • the content of the organic solvent can be reduced by containing the thickener, and the drying property of the ink is improved.
  • the content of the organic solvent in the ink is not particularly limited, but is preferably within the range of 5 to 25% by mass with respect to the total mass of the ink. When the amount is 5% by mass or more, it is possible to suppress ink clogging and ink bubbling in head nozzles.
  • the organic solvent is preferably a water-soluble organic solvent such as alcohols, polyhydric alcohols, amines, amides, glycol ethers, and 1,2-alkanediols having 4 or more carbon atoms. etc.
  • Alcohols include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, t-butanol, 3-methoxy-1-butanol, 3-methoxy -3-methylbutanol, 1-octanol, 2-octanol, n-nonyl alcohol, tridecyl alcohol, n-undecyl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol and the like.
  • polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having 5 or more ethylene oxide groups, propylene glycol, dipropylene glycol, tripropylene glycol, and the number of propylene oxide groups. are 4 or more, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, and the like.
  • amines include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, and the like.
  • amides include formamide, N,N-dimethylformamide, N,N-dimethylacetamide and the like.
  • glycol ethers examples include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl. ether and the like.
  • 1,2-alkanediols having 4 or more carbon atoms examples include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, and 1,2-heptanediol. .
  • the organic solvent is preferably a polyhydric alcohol, especially ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.
  • ethylene glycol diethylene glycol
  • triethylene glycol triethylene glycol
  • tetraethylene glycol propylene glycol
  • propylene glycol dipropylene glycol
  • tripropylene glycol preferably ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.
  • These organic solvents may be used alone or in combination of two or more.
  • the ink according to the invention may further contain a resin.
  • a resin By containing a resin, fixability to a recording medium can be improved.
  • the fixation resin that enhances the fixability is not particularly limited, and examples thereof include vinyl chloride resins, (meth)acrylic resins, urethane resins, polyether resins, and polyester resins.
  • the water-insoluble resin fine particles described above may be contained as a fixing resin.
  • the average particle diameter of the fine resin particles is preferably in the range of 10 to 500 nm, more preferably in the range of 10 to 300 nm, even more preferably in the range of 10 to 200 nm.
  • the resin content in the ink is preferably in the range of 2 to 15% by mass with respect to the total mass of the ink.
  • the ink according to the present invention may contain various known additives according to other purposes such as ejection stability, compatibility with print heads and ink cartridges, storage stability, and image storage stability.
  • Additives include, for example, surfactants. By adding a surfactant, it is possible to improve the ejection stability of the ink and to control the spread (dot diameter) of the ink droplets that have landed on the recording medium.
  • the surfactant is not particularly limited, but when an anionic compound is included in the constituents of the ink, the ionicity of the surfactant may be anionic, nonionic (also referred to as "nonionic"), or amphoteric. and the amphoteric ionic surfactant is preferably a betaine type.
  • the anionic surfactant contains an alkaline component
  • the fine resin particles contained as the fixing resin tend to agglomerate and the fixability decreases, so the surfactant is preferably nonionic.
  • Surfactants include fluorine-based or silicone-based surfactants with high static surface tension lowering ability, anionic surfactants such as dioctyl sulfosuccinate with high dynamic surface tension lowering ability, relatively Nonionic surfactants such as low-molecular-weight polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, acetylene glycols, Pluronic (registered trademark) type surfactants, and sorbitan derivatives are preferred.
  • a surfactant having a high static surface tension lowering ability and a surfactant having a high dynamic surface tension lowering ability may be used in combination.
  • the content of the surfactant in the ink is not particularly limited, but is preferably within the range of 0.1 to 5.0% by mass with respect to the total mass of the ink.
  • various known additives such as polysaccharides, viscosity modifiers, resistivity modifiers, film-forming agents, ultraviolet absorbers, antioxidants, etc. agents, anti-fading agents, anti-mold agents, anti-rust agents, etc. can be used by appropriately selecting them. No. 74193, No. 57-87988, No. 62-261476, etc. ultraviolet absorbers, JP-A-57-74192, No. 57-87989, No. 60-72785, No.
  • JP-A-1-95091 anti-fading agents described in JP-A-1-95091, JP-A-3-13376, JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, Fluorescent whitening agents described in JP-A-61-242871, JP-A-4-219266 and the like.
  • the viscosity of the ink according to the present invention at a shear rate of 1000 [1/s] at 25° C. is preferably 15 mPa ⁇ s (15 cP) or less, and 5 to 10 mPa ⁇ s. is preferably within the range of The viscosity at a shear rate of 1000 [1/s] at 25° C. can be measured using a rotational rheometer such as MCR-102 manufactured by Anton Paar in the same manner as the apparent viscosity ⁇ a below.
  • the ink according to the present invention preferably has relatively low thixotropy, and preferably has a thixotropic index at 25° C. within the range of 0.85 to 1.0.
  • Thixotropy refers to the property that the viscosity gradually decreases when subjected to shear stress and the viscosity gradually increases when standing still.
  • relatively low thixotropy refers to the It means that the thixotropic index is relatively close to 1.0.
  • the thixotropic index n in the viscosity equation can be calculated by the following method.
  • the treatment liquid according to the present invention is characterized by containing a coagulant, water and an organic solvent.
  • a coagulant e.g., water, water and an organic solvent.
  • the aggregating agent can aggregate the coloring material in the ink and improve the image quality of the recorded matter when used in combination with the ink. It may be liquid.
  • pre-treatment liquid refers to a treatment liquid that is applied to the surface of the recording medium before or at the same time as the application of ink to the surface of the recording medium
  • post-treatment liquid refers to the application of ink to the surface of the recording medium. It refers to a treatment liquid that is applied to the surface of the recording medium after the treatment.
  • the treatment liquid according to the present invention can aggregate the coloring material in the ink, and can improve the image quality of the recorded matter.
  • the aggregating agent is not particularly limited as long as it can aggregate the coloring material, but since the coloring material is usually an anionic component, examples thereof include metal salts, cationic compounds, acids, and the like.
  • the flocculants may be used singly or in combination of two or more.
  • the polyvalent metal salt can aggregate anionic components such as the coloring material in the ink by salting out.
  • polyvalent metal salts salts of metals having a valence of two or more can be used.
  • the type of metal (cation ) that constitutes the polyvalent metal salt is not particularly limited . , Cr 3+ , Y 3+ and other trivalent metal ions, and Zr 4+ and other tetravalent metal ions. From the viewpoint of water solubility, Ca 2+ , Mg 2+ , Zn 2+ or Al 3+ is preferable, and Ca 2+ or Mg 2+ is more preferable.
  • the type of anion that constitutes the polyvalent metal salt is not particularly limited, and may be an inorganic ion or an organic ion.
  • inorganic ions include carbonate ions, sulfate ions, nitrate ions, phosphate ions, chloride ions, and hydroxide ions.
  • organic ions include organic ions such as borate ions and carboxylate ions. acid ions.
  • polyvalent metal salts include calcium carbonate such as heavy calcium carbonate and light calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium acetate, magnesium acetate, aluminum acetate and the like. These may be used singly or in combination of two or more.
  • magnesium sulfate, calcium nitrate, or calcium chloride is preferable from the viewpoints of having good water solubility and reducing traces left by the treatment liquid, that is, from the viewpoint of inconspicuous traces.
  • these metal salts may have water of hydration in the raw material form.
  • metal salts other than polyvalent metal salts include monovalent metal salts such as sodium salts and potassium salts, such as sodium sulfate and potassium sulfate.
  • the content of the metal salt is preferably 5% by mass or less, more preferably in the range of 0.1 to 3% by mass, more preferably 0.5 to 1.0% by mass, based on the total mass of the treatment liquid. It is more preferable to be within the mass % range. Within the above range, the anionic components such as the coloring material in the ink can be effectively aggregated, so that both image quality and hot water resistance can be achieved.
  • the metal salt content can be measured by a known method such as ICP emission spectrometry.
  • the applied amount of the metal salt is preferably within the range of 0.1 to 20 g/m 2 , and the applied amount of the treatment liquid is adjusted so as to fall within the above range. is preferred.
  • cationic polymers examples include cationic urethane-based resins, cationic olefin-based resins, and cationic amine-based resins.
  • cationic urethane resin commercially available products can be used, for example, Hydran (registered trademark) CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP- 7610 (trade name, manufactured by Dainippon Ink and Chemicals), Superflex (registered trademark) 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), urethane emulsion WBR-2120C, WBR -2122C (trade name, manufactured by Taisei Fine Chemical Co., Ltd.) or the like can be used.
  • Hydran registered trademark
  • CP-7010 CP-7010
  • CP-7020 CP-7030, CP-7040, CP-7050, CP-7060
  • CP- 7610 trade name, manufactured by Dainippon Ink and Chemicals
  • Superflex registered trademark
  • the cationic olefin-based resin is a resin having an olefin such as ethylene, propylene, or the like in its structural skeleton, and a known one can be appropriately selected and used. Moreover, the cationic olefin resin may be in an emulsion state dispersed in a solvent containing water, an organic solvent, or the like. As the cationic olefin resin, commercially available products can be used, such as Arrowbase (registered trademark) CB-1200 and CD-1200 (trade name, manufactured by Unitika Ltd.).
  • any one having an amino group in its structure can be used, and a known one can be appropriately selected and used.
  • examples thereof include polyamine resins having amino groups in the main skeleton of the resin, polyamide resins having amide groups in the main skeleton of the resin, and polyallylamine resins having allyl groups in the main skeleton of the resin.
  • cationic polyamine resin a commercially available product can be used. mPa s), aqueous solution with a solid concentration of 50% by mass), Unisense KHE104L (trade name, manufactured by Senka Co., Ltd., dimethylamine/epichlorohydrin resin, pH of 1% aqueous solution of about 7.0, viscosity 1 to 10 (mPa s) , an aqueous solution having a solid concentration of 20% by mass), and the like.
  • Unisense KHE104L trade name, manufactured by Senka Co., Ltd., dimethylamine/epichlorohydrin resin, pH of 1% aqueous solution of about 7.0, viscosity 1 to 10 (mPa s) , an aqueous solution having a solid concentration of 20% by mass
  • FL-14 (trade name, manufactured by SNF), Arafix (registered trademark) 100, 251S, 255, 255LOX (trade name, manufactured by Arakawa Chemical Co., Ltd.), DK-6810, 6853, 6885; WS-4010, 4011 , 4020, 4024, 4027, 4030 (trade name, manufactured by Seiko PMC), Papiogen (registered trademark) P-105 (trade name, manufactured by Senka), Sumilaze Resin 650 (30), 675A, 6615, SLX-1 (trade name, manufactured by Taoka Chemical Co., Ltd.), Catiomaster (registered trademark) PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (trade name, manufactured by Yokkaichi Gosei Co., Ltd.), Jetfix 36N, 38A, and 5052 (trade name, manufactured by Satoda Kako Co., Ltd.).
  • polyallylamine resins include polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride/diallylamine hydrochloride copolymer, allylamine acetate/diallylamine acetate copolymer, allylamine acetate/diallylamine acetate copolymer, allylamine hydrochloride/ Dimethylallylamine hydrochloride copolymer, allylamine/dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate/sulfur dioxide copolymer, diallylmethylethylammonium ethylsulfate/sulfur dioxide copolymer, methyldiallylamine hydrochloride/sulfur dioxide copolymer
  • a free-type polyallylamine resin that is not neutralized with an acid may be used, other than the above acid salt type.
  • the free type type is used for a processing liquid containing water, the pH of the processing liquid can be easily adjusted from neutral to alkaline side, and durability and corrosion of ink jet recording device members are prevented.
  • free-type polyallylamine resins include PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, and PAA-25 (trade names, manufactured by Nittobo Medical). .
  • the content of the cationic polymer is preferably within the range of 1 to 5% by mass with respect to the total mass of the treatment liquid.
  • organic acid From the viewpoint of the storage stability of the treatment liquid and from the viewpoint of suppressing blocking after coating and drying the treatment liquid, organic acids are preferred among the acids.
  • the organic acid can aggregate the anionic components such as the coloring material in the ink by changing the pH.
  • organic acids include formic acid, acetic acid, propionic acid, isobutyric acid, oxalic acid, fumaric acid, malic acid, citric acid, malonic acid, succinic acid, maleic acid, benzoic acid, 2-pyrrolidone-5-carboxylic acid, Examples include lactic acid, acrylic acid or derivatives thereof, methacrylic acid or derivatives thereof, acrylamide or derivatives thereof, sulfonic acid derivatives and the like. These may be used singly or in combination of two or more.
  • an organic acid that has not been completely neutralized with a base.
  • Neutralization with a base means that the acidic groups of these acids are ionically bonded with other positively charged elements or compounds (eg, inorganic compounds such as metals).
  • not completely neutralized means that among the acidic groups of the organic acid, there are acidic groups that do not form the above ionic bond.
  • Acids other than organic acids include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. These may be used singly or in combination of two or more.
  • the content of the acid is preferably 5% by mass or less, more preferably in the range of 0.1 to 3% by mass, more preferably 0.5 to 1.0% by mass, relative to the total mass of the treatment liquid. % range is more preferred. Within the above range, the anionic components such as the coloring material in the ink can be effectively aggregated, so that both image quality and hot water resistance can be achieved.
  • the acid content can be measured by a known method such as high performance liquid chromatography (HPLC).
  • the amount of acid applied is preferably equal to or less than the neutralization equivalent of the anionic component in the ink, and the amount of application of the treatment liquid is preferably adjusted so as to fall within the above range. .
  • the treatment liquid according to the present invention can reduce the content of organic solvents such as VOCs (volatile organic compounds) as compared with solvent inks.
  • Water is not particularly limited, and ion-exchanged water, distilled water, or pure water can be used.
  • the content of water in the treatment liquid is preferably in the range of 50 to 90% by weight with respect to the total weight of the treatment liquid.
  • the treatment liquid according to the present invention can improve the wettability of the treatment liquid on the recording medium and the moisture retention of the treatment liquid.
  • the organic solvent is preferably a water-soluble organic solvent such as alcohols, polyhydric alcohols, amines, amides, glycol ethers, and 1,2-alkanediols having 4 or more carbon atoms. and the like, and the same organic solvents as those contained in the ink described above can be used.
  • the content of the organic solvent in the treatment liquid is preferably in the range of 5 to 45% by weight with respect to the total weight of the treatment liquid.
  • the treatment liquid according to the present invention may appropriately contain other components such as a surfactant, a cross-linking agent, an antifungal agent, and a bactericide within a range that does not impair the effects of the present invention.
  • Various known additives such as lubricants, preservatives, thickeners and antistatic agents may be incorporated.
  • the viscosity of the treatment liquid according to the present invention at a shear rate of 1000 [1/s] at 25° C. is preferably 15 mPa ⁇ s (15 cP) or less, and preferably 5 to 10 mPa ⁇ s. It is preferably within the range of s.
  • the viscosity at a shear rate of 1000 [1/s] at 25° C. can be measured using a rotational rheometer such as MCR-102 manufactured by Anton Paar in the same manner as the apparent viscosity ⁇ a below.
  • the ink set for inkjet recording of the present invention is an ink set for inkjet recording containing an ink and a treatment liquid, and it is preferable that the ink and the treatment liquid coalesce with each other on the surface of the recording medium. That is, it is preferable that the ink in the liquid state and the treatment liquid are mixed on the surface of the recording medium, and the mixed liquid is used to form an image.
  • the ink and the treatment liquid do not have to be completely mixed, and only need to be partially mixed.
  • a mixture in which the ink and the treatment liquid are completely mixed or partially mixed is referred to as a "mixed liquid”.
  • liquid ink and treatment liquid can be mixed on the surface of the recording medium.
  • the wet-on-wet method will be described later in detail.
  • the ink according to the present invention (including the thickener) and the ink excluding the thickener are examined. can be determined by mixing with the processing liquid and comparing the viscosities of the mixture.
  • the coloring material in the ink reacts with the coagulant in the treatment liquid, causing the coloring material in the ink to aggregate, and the viscosity of the mixed liquid of the ink and the treatment liquid increases.
  • the pinning property is good, and bleeding between ink droplets and color unevenness can be suppressed.
  • inks that do not contain a compound that inhibits overaggregation of the colorant when the ink and treatment liquid are applied onto the recording medium in the wet-on-wet method, overaggregation tends to occur, and the mixing of the ink and the treatment liquid tends to occur.
  • the viscosity of the liquid increases greatly.
  • the ink contains a compound having a function of inhibiting overaggregation of the coloring material
  • the viscosity of the mixed liquid increases, but the rate of change in viscosity becomes moderate. Therefore, in the present invention, whether or not the thickener has a function of inhibiting overaggregation of the coloring material is determined by the ink (including the thickener) according to the present invention and the thickener in the ink. can be determined by comparing the rate of change in the viscosity of a sample obtained by mixing each sample with the treatment liquid and the sample obtained by mixing the sample with the processing liquid.
  • the following method can be used to determine whether or not the thickener has a function of inhibiting excessive aggregation of the coloring material.
  • composition A The ink of the present invention (including the thickener of the present invention) is designated as composition A, and the ink excluding the thickener of the present invention (water is added instead of the thickener) is composed.
  • Composition B is obtained by mixing Composition A and the treatment liquid according to the present invention
  • Composition C is obtained by mixing Composition A and the treatment liquid according to the present invention
  • Composition D is obtained by mixing Composition B and the treatment liquid according to the present invention.
  • the viscosities of compositions A and B at a shear rate of 1000 [1 / s] at 25 ° C. are V A and V B
  • V C and V D are V C and V D respectively, and when V A to V D satisfy the following relational expressions (1) and (2), it can be determined that the thickener has a function of inhibiting excessive aggregation of the coloring material.
  • composition C and composition D the mixing ratio (mixing ratio of composition A or B and treatment liquid) is not particularly limited, and the preferred range is Although different, it is preferable to mix the treatment liquid within the range of 10 to 100% by mass with respect to the total mass of composition A or B.
  • the viscosity at a shear rate of 1000 [1/s] at 25° C. can be measured using a rotary rheometer, for example, MCR-102 manufactured by Anton Paar, in the same manner as the apparent viscosity ⁇ a described above.
  • the viscosity of the mixture according to the present invention at a shear rate of 2 [1/s] at 25°C is preferably 15 mPa ⁇ s (15 cP) or more.
  • the viscosity at a shear rate of 2 [1 / s] at 25 ° C. is measured using a rotary rheometer, such as MCR-102 manufactured by Anton Paar, E-type viscometer (TVE-33LT, manufactured by Toki Sangyo Co., Ltd.), etc. can be measured
  • the viscosity of a sample can be measured at a prescribed shear rate by varying the rotational speed (rotational speed) of the cone rotor of the E-type viscometer. Specifically, the viscosity is measured under the condition that the rotation speed is 20 rpm, that is, the shear rate is 2 [1/s].
  • the thickener has a function of inhibiting overaggregation of the coloring material is determined by comparing the ink (including the thickener) according to the present invention and the ink excluding the thickener. , are mixed with the treatment liquid, and the ratio of the number of coarse particles in the mixture is compared.
  • the ratio of the number of coarse particles of 5 ⁇ m or more can be calculated by the following method. After diluting the compositions C and D 10,000 times with pure water, using a particle counter (manufactured by RION, sensor: PARTICLE SENSOR KS-42C, controller: CONTROLLER KE-40B1, pump: SYRINGE SAMPLER KZ-31W) , and the flow rate is 10 mL/min. The number of particles is measured three times, and the average value is adopted.
  • composition C and composition D the ratio of the number of particles with a particle size of 5 ⁇ m or more to the total number of particles (total number of particles with the above particle size) is defined as R C and R D respectively, and the ratio (R C / R D ) is calculated.
  • the ink jet recording method of the present invention is characterized in that the ink set for ink jet recording of the present invention is used, and the ink and the treatment liquid are united with each other on the surface of the recording medium.
  • a recording method in which the ink and the treatment liquid are combined with each other on the surface of the recording medium for recording is called a “wet-on-wet method”.
  • the liquid ink and the treatment liquid coalesce (mix) on the surface of the recording medium, increasing the chances of contact between the coloring material in the ink and the coagulant in the treatment liquid. Aggregation progresses sufficiently.
  • the particle size of aggregates composed of the aggregating agent and the colorant becomes too large, that is, excessive aggregation tends to occur, resulting in a problem of deterioration in image quality.
  • the ink set of the present invention over-aggregation is suppressed, and a good image quality recorded matter can be obtained.
  • the ink set of the present invention exhibits remarkable effects during wet-on-wet inkjet recording.
  • wet-on-wet recording by inkjet recording not only provides good image quality, but also allows ink to be applied immediately after applying the treatment liquid. Drying time can be shortened, treatment liquid is not applied to areas not coated with ink, so the texture of the base material can be utilized, and treatment liquid application and ink application can be performed with a single printer. and other advantages.
  • the inkjet recording method of the present invention comprises: 1) a treatment liquid application step of applying a treatment liquid to the surface of a recording medium; 2) an ink application step of applying ink onto the applied treatment liquid; and 3) application to the surface of a recording medium. and a mixed liquid drying step of drying the mixed liquid of the treated liquid and the ink.
  • the treatment liquid application process may be performed before, after, or at the same time as the ink application process, and the mixed liquid drying process is performed after the treatment liquid application process and the ink application process.
  • the recording medium that can be used in the present invention is not particularly limited, but by using the ink set for inkjet recording described above, the ejection stability of the ink is good, and the image quality of the recorded matter is improved. Therefore, it is preferable that the recording medium has low or no absorbency.
  • absorbency refers to absorbency for water-based ink.
  • a well-known plastic film can be used as a recording medium with low or no absorbency.
  • Specific examples include polyester films such as polyethylene terephthalate, polyethylene films, polypropylene films, polyamide films such as nylon, polystyrene films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, biodegradable films such as polylactic acid films, and the like. is mentioned.
  • a film coated with polyvinylidene chloride on one or both sides thereof, or a film deposited with a metal oxide can also be preferably used.
  • the film can be preferably used whether it is an unstretched film or a stretched film.
  • the thickness of the recording medium is preferably in the range of 10-120 ⁇ m, more preferably in the range of 12-60 ⁇ m.
  • metals such as tin plates for three-piece cans and tin-free steel plates (TFS plates, thickness within the range of 0.1 to 0.6 ⁇ m) are preferably used.
  • TFS plates tin-free steel plates
  • the packaging materials for canned foods for example, block air, moisture, and light, and seal the food inside. It is common to use acrylic or acrylic thermosetting paints.
  • Treatment liquid application process In the treatment liquid application process, the above-described treatment liquid is applied to the surface of the recording medium.
  • the treatment liquid is applied to the surface of the recording medium using an inkjet method, similar to the ink described later.
  • the application amount can be finely controlled, and an appropriate amount of treatment liquid can be applied according to the application amount of the ink.
  • the ink coating film may crack and image quality may deteriorate. There is a possibility that the image quality will deteriorate due to the appearance of graininess due to waves. Therefore, it is preferable to finely control the application amount of the treatment liquid, and the application amount of the treatment liquid is controlled by changing the printing rate or the droplet amount of the treatment liquid according to the absorbency of the recording medium and the application amount of the ink. is preferred.
  • a suitable amount of the treatment liquid to be applied varies depending on the constituents of the ink and the treatment liquid, but is preferably in the range of 10 to 100% by mass with respect to the total mass of the ink.
  • the ink is applied to the surface of the recording medium using an inkjet method.
  • the application amount can be finely controlled.
  • a printer equipped with an inkjet head loaded with ink can be used.
  • recording can be performed by ejecting ink droplets from nozzles of an inkjet head based on a digital signal and then landing the droplets on the surface of a recording medium.
  • the inkjet head may be either an on-demand type or a continuous type.
  • on-demand inkjet heads include electro-mechanical conversion, including single-cavity, double-cavity, bender, piston, shear mode and shared wall, and thermal inkjet and bubble jet. (registered trademark, Canon Inc.) type, and other electric-heat conversion methods.
  • an inkjet head (also referred to as a "piezo inkjet head") using a piezoelectric element as an electro-mechanical conversion element used in an electro-mechanical conversion system is preferable.
  • the inkjet head may be either a scanning type inkjet head or a single-pass type inkjet head, but the single-pass type is preferable.
  • the single pass method it is preferable to use a line head type inkjet head.
  • a line head type inkjet head is an inkjet head that has a length greater than the width of the recording area.
  • a single head having a width equal to or larger than the recording range may be used, or a plurality of heads may be combined to form an ink jet head having a width equal to or larger than the recording range.
  • a plurality of heads may be arranged side by side so that their nozzles are staggered to increase the resolution of the heads as a whole.
  • the transport speed of the recording medium can be set, for example, within the range of 1 to 120 m/min.
  • the faster the conveying speed the faster the recording speed.
  • even at a very high linear velocity in the range of 50 to 120 m/min, which is applicable to the single-pass inkjet recording method the ink fixability is high and high-definition recorded matter is produced. can be obtained.
  • the drying temperature is preferably 220°C or less, preferably in the range of 50 to 150°C.
  • the drying time is not particularly limited, but it is preferably a time during which the solvent can be sufficiently removed.
  • the mixed liquid may be dried, for example, using a non-contact heating drying device such as a drying furnace or a hot air blower, or using a contact heating drying device such as a hot plate or a hot roller. you can go
  • the drying temperature is (a) when using a non-contact heating drying device such as a drying furnace or a hot air blower, the temperature in the furnace or the atmosphere temperature such as the hot air temperature, and (b) the temperature of the hot plate, the heat roller, etc.
  • a non-contact heating drying device such as a drying furnace or a hot air blower
  • the temperature in the furnace or the atmosphere temperature such as the hot air temperature
  • the temperature of the hot plate, the heat roller, etc is measured during the entire period of the mixed liquid drying process. obtained by As for the drying temperature, it is preferable to measure (c) the surface temperature of the surface to be dried.
  • the inkjet recording apparatus of the present invention uses the inkjet recording ink set of the present invention, the inkjet recording apparatus has an inkjet head for ink and an inkjet head for treatment liquid, and the inkjet head for ink and the inkjet head for treatment liquid.
  • the heads are mounted on the same carriage, or the inkjet head for ink and the inkjet head for treatment liquid are mounted on separate carriages, and the carriages are adjacent to each other without a drying mechanism in between. and
  • the ink set for inkjet recording of the present invention can use a wet-on-wet method. Ink can be ejected immediately thereafter. Therefore, the inkjet head for ink and the inkjet head for treatment liquid can be mounted on the same carriage.
  • the inkjet recording apparatus of the present invention can be downsized and the recording time can be shortened.
  • the inkjet recording apparatus 200 includes a paper feed section 210, an image recording section 220, a paper discharge section 230, an ink circulation device 8 (see FIG. 3) as ink supply means, and a controller. section (see FIG. 4) and the like.
  • the inkjet recording apparatus 200 conveys the recording medium M stored in the paper feeding section 210 to the image recording section 220, forms an image on the recording medium M in the image recording section 220, and ejects the recording medium M on which the image is formed. It is conveyed to the paper section 230 .
  • the paper feed unit 210 has a paper feed tray 211 that stores the recording medium M, and a medium supply unit 212 that conveys and supplies the recording medium M from the paper feed tray 211 to the image recording unit 220 .
  • the medium supply unit 212 includes a ring-shaped belt whose inner side is supported by two rollers, and the recording medium M is fed from the paper feed tray 211 by rotating the rollers while the recording medium M is placed on the belt. It is conveyed to the image recording section 220 .
  • the image recording section 220 has a conveying drum 221, a delivery unit 222, a heating section 223, a carriage 224, a fixing section 225, a delivery section 226, and the like.
  • the transport drum 221 has a cylindrical surface, and its outer peripheral surface serves as a transport surface on which the recording medium M is placed.
  • the conveying drum 221 conveys the recording medium M along the conveying surface by rotating in the direction of the arrow in FIG. 1 while holding the recording medium M on the conveying surface.
  • the conveying drum 221 includes a claw portion and a suction portion (not shown). holds the recording medium M.
  • the transfer unit 222 is provided between the medium supply unit 212 of the paper supply unit 210 and the transport drum 221, and picks up the recording medium M transported from the medium supply unit 212 by holding one end of the recording medium M transported from the medium supply unit 212 with the swing arm 222a. , to the transport drum 221 via the delivery drum 222b.
  • the heating unit 223 is provided between the arrangement position of the delivery drum 222b and the arrangement position of the carriage 224, and heats the recording medium M conveyed by the conveying drum 221 so that the temperature of the recording medium M is within a predetermined temperature range. to heat.
  • the heating unit 223 has, for example, an infrared heater or the like, and energizes the infrared heater based on a control signal supplied from a control unit (not shown) to cause the heater to generate heat.
  • the "carriage” refers to what supports the inkjet head.
  • the carriage is not particularly limited as long as it can support the inkjet head, and the carriage may or may not be equipped with an ink tank.
  • the inkjet head 100 arranged in the carriage 224 ejects ink onto the recording medium M at an appropriate timing according to the rotation of the transport drum 221 holding the recording medium M based on the image data to form an image.
  • the carriage 224 is arranged with an ink ejection surface facing the transport drum 221 at a predetermined distance.
  • four carriages 224 corresponding to four colors of ink, yellow (Y), magenta (M), cyan (C), and black (K), move the recording medium M.
  • the colors are arranged in the order of Y, M, C, and K from the upstream side in the transport direction so as to be arranged at predetermined intervals.
  • a pair of inkjet heads 100 adjacent in the front-rear direction are arranged in a zigzag pattern at different positions in the front-rear direction.
  • drying of the ink by heating the ink or the recording medium is usually used as a method of fixing (pinning) the ink on the recording medium.
  • this method is applied to an inkjet head arranged in a zigzag arrangement, the timing at which the ink droplets land is shifted, and color unevenness is likely to occur due to the difference in the drying time of the droplets.
  • the ink is fixed using the treatment liquid, and pinning due to drying is unnecessary, so color unevenness and image quality unevenness due to drying time differences are less likely to occur.
  • the present invention employs a wet-on-wet method using inkjet recording, even if there is a difference in the landing timing of the treatment liquid and the ink, it has little effect on the image quality, and good image quality can be obtained. , and an ink jet head arranged in a zigzag manner.
  • the inkjet recording apparatus 200 is an inkjet recording apparatus 200 that performs image recording by a one-pass drawing method using a line head, and the carriage 224 is moved relative to the rotating shaft of the conveying drum 221 during image recording. Position is fixed and used.
  • the ink jet recording apparatus of the present invention may be of a scanning type, in which the carriage reciprocates in the sub-scanning direction.
  • the fixing unit 225 dries and fixes the mixed liquid of the ink and the treatment liquid ejected onto the recording medium M.
  • the delivery unit 226 has a belt loop 226b having a ring-shaped belt whose inside is supported by two rollers, and a cylindrical delivery drum 226a that delivers the recording medium M from the transport drum 221 to the belt loop 226b.
  • the recording medium M transferred from the conveying drum 221 onto the belt loop 226b by the transfer drum 226a is conveyed by the belt loop 226b and delivered to the paper ejection section 230.
  • the paper discharge section 230 has a plate-shaped paper discharge tray 231 on which the recording medium P delivered from the image recording section 220 by the delivery section 226 is placed.
  • the ink set for inkjet recording of the present invention is preferably discharged from an inkjet recording apparatus having a circulation mechanism.
  • inks according to the present invention inks with relatively high thixotropic properties can suppress an increase in the viscosity of the ink by circulating the ink, and good ejection stability can be obtained.
  • the ink circulation device 8 is an ink supply means for generating a circulation flow of ink from pressure chambers (not shown) in the inkjet head 100 to individual ink discharge paths (not shown).
  • the ink circulation device 8 is composed of a supply sub-tank 81, a circulation sub-tank 82, a main tank 83, and the like (see FIG. 3).
  • the supply sub-tank 81 is filled with ink to be supplied to the ink reservoir 51 of the manifold 5 and is connected to the first ink port 53 by an ink flow path 84 .
  • the circulation sub-tank 82 is filled with ink discharged from a discharge liquid chamber (not shown) of the manifold 5 and is connected to the fourth ink port 56 by an ink channel 85 .
  • the supply sub-tank 81 and the circulation sub-tank 82 are provided at different positions in the vertical direction (gravitational direction) with respect to the nozzle surface of the inkjet head 100 (hereinafter also referred to as the "position reference plane").
  • a pressure P1 due to a water head difference between the position reference plane and the supply sub-tank 81 and a pressure P2 due to a water head difference between the position reference plane and the circulation sub-tank 82 are generated.
  • the supply sub-tank 81 and the circulation sub-tank 82 are connected by an ink flow path 86 . Then, the pressure applied by the pump 88 can return the ink from the circulation sub-tank 82 to the supply sub-tank 81 .
  • the main tank 83 is filled with ink to be supplied to the supply sub-tank 81 and is connected to the supply sub-tank 81 by an ink flow path 87 . Ink can be supplied from the main tank 83 to the supply sub-tank 81 by the pressure applied by the pump 89 .
  • the pressure P1 and the pressure P2 can be adjusted by appropriately changing the amount of ink filled in each sub-tank and the position of each sub-tank in the vertical direction (the direction of gravity).
  • the pressure difference between the pressures P1 and P2 allows the ink in the inkjet head 100 to circulate at an appropriate circulation flow rate. As a result, it is possible to remove air bubbles, foreign matter, and the like generated in the head chip of the inkjet head, thereby suppressing nozzle clogging, ejection failure, and the like.
  • the ink circulation device 8 As an example of the ink circulation device 8, the method of controlling the circulation of ink by using the difference in water head has been described, but it is naturally possible to make appropriate modifications as long as the configuration is capable of generating a circulating flow of ink.
  • the ink circulation mechanism is bidirectional circulation. By switching the driving direction of the pump between the forward direction and the reverse direction, the direction of the circulating flow of ink can be changed.
  • FIG. 4 is a block diagram showing the main functional configuration of the inkjet printing apparatus.
  • the inkjet recording apparatus 200 includes the paper feeding section 210, the image recording section 220 (the conveying drum 221, the transfer unit 222, the heating section 223, the carriage 224, the fixing section 225, and the delivery section 226), and the paper discharging section 230. , an ink circulation device 8 as ink supply means, a controller 240 and the like.
  • the control section 240 is connected to each section that configures the inkjet recording apparatus 200 and controls each section that configures the inkjet recording apparatus 200 .
  • the control unit 240 has a CPU 241, a RAM 242, a ROM 243, and the like.
  • the CPU 241 reads and executes various programs, data, and the like according to the content of processing from a storage device such as the ROM 243, and controls the operation of each unit of the inkjet recording apparatus 200 according to the content of the executed processing.
  • the RAM 242 temporarily stores various programs and data processed by the CPU 241 .
  • the ROM 243 stores various programs and data read by the CPU 241 and the like.
  • the control unit 240 performs the following processing on the ink circulation device 8 of the inkjet recording device 200 .
  • the control unit 240 controls the flow rate (circulation flow rate Q) of ink flowing through the flow path R communicating with the nozzles of the inkjet head, that is, the circulation differential pressure ⁇ P, so that the average shear velocity of the flow path R communicating with the nozzle is can be adjusted.
  • the average shear rate of the flow path R is preferably 100 [1/s] or more.
  • the pressure P1 and the pressure P1 and the The pressure P2 is adjusted, and the circulation flow rate Q is controlled by the pressure difference (circulation differential pressure ⁇ P) between the pressures P1 and P2.
  • the circulation differential pressure ⁇ P is preferably within the range of 5 to 30 kPa.
  • a recorded matter formed using the ink set for inkjet recording of the present invention preferably has an ink layer formed using a mixture of ink and treatment liquid on the surface of the recording medium.
  • another functional layer may be provided between the recording medium and the ink layer. may be pasted together.
  • a layer containing a thermosetting resin, the ink layer, and a layer containing a thermosetting resin are preferably laminated in this order on a metal substrate.
  • examples include packaging materials for packaging canned foods, retort-packed foods, beverages, and the like.
  • Recording media with low or no absorbency include, for example, PET film (FE2001, manufactured by Futamura Chemical Co., Ltd.). Thus, a recorded matter with improved image quality can be obtained.
  • thermosetting resin for example, TW-1407 series manufactured by T&K TOKA
  • base coat a thermosetting resin layer
  • thermosetting resin layer a thermosetting resin layer (base coat)
  • thermosetting resin layer top coat
  • thermosetting resin layer top coat
  • composition A ⁇ Preparation and Evaluation of Ink (Composition A)>> Ink compositions 1A to 37A were prepared and evaluated.
  • Pigment Dispersions D1-D3 were prepared as follows. The average particle size of the pigment particles contained in each pigment dispersion was D1: 150 nm, D2: 100 nm, and D3: 220 nm. The average particle size was measured using "Zetasizer Nano S-90" manufactured by Maruballoon.
  • Pigment Dispersion D1 Preparation of Pigment Dispersion D1 After mixing and premixing the following components, the mixture was dispersed using a bead mill filled with 50% by volume of 0.3 mm zirconia beads to prepare a pigment dispersion D1 having a pigment content of 20% by mass.
  • Magenta pigment (mixed crystal of Pigment Red 122 and Pigment Violet 19) 20% by mass Pigment dispersant (acrylic dispersant having a carboxyl group neutralized with dimethylaminoethanol (manufactured by BASF, Joncryl (registered trademark) 819, acid value 75 mgKOH/g, solid content 20% by mass)) 8% by mass Propylene glycol 20% by mass Antifungal agent (Proxel GXL (S) manufactured by Lonza) 0.1% by mass Ion-exchanged water (Remainder; amount to make the total amount 100% by mass)
  • Pigment Dispersion D2 was prepared in the same manner as Pigment Dispersion D1, except that the magenta pigment of Pigment Dispersion D1 was changed to cyan pigment (pigment blue 15:3) at 20% by weight.
  • Pigment Dispersion D3 After mixing and premixing the following components, the mixture was dispersed using a bead mill filled with 50% by volume of 0.3 mm zirconia beads to prepare a pigment dispersion D3 having a pigment content of 40% by mass.
  • Titanium oxide pigment 40% by mass Pigment dispersant (Joncryl (registered trademark) 819, acid value 75 mgKOH/g, solid content 20% by mass, manufactured by BASF) 4% by mass Propylene glycol 20% by mass Antifungal agent (Proxel GXL (S) manufactured by Lonza) 0.1% by mass Ion-exchanged water (Remainder; amount to make the total amount 100% by mass)
  • Pigment dispersant Joncryl (registered trademark) 819, acid value 75 mgKOH/g, solid content 20% by mass, manufactured by BASF
  • Propylene glycol 20% by mass
  • Antifungal agent Proxel GXL (S) manufactured by Lonza
  • Ion-exchanged water Remainder; amount to make the total amount 100% by mass
  • composition 1A The following components were mixed, and the resulting mixture was filtered through a 1 ⁇ m filter to prepare composition 1A. There was no substantial compositional change before and after filtration.
  • Pigment dispersion D1 20% by mass (4% by mass as solid content)
  • Thickener a manufactured by BYK-Chemie, BYK (registered trademark)-425
  • Resin fine particle dispersion P1 the amount added is adjusted so that the resin fine particles (solid content) is 5% by mass in composition 1A
  • Surfactant TEGO (registered trademark) WET-KL245, manufactured by Evonik
  • TEGO registered trademark
  • WET-KL245 manufactured by Evonik
  • Antifungal agent Proxel GXL (S), manufactured by Lonza
  • Ion-exchanged water Remainder; amount to make the total amount 100% by mass
  • composition 2A was prepared in the same manner as in the preparation of composition 1A, except that the types and amounts of the thickener, pigment dispersion, organic solvent, resin and surfactant were changed as shown in Tables I and II below.
  • ⁇ 37A was prepared. Numerical values for thickeners, pigment dispersions, organic solvents, resins, surfactants, and antifungal agents in Tables I and II represent the percentage of the total mass of composition A, and the "-" indicates the corresponding component. indicates that it does not contain
  • the numerical values in the "thickening agent ratio" in Tables I and II are the amount of coloring material added (3A: 8% by mass, 33A: 10% by mass, 34A: 3% by mass, others: 4% by mass).
  • the ratio of the added amount of the sticky agent is represented, and the numerical value in the "organic solvent total amount” represents the ratio of the total amount of the organic solvents a to e and the organic solvent contained in the pigment dispersion with respect to the total mass of the composition A.
  • all units of numerical values are [% by mass].
  • compositions 1B-37B were prepared in the same manner as in the preparation of compositions 1A to 37A, except that the thickener was changed to pure water.
  • 36B was the same component and addition amount as 36A.
  • each component in Tables I and II is as follows.
  • Viscosity> The viscosities of the compositions A and B were measured in the rotation mode of MCR-102 at a temperature of 25 ° C., a time setting of 150 measurement points, a measurement interval of 2 s, and a shear rate of 1000 [1 / s] to 1 [. 1/s], and the values at a shear rate of 1000 [1/s] were taken as VA and VB .
  • ⁇ Thixotropic Index> Create a logarithmic graph with the viscosity ⁇ a [mPa s] measured above on the vertical axis (Y-axis) and the shear rate [1/s] on the horizontal axis (X-axis).
  • the thixotropic index n was obtained from 1).
  • ⁇ Ejection stability> A Konica Minolta independently driven inkjet head (360 npi, ejection volume 6 pL, 1024 nozzles) was filled with Composition A, and a continuous ejection test was conducted for 30 minutes using a stroboscope-synchronized droplet observation device. After that, ejection stability was evaluated according to the following criteria. In addition, ⁇ or more was regarded as practically no problem. A: Out of the 256 nozzles evaluated, all 256 nozzles ejected normally. ⁇ : Out of the 256 nozzles evaluated, 1 or more and 4 or less abnormal nozzles were observed. ⁇ : Out of the 256 nozzles evaluated, 5 to 9 abnormal ejection nozzles were observed. x: Out of the 256 nozzles evaluated, 10 or more abnormal discharge nozzles were observed.
  • ⁇ A coating film was formed, and color transfer occurred when the coating film was rubbed with a finger, but no color transfer occurred when the coating film was pressed with a finger.
  • ⁇ A coating film was formed, and color transfer occurred even when the coating film was pressed with a finger.
  • x A coating film was not formed.
  • the ink according to the present invention has good ejection stability, has a viscosity of 15 mPa s or less at a shear rate of 1000 [1/s] at 25°C, and has a thixotropic index at 25°C. is in the range of 0.85 to 1.0, more favorable ejection stability can be obtained.
  • the ink according to the present invention has good drying properties, and furthermore, the content of the organic solvent in the ink (composition A) is 25% by mass or less in comparison with composition 22A and others. It can be seen that the effect is remarkable. Further, from a comparison of Composition 32A with Compositions 1A and 31A, it was found that good ejection stability can be obtained when the content of the organic solvent in the ink (Composition A) is 5% by mass or more. Recognize.
  • Treatment liquids 1 to 12 according to the present invention were prepared and evaluated.
  • a treatment liquid 1 was prepared by mixing the following components and filtering the resulting mixed liquid through a 1 ⁇ m filter.
  • Treatment solutions 2 to 12 were prepared in the same manner as in the preparation of treatment solution 1, except that the types and amounts of flocculants, organic solvents, surfactants, and thickeners were changed as shown in Table IV below. .
  • the organic solvents, surfactants and thickeners in Table IV are synonymous with the components used in the preparation of the ink, and other organic solvents and flocculants not used in the preparation of the ink are described below It is as follows.
  • the ejection stability was evaluated for the treatment liquids 1 to 12.
  • the evaluation method has the same meaning as the method for evaluating the ejection stability of the ink. Evaluation results are shown in Table IV.
  • composition C and composition D the ratio of the number of particles with a particle size of 5 ⁇ m or more to the total number of particles (total number of particles with the above particle size) is defined as R 1C and R 1D , respectively, and the ratio (R 1C / R 1D ) was calculated.
  • Printing was carried out unidirectionally in the direction recorded in the The conveying speed of the carriage was set to 300 mm/sec, and no drying process was provided between the recording of the treatment liquid and the ink.
  • a PET film (FE2001, thickness 50 ⁇ m, manufactured by Futamura Chemical Co., Ltd.) was used as a recording medium. After printing, the recording medium was placed in a dryer set at 90° C. and dried by heating for 5 minutes to obtain a recorded matter.
  • the recorded matter was subjected to the following image quality evaluation.
  • ⁇ Smoothness> A solid image of 5 cm ⁇ 5 cm was recorded by the above method, and the presence or absence of surface gloss and unevenness was evaluated. In addition, 0 or more was regarded as no practical problem.
  • ⁇ Reflection of light was observed when observed in a bright place, and no surface unevenness was observed when traced with a finger.
  • ⁇ No light reflection was observed when observed in a bright place, but no surface unevenness was observed when traced with a finger.
  • x No reflection of light was observed when observed in a bright place, and surface unevenness was felt when traced with a finger.
  • ink set 47 does not provide good ejection stability for composition A, and does not provide good image quality (printing quality and smoothness) of recorded matter.
  • Ink set 48 does not provide good smoothness of the recorded matter, and it can be seen that the thickener g contained in composition A does not have the function of inhibiting overaggregation of the coloring material.
  • the ink set of the present invention has good ink ejection stability, and furthermore, the image quality of the printed matter is improved.
  • a comparison between ink sets 6 and 7 and others shows that the print quality is improved when V C ⁇ V D .
  • a comparison of ink sets 4 to 7 and 11 to 12 with others shows that printing quality is improved when R C /R D ⁇ 1.
  • the content of the thickening agent It can be seen that printing quality is improved when the content is in the range of 5 to 100% by mass.
  • a comparison between ink set 27 and ink sets 1 and 23 to 25 shows that printing quality is improved when the thickener has at least a hydrophilic portion and a hydrophobic portion in the same particle.
  • a comparison of ink set 11 with ink sets 1 to 5 and 12 shows that the use of a polyvalent metal salt, cationic polymer, or organic acid as the aggregating agent improves print quality and smoothness.
  • a comparison between Set 12 and Ink Sets 1 to 3 shows that the polyvalent metal salt containing at least calcium salt or magnesium salt improves print quality and smoothness.
  • a comparison of the ink sets 22 and 43 with the others shows that the printing quality is improved when the V C is 15 mPa ⁇ s or more.
  • the ink set for ink jet recording of the present invention it is possible to record with good image quality on a recording medium with low or no absorbency. can be applied.
  • Manifold 6 Housing 8 Ink circulation device 53 First ink port 56 Fourth ink port 81 Supply sub-tank 82 Circulation sub-tank 83 Main tank 86 Ink flow path 88 Pump 100 Inkjet head 200 Inkjet recording device 210 Paper feed unit 220 Image recording Unit 224 Carriage 230 Paper discharge unit 240 Control unit M Recording medium P Recording medium

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

La présente invention aborde le problème consistant à fournir : un jeu d'encre pour impression à jet d'encre qui présente une stabilité de distribution d'encre satisfaisante et donne des impressions présentant une qualité d'image améliorée ; un procédé d'impression à jet d'encre ; et un dispositif d'impression à jet d'encre.　Ce jeu d'encre pour impression à jet d'encre comprend une encre et un liquide de traitement, et est caractérisé en ce que l'encre comprend un épaississant, un colorant, de l'eau et un solvant organique et le liquide de traitement comprend un coagulant, de l'eau et un solvant organique, l'épaississant ayant pour fonction d'empêcher le colorant de se coaguler excessivement.
PCT/JP2021/045458 2021-12-10 2021-12-10 Jeu d'encre pour impression à jet d'encre, procédé d'impression à jet d'encre et dispositif d'impression à jet d'encre WO2023105737A1 (fr)

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JP2019218418A (ja) * 2018-06-15 2019-12-26 コニカミノルタ株式会社 インクジェット記録液セット及びインクジェット記録方法
JP2020100005A (ja) * 2018-12-20 2020-07-02 セイコーエプソン株式会社 記録方法、インクセット、及び、印刷装置
WO2021065682A1 (fr) * 2019-09-30 2021-04-08 富士フイルム株式会社 Ensemble d'encre pour impression sur tissu, et procédé d'impression sur tissu
WO2021084960A1 (fr) * 2019-10-29 2021-05-06 富士フイルム株式会社 Produit d'enregistrement d'image et procédé de production de celui-ci
WO2021140772A1 (fr) * 2020-01-10 2021-07-15 富士フイルム株式会社 Procédé d'enregistrement d'image
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JP2005306025A (ja) * 2004-03-25 2005-11-04 Fuji Photo Film Co Ltd インクジェット記録装置及び液塗布方法
JP2010155908A (ja) * 2008-12-26 2010-07-15 Fujifilm Corp インクジェット記録液
JP2015044408A (ja) * 2009-03-25 2015-03-12 コニカミノルタ株式会社 画像形成方法
WO2013179838A1 (fr) * 2012-05-29 2013-12-05 Dic株式会社 Jeu d'encres aqueuses pour enregistrement par jet d'encre
WO2017013983A1 (fr) * 2015-07-22 2017-01-26 コニカミノルタ株式会社 Corps d'impression d'image et procédé d'impression d'image à jet d'encre
WO2017013984A1 (fr) * 2015-07-22 2017-01-26 コニカミノルタ株式会社 Agent de prérevêtement pour jet d'encre et procédé de formation d'image utilisant celui-ci
JP2017024365A (ja) * 2015-07-27 2017-02-02 富士フイルム株式会社 画像記録方法
JP2019162741A (ja) * 2018-03-19 2019-09-26 コニカミノルタ株式会社 画像形成物、インクセットおよび画像形成方法
JP2019218418A (ja) * 2018-06-15 2019-12-26 コニカミノルタ株式会社 インクジェット記録液セット及びインクジェット記録方法
JP2020100005A (ja) * 2018-12-20 2020-07-02 セイコーエプソン株式会社 記録方法、インクセット、及び、印刷装置
WO2021065682A1 (fr) * 2019-09-30 2021-04-08 富士フイルム株式会社 Ensemble d'encre pour impression sur tissu, et procédé d'impression sur tissu
WO2021084960A1 (fr) * 2019-10-29 2021-05-06 富士フイルム株式会社 Produit d'enregistrement d'image et procédé de production de celui-ci
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JP2021155556A (ja) * 2020-03-27 2021-10-07 セイコーエプソン株式会社 組成物セット及び記録方法

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