WO2024004895A1 - Composition d'encre aqueuse, procédé d'enregistrement, procédé de fabrication d'enregistrement, enregistrement, et dispositif d'enregistrement à jet d'encre - Google Patents

Composition d'encre aqueuse, procédé d'enregistrement, procédé de fabrication d'enregistrement, enregistrement, et dispositif d'enregistrement à jet d'encre Download PDF

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Publication number
WO2024004895A1
WO2024004895A1 PCT/JP2023/023458 JP2023023458W WO2024004895A1 WO 2024004895 A1 WO2024004895 A1 WO 2024004895A1 JP 2023023458 W JP2023023458 W JP 2023023458W WO 2024004895 A1 WO2024004895 A1 WO 2024004895A1
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Prior art keywords
mass
ink composition
aqueous ink
monomer
water
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PCT/JP2023/023458
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English (en)
Japanese (ja)
Inventor
菜美 宮沢
祐二 牧本
充功 田村
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株式会社Ｄｎｐファインケミカル
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Publication of WO2024004895A1 publication Critical patent/WO2024004895A1/fr

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Classifications

    • 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
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • 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
    • C09D11/16—Writing inks
    • C09D11/20—Writing inks indelible
    • 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
    • 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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to an aqueous ink composition, a recording method, a method for producing a recorded matter, a recorded matter, and an inkjet recording device.
  • ink compositions water-based inks in which various coloring materials are dissolved in water or a mixture of water and a water-soluble organic solvent are widely used.
  • aqueous ink compositions containing water as a main component have little impact on the environment, do not catch fire, and are therefore highly safe for workers.
  • the dispersible resin is a resin having dispersibility, such as a resin emulsion in which the resin is dispersed in the ink composition as fine resin particles due to electrostatic repulsion, or a colloidal dispersion containing a partially dissolved resin.
  • a dispersible resin as a binder resin, dispersion stability, ejection stability, etc. can be made preferable.
  • Patent Document 1 in the presence of an emulsifier containing a radically polymerizable emulsifier having a sulfonic acid group, an unsaturated monomer having a silyl group and an unsaturated monomer having a 6-membered ring in the side chain are combined.
  • a technique relating to a composition containing a dispersible resin obtained by emulsion polymerization of and is described.
  • Patent Document 1 describes that this composition maintains rapid ink permeability to the ink-receiving layer, further improves gloss, and forms a stable film with particularly excellent color development and no aggregation of the coating liquid. It is stated that it can be done.
  • the resin component constituting the polymer fine particle dispersion contains a hydrophilic component
  • the dispersibility of the polymer fine particle dispersion is improved.
  • a coating film containing a hydrophilic component is easily swollen by water or an organic solvent, resulting in a decrease in solvent resistance.
  • An object of the present invention is to provide an aqueous ink composition that has high storage stability and high solvent resistance of the resulting recorded material even if the aqueous ink composition contains a polymer fine particle dispersion as a binder resin. shall be.
  • an aqueous ink composition containing an acrylic resin and a copolymer containing a specific monomer as a constituent unit can solve the above problems.
  • the inventors have discovered that the problem can be solved, and have completed the present invention. Specifically, the present invention provides the following.
  • a method for producing a recorded matter comprising obtaining a recorded matter by inkjet discharging the aqueous ink composition according to any one of (1) to (3).
  • An inkjet recording device comprising an ink storage mechanism loaded with the aqueous ink composition according to any one of (1) to (3).
  • an aqueous ink composition containing a polymer fine particle dispersion as a binder resin has high storage stability and the obtained recorded matter has high solvent resistance.
  • the aqueous ink composition according to this embodiment contains water and a resin. At least a part of this resin is contained as a polymer fine particle dispersion, the resin contains an acrylic resin, and the acrylic resin is a copolymer containing the following monomers A and monomer B as constituent units. It is characterized by containing.
  • Monomer B a monomer other than monomer A that has an acidic group or a basic group
  • the storage stability of the aqueous ink composition is increased, and the solvent resistance of recorded materials obtained with the aqueous ink composition is increased. be able to.
  • the aqueous ink composition according to this embodiment may be a colored ink containing a coloring material.
  • coloring material includes dyes and pigments, such as dyes or pigments contained in colored inks that form images such as yellow, magenta, cyan, black, and intermediate or light colors thereof. The concept is used to include pigments, white dyes or white pigments contained in white ink, and glitter pigments contained in metallic ink.
  • This colored ink may be a colored ink that forms an image in yellow, magenta, cyan, black, or an intermediate color or light color thereof. Further, the colored ink may be a white ink containing a white coloring material, a metallic ink containing a glittering pigment, or the like.
  • the aqueous ink composition according to the present embodiment may be a receiving solution (pretreatment liquid) that is applied to the substrate before the colored ink is applied to the substrate. Furthermore, it may be a clear ink that does not contain a coloring material, a primer agent for forming a primer layer on the surface of a substrate, etc., or a primer agent for forming an overcoat layer on the surface of a recorded object. It may be an overcoat ink, or it may be something called a paint or a coating agent.
  • the aqueous ink composition according to this embodiment contains a resin. At least a portion of this resin is contained as a polymer fine particle dispersion.
  • a polymer fine particle dispersion refers to a resin in the form of a resin emulsion in which the resin is dispersed as fine resin particles in an ink composition due to electrostatic repulsion, or a colloidal dispersion containing a partially dissolved resin. and is different from, for example, a soluble resin such as that dissolved in an aqueous ink composition.
  • This resin contains an acrylic resin, and this acrylic resin contains a copolymer containing the following monomer A and monomer B as constituent units.
  • Monomer B an acrylic monomer other than monomer A that has an acidic group or a basic group
  • the storage stability of the aqueous ink composition is increased, and the solvent resistance of recorded materials obtained with the aqueous ink composition is increased. be able to.
  • the acrylic resin refers to a resin that has an acrylic skeleton in at least one of its constituent monomers, and may include, for example, a monomer that does not have an acrylic skeleton.
  • the constituent monomer is a monomer that constitutes a polymer before reaction, and is explained as meaning a polymerizable compound having a reactive group such as an ethylenically unsaturated multiple bond.
  • a monomer when a monomer is contained as a constituent unit, it is not contained in the monomer state before reaction, but one of the multiple bonds is polymerized and lost, forming a copolymer. It will be included as a constituent monomer after polymerization.
  • the monomer may be a monomeric polymerizable compound having a reactive group such as an ethylenically unsaturated multiple bond, and may be a monomer with a large molecular weight, which is referred to herein as an oligomer. It is called a monomer.
  • Monomer A is an acrylic monomer having a side chain portion SP value of 8.5 or more and 13.0 or less, which is the SP value calculated for the chemical structure portion defined by R 2 in the following formula (1).
  • the side chain part SP value means the SP value (solubility parameter) of the "-R 2 " part in formula (1), and like the SP value, the functional group constituting "-R 2 " is decomposed. It means the ⁇ (A/B) value when the total value of ⁇ Eoh (cal/mol) is defined as A and the total value of ⁇ V (cm 3 /mol) is defined as B. Note that ⁇ Eoh and ⁇ V are numerical values specific to each substituent, and the Fedors' numerical values were used as reference.
  • the solvent resistance of the resulting recorded material can be increased (among others, the ethanol resistance can be increased).
  • the research conducted by the present inventors has revealed that the physical properties of coating films containing polymers are often greatly influenced by the side chain portions of the polymers rather than by the main chains of the polymers contained in the coating films.
  • a monomer whose side chain moiety SP value, which is the SP value of the "-R 2 " portion of formula (1), is controlled within a predetermined range it is possible to influence the physical properties of the coating film. It is believed that it becomes possible to form a coating film that exhibits the effects of the present invention.
  • the SP value is called a solubility parameter, and it is known that the smaller the difference between the SP values of two components, the higher the solubility. Since the SP value of ethanol is 12.7, the further the distance, the higher the solvent resistance of the coating film to ethanol. On the other hand, when a coating film is formed using a polymer fine particle dispersion, the fine particles are fused together by a water-soluble solvent and the resin chains are diffused, resulting in a strong coating film. Therefore, a certain degree of solubility in water-soluble solvents is also required. Therefore, by setting the SP value within the above range, the coating film will diffuse to a certain extent and be strong in water-soluble solvents, but will not swell easily with solvents such as ethanol, improving solvent resistance. it is conceivable that.
  • the SP value of the side chain portion is preferably 8.5 or more, more preferably 8.8 or more, and even more preferably 9.0 or more.
  • the side chain moiety SP value is preferably 13.0 or less, more preferably 12.0 or less, and even more preferably 11.0 or less.
  • the side chain moiety SP value is preferably 8.5 or more and 13.0 or less, more preferably 8.8 or more and 12.0 or less, and even more preferably 9.0 or more and 11.0 or less. . This makes it possible to increase the solvent resistance of the resulting recorded material (among others, the ethanol resistance).
  • the water/1-octanol partition coefficient (LogP) of this monomer A is 1.0 or more.
  • Water/1-octanol partition coefficient (LogP) is an index of hydrophobicity
  • water/1-octanol partition coefficient (LogP)” is above a certain value (that is, relatively high hydrophobicity).
  • Monomer) as a constituent unit the copolymer becomes difficult to swell in solvents such as ethanol. Therefore, if the copolymer contains monomer A as a constituent unit, it is possible to further improve the solvent resistance of the resulting recorded material.
  • the water/1-octanol partition coefficient (LogP) of monomer A is preferably 1.2 or more, more preferably 1.7 or more, and even more preferably 1.9 or more. .
  • the water/1-octanol partition coefficient (LogP) of this monomer A is preferably 5.0 or less, more preferably 4.8 or less, and even more preferably 3.2 or less.
  • the water/1-octanol partition coefficient (LogP) of monomer A is preferably 1.2 or more and 5.0 or less, more preferably 1.7 or more and 4.8 or less, and 1.9 More preferably, it is 3.2 or less.
  • the homopolymer Tg of this monomer A is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 15°C or higher.
  • the homopolymer Tg of this monomer A is preferably 120°C or lower, more preferably 115°C or lower. Thereby, even when drying at a low temperature, it becomes possible to form a film sufficiently, and the solvent resistance of the obtained recorded material can be further improved.
  • the Tg of the homopolymer of monomer A is preferably 0°C or more and 120°C or less, more preferably 10°C or more and 115°C or less, and even more preferably 15°C or more and 115°C or less.
  • Examples of monomer A include cyclohexyl acrylate (side chain moiety SP value: 9.96, LogP: 2.760 ⁇ 0.226, Tg: 19°C), cyclohexyl methacrylate (side chain moiety SP value: 9.96, LogP :3.179 ⁇ 0.252, Tg: 83°C), phenyl acrylate (side chain part SP value: 10.75, LogP: 1.940 ⁇ 0.404, Tg: 57°C), phenyl methacrylate (side chain part SP value: 10.75, LogP: 2.359 ⁇ 0.429, Tg: 110), methyl acrylate (side chain moiety SP value: 10.26, LogP: 0.788 ⁇ 0.223, Tg: 8°C) , methyl methacrylate (side chain portion SP value: 10.26, LogP: 1.207 ⁇ 0.250, Tg: 105°C,), butyl acrylate (side chain portion SP value: 9.48, LogP: 2.317 ⁇ 0.224, Tg: -54°C
  • the "side chain moiety SP value" in parentheses means the SP value calculated for the chemical structure moiety defined by R2 in formula (1), and "LogP” in parentheses means water/1 - Means the partition coefficient (LogP) in octanol, and "Tg” in parentheses means the Tg of the homopolymer of that monomer.
  • monomer A is preferably a monomer having a ring structure. This makes it possible to form a coating film that not only exhibits the effects of the present invention but also has anti-blocking properties.
  • Examples of the ring structure include an alicyclic structure, a heterocyclic structure, and an aromatic ring structure.
  • Alicyclic structures include cycloalkanes, which are monocyclic compounds composed of three or more carbon-carbon single bonds (e.g., cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane), Examples include cycloalkanes (dicyclopentane, norbornane, adamantane), which are polycyclic compounds.
  • a heterocyclic structure is a cyclic compound containing carbon and one or more other elements (for example, at least one selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus, boron, and silicon) in the ring. be.
  • the aromatic ring structure is a cyclic hydrocarbon exhibiting aromaticity such as a benzene ring or a naphthalene ring.
  • monomers A monomers having an alicyclic structure and/or a heterocyclic structure as the ring structure are preferable.
  • monomer A may contain a monomer having two or more ethylenically unsaturated bonds
  • monomer A is preferably composed of only a monomer having one ethylenically unsaturated bond.
  • the content of monomer A which is a constituent monomer, is not particularly limited, but the lower limit of the content of monomer A is preferably 50% by mass or more, and 70% by mass or more based on the total amount of the copolymer. It is more preferable that the amount is 90% by mass or more. This increases the content of monomer A whose side chain moiety SP value is within a predetermined value range, making it possible to further increase the solvent resistance of the resulting recorded material.
  • Monomer B is a monomer other than monomer A that has an acidic group or a basic group. By including a monomer having an acidic group or a basic group, electrostatic repulsion is imparted to the dispersible resin and the dispersion stability of the dispersible resin is improved, thereby improving the storage stability of the aqueous ink composition. becomes possible.
  • the acidic group included in monomer B includes a carboxyl group, a sulfone group, a phosphoric acid group, and the like. Among these, a carboxyl group is preferred.
  • Examples of the basic group included in monomer B include amino groups (-NH 2 , -NHR, and -NRR'). Among these, a tertiary amino group (-NRR') is preferred.
  • monomer B examples include acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, mono-2-(methacryloyloxy)ethyl phthalate, monohydroxyethyl phthalate, ⁇ -carboxypolycaprolactone ( n ⁇ 2) Monoacrylate, 4-carboxystyrene, 6-acrylamidohexanoic acid, 2-(dimethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl acrylate, dimethylaminopropylacrylamide, 2-aminoethyl methacrylate, Examples include 2-aminoethylmethacrylamide, N-(3-aminopropyl)methacrylamide, 2-(diisopropylamino)ethyl methacrylate, and N-(2-dimethylaminoethyl)methacrylamide. Monomer B is preferably an acrylic monomer. These monomers B may be
  • the content of monomer B which is a constituent monomer, is not particularly limited, but the lower limit of the content of monomer B is preferably 0.1% by mass or more based on the total amount of the copolymer, and 0.5% by mass. % or more, and even more preferably 1.0% by mass or more. This more effectively improves the dispersion stability of the polymer fine particle dispersion, making it possible to further improve the storage stability of the aqueous ink composition.
  • the upper limit of the content of monomer B is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and even more preferably 10.0% by mass or less based on the total amount of the copolymer. preferable.
  • the content range of monomer B is preferably 0.1% by mass or more and 20.0% by mass or less, more preferably 0.5% by mass or more and 15.0% by mass or less based on the total amount of the copolymer. , more preferably 1.0% by mass or more and 0.0% by mass or less.
  • the copolymer contained in the aqueous ink composition according to the present embodiment may or may not contain other monomers different from monomer A and monomer B as constituent units.
  • examples of other monomers include acrylic monomers that do not fall under monomer A and monomer B, and monomers having reactive groups such as ethylenically unsaturated multiple bonds different from acrylic monomers. Examples include 2,2,2-trifluoroethyl (meth)acrylate, styrene, t-butyl-4-ethynylcyclohexane, and vinylcyclohexane. These other monomers may be used alone or in combination.
  • the resin containing the polymer has a crosslinked structure.
  • the resin composition containing a polymer containing such a monomer containing a carbonyl group as a constitutional unit the abrasion resistance of the resulting coating film can be improved.
  • carbonyl group-containing monofunctional ethylenically unsaturated monomer for example, 2-(acryloylamino)-2-methyl-4-pentanone (side chain moiety SP value: 12.04, LogP: 0.037 ⁇ 0.
  • the resin according to the present embodiment may contain a polymer containing a monomer containing a carbonyl group as a constituent unit, but in particular, a crosslinking agent may be added to introduce a crosslinked structure into the resin containing the polymer. Unless it is, it is preferable not to contain a polymer containing a monomer containing a carbonyl group as a constitutional unit.
  • the other monomers may include monomers having two or more ethylenically unsaturated bonds, but it is preferable that the other monomers are composed of only monomers having one ethylenically unsaturated bond.
  • the hardness and brittleness of the coating film due to the increase in the crosslinking points of the resin can be alleviated, and the solvent resistance of the resulting recorded product can be further improved.
  • the content of other monomers is not particularly limited, but the lower limit of the content of other monomers is preferably 45% by mass or less, and preferably 35% by mass or less based on the total amount of the copolymer.
  • the content is more preferably 20% by mass or less.
  • the aqueous ink composition according to the present embodiment contains a copolymer containing monomer A and monomer B as constituent units. As a result, the storage stability of the aqueous ink composition can be increased, and the solvent resistance of recorded materials obtained with the aqueous ink composition can be increased.
  • this copolymer is contained in the aqueous ink composition as a polymer fine particle dispersion.
  • This copolymer can be obtained by a conventionally known radical polymerization method such as an emulsion polymerization method or a suspension polymerization method using monomers including monomer A and monomer B. Among these, this copolymer is preferably an emulsion polymer.
  • emulsifiers include anionic, cationic, and nonionic surfactants.
  • a non-reactive emulsifier that does not have multiple bonds in its structure (that is, the resin contained as a polymer fine particle dispersion contains a non-reactive emulsifier).
  • non-reactive emulsifiers include sodium alkyl sulfates such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and sodium tetradecyl sulfate, ammonium lauryl sulfate, sodium diphenyl ether sulfonate, polyoxyethylene alkyl ether, and polyoxyethylene fatty acid ester.
  • sodium alkyl sulfates such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and sodium tetradecyl sulfate, ammonium lauryl sulfate, sodium diphenyl ether sulfonate, polyoxyethylene alkyl ether, and polyoxyethylene fatty acid ester.
  • the reactive emulsifiers include "Adekaria Soap SE-20N”, “Adekaria Soap SE-10N”, “Adekaria Soap PP-70", “Adekaria Soap PP-710", "Adekarya Soap Rear Soap SR-10'', ⁇ Adekaria Soap SR-20'' (manufactured by Adeka), ⁇ Eleminol JS-2'', ⁇ Eleminol RS-30'' (manufactured by Sanyo Chemical Industries, Ltd.), ⁇ Latemur S-'' 180A'', ⁇ Latemul S-180'', ⁇ Latemul PD-104'' [manufactured by Kao Corporation], ⁇ Aqualon BC-05'', ⁇ Aqualon BC-10'', ⁇ Aqualon BC-20'', ⁇ Aqualon HS-05''.
  • the amount of the emulsifier to be used may be adjusted as appropriate, but it is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more in terms of solid content, per 100 parts by mass of the monomer. , more preferably 1 part by mass or more.
  • the amount of emulsifier used is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the monomer.
  • the amount of emulsifier used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, in terms of solid content, per 100 parts by mass of the monomer. , more preferably 1 part by mass or more and 10 parts by mass or less.
  • polymerization initiator examples include alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and octanoyl peroxide.
  • the amount of the polymerization initiator used may be adjusted appropriately, but it is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, based on 100 parts by mass of the monomer. More preferably, the amount is .05 parts by mass or more.
  • the amount of the polymerization initiator used is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, based on 100 parts by mass of the monomer.
  • the amount of the polymerization initiator used is preferably 0.01 parts by weight or more and 5 parts by weight or less, more preferably 0.03 parts by weight or more and 3 parts by weight or less, based on 100 parts by weight of the monomer. More preferably, the amount is .05 parts by mass or more and 1 part by mass or less.
  • polymerization regulators examples include alcohols such as methanol, ethanol, propanol, and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, furfural, and benzaldehyde; n-dodecylmercaptan, thioglycolic acid, and octyl thioglycolate. and mercaptans such as thioglycerol. These may be used alone or in combination of two or more.
  • the amount of the polymerization regulator used may be adjusted as appropriate, but it is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, based on 100 parts by mass of the monomer. More preferably, the amount is .1 part by mass or more.
  • the amount of the polymerization regulator used is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the monomer.
  • the amount of the polymerization modifier used is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the monomer. It is more preferably .1 part by mass or more and 3 parts by mass or less.
  • a crosslinking agent may be used, it is preferable not to use it (that is, the resin contained as a polymer fine particle dispersion does not contain a crosslinking agent).
  • examples of the crosslinking agent include aliphatic dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide, as well as carbonic acid polyhydrazide, aliphatic, Examples include alicyclic and aromatic bissemicarbazides, aromatic dicarboxylic acid dihydrazides, polyacrylic acid polyhydrazides, aromatic hydrocarbon dihydrazides, hydrazine-pyridine derivatives, and unsaturated dicarboxylic acid dihydrazides such as maleic dihydrazide.
  • aliphatic dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and sebacic acid di
  • the amount of the crosslinking agent used may be adjusted appropriately, but it is preferably less than 2 parts by mass, more preferably less than 1 part by mass, and less than 0.5 parts by mass, based on 100 parts by mass of the monomer. It is more preferable that
  • the neutralizing agent is used to neutralize the acidic or basic groups derived from monomer B.
  • the neutralizing agent By neutralizing the acidic group or basic group derived from monomer B (that is, the copolymer contains monomer B having a neutralized acidic group or basic group as a constituent unit), the present invention This results in an aqueous ink composition that more effectively exhibits the above effects.
  • acids that neutralize the basic groups derived from monomer B include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid, as well as formic acid, acetic acid, propionic acid, benzoic acid, succinic acid, butyric acid, fumaric acid, and paratoluene.
  • examples include organic acids such as sulfonic acid, citric acid, and oxalic acid.
  • benzoic acid is preferably used from the viewpoint of solvent resistance during low temperature drying.
  • bases that neutralize the acidic groups derived from monomer B include inorganic bases such as alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, and alkaline earth metal carbonates, ammonia, and methylamine.
  • the Tg of the acrylic resin containing this copolymer is not particularly limited, but is preferably 0° C. or higher. When the Tg of the acrylic resin is 0° C. or higher, the abrasion resistance of the resulting recorded material can be improved.
  • the Tg of the acrylic resin containing this copolymer is preferably 120°C or less. Since the Tg of the acrylic resin is 120°C or less, it is possible to form a film sufficiently even when drying at a low temperature, and the solvent resistance of the resulting recorded material can be further improved. .
  • the Tg of the acrylic resin containing this copolymer is more preferably 20°C or higher, even more preferably 30°C or higher, and even more preferably 40°C or higher.
  • the Tg of the acrylic resin containing this copolymer is more preferably 100°C or less, even more preferably 90°C or less, and even more preferably 80°C or less.
  • the Tg of the acrylic resin containing this copolymer is preferably 0°C or more and 120°C or less, more preferably 20°C or more and 100°C or less, and even more preferably 30°C or more and 90°C or less.
  • the temperature is preferably 40°C or higher and even more preferably 80°C or lower.
  • the arrangement of the monomers contained in the copolymer containing monomer A and monomer B as constituent units obtained in this way is such that even if the arrangement of the monomers is a random copolymer with no order in the arrangement of the monomers, the same type of monomers Although it may be a long continuous block copolymer or a graft copolymer in which monomers are arranged in a branched manner, a random copolymer is preferable.
  • aqueous ink composition By dispersing a random copolymer containing monomer A and monomer B as constituent units into the aqueous ink composition as a dispersing resin, it is possible to improve the dispersion stability of the copolymer, so the aqueous ink composition It becomes possible to further improve the storage stability of objects.
  • ejection stability can be improved.
  • the average particle diameter of the polymer fine particle dispersion is preferably 10 nm or more, more preferably 20 nm or more, from the viewpoints of dispersion stability in the ink composition and inkjet ejectability.
  • the thickness is preferably 30 nm or more, and more preferably 30 nm or more.
  • the average particle diameter of the polymer fine particle dispersion is preferably 500 nm or less, more preferably 350 nm or less, and even more preferably 250 nm or less, from the viewpoints of dispersion stability in the ink composition and inkjet ejectability.
  • the average particle diameter of the polymer fine particle dispersion is preferably 10 nm or more and 500 nm or less, more preferably 20 nm or more and 350 nm or less, and even more preferably 30 nm or more and 250 nm or less.
  • the average particle diameter of the polymer fine particle dispersion can be measured using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000) at a measurement temperature of 25°C.
  • the weight average molecular weight of the polymer fine particle dispersion is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 100,000 or more. From the viewpoint of storage stability of the aqueous ink composition, it is preferably 2,000,000 or less, more preferably 1,750,000 or less, and even more preferably 1,500,000 or less.
  • the weight average molecular weight of the polymer fine particle dispersion is preferably 5,000 or more and 2,000,000 or less, more preferably 10,000 or more and 1,750,000 or less, even more preferably 100,000 or more and 1,500,000 or less.
  • the molecular weight of the resin indicates the weight average molecular weight Mw, which is a value measured by GPC (gel permeation chromatography), using "HLC-8120GPC” manufactured by Tosoh Corporation. , it can be measured using a polystyrene standard for a calibration curve as a standard.
  • the copolymer containing monomer A and monomer B as constituent units may be obtained by conventionally known polymerization methods, but among commercially available resins, those containing copolymers containing monomer A and monomer B as constituent units may be used. You can get it and get it.
  • the aqueous ink composition according to the present embodiment may contain a resin different from the copolymer containing monomer A and monomer B as constituent units.
  • the resins include acrylic resins different from the above copolymers (including copolymers such as styrene-acrylic resins), polyurethane resins, polyester resins, vinyl chloride resins, One selected from the group consisting of vinyl acetate resin, polyether resin, vinyl chloride vinyl acetate copolymer resin, polyethylene resin, acrylamide resin, epoxy resin, polycarbonate resin, silicone resin, and polystyrene resin. Those containing the above resins or copolymer resins, or mixtures thereof can be used.
  • polymer fine particle dispersions include, for example, Acrit WEM-031U, WEM-200U, WEM-321, WEM-3000, WEM-202U, WEM-3008, acrylic-urethane resin emulsion (manufactured by Taisei Fine Chemical Co., Ltd.) ), Akrit UW-550CS, UW-223SX, AKW107, RKW-500 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic resin emulsion), LUBRIJET N240 (manufactured by Lubrizol, acrylic resin emulsion), Superflex 150, 210, 470, 500M , 620, 650, E2000, E4800, R5002 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion), Viniblan 701FE35, 701FE50, 701FE65, 700, 701, 711, 737, 747 (manufact
  • the content of the resin containing the copolymer containing monomer A and monomer B as constituent units is not particularly limited, but the lower limit of the resin content is 0.05% by mass or more based on the total amount of the aqueous ink composition. It is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more.
  • the upper limit of the resin content is preferably 20% by mass or less, more preferably 17.5% by mass or less, and even more preferably 15% by mass or less based on the total amount of the aqueous ink composition.
  • the content of the resin containing the copolymer containing monomer A and monomer B as constituent units is preferably 0.05% by mass or more and 20% by mass or less, and 0.1% by mass based on the total amount of the aqueous ink composition. It is more preferably 17.5% by mass or less, and even more preferably 1% by mass or more and 15% by mass or less.
  • the aqueous ink composition according to this embodiment contains water.
  • water it is preferable to use deionized water rather than water containing various ions.
  • the water content is not particularly limited as long as it can disperse or dissolve each component, but the lower limit of the water content is within the range of 30% by mass or more based on the total amount of the aqueous ink composition. It is preferably within the range of 45% by mass or more, more preferably within the range of 50% by mass or more.
  • the upper limit of the water content is preferably 85% by mass or less, more preferably 80% by mass or less, and 75% by mass or less based on the total amount of the aqueous ink composition. It is even more preferable.
  • the content of water is preferably in the range of 30% by mass or more and 85% by mass or less, more preferably 45% by mass or more and 80% by mass or less, and 50% by mass or less, based on the total amount of the aqueous ink composition. It is more preferably within the range of 75% by mass or more.
  • the aqueous ink according to this embodiment may contain a water-soluble solvent.
  • the solvent is one that can disperse or dissolve the coloring material and the like.
  • water-soluble solvents include those having 1 to 5 carbon atoms, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, and n-pentanol.
  • Alkyl alcohols; 1 such as 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, 3-methoxy-n-butanol, etc.
  • oxyethylene or oxypropylene copolymers such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, isobutylene glycol , triethylene glycol, tripropylene glycol, tetraethylene glycol, 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,2-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 2- Diols such as methyl-2,4-pentanediol, 3-methyl-1,
  • Monoalkyl ethers diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol ethyl Methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol Dialkyl ethers of polyhydric alcohols such as ethyl methyl ether; ethylene
  • unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene, cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin, cyclohexene, cycloheptene, cyclooctene, 1,1 , 3,5,7-cyclooctatetraene, cyclic unsaturated hydrocarbons such as cyclododecene, aromatic hydrocarbons such as benzene, toluene, xylene; N-methyl-2-pyrrolidone, 2-pyrrolidone, ⁇ -lactam , ⁇ -lactam, ⁇ -caprolactam, N-methyl-epsilon-caprolactam, 2-hydroxylethylpyrrolidone, N-2-hydroxyethyl-2-pyrrolidone, 3-methyl-2-pyrrolidinone, 1,3-di
  • Examples include morpholines and terpene solvents. Among these, it is preferable to select a water-soluble solvent so that the aqueous ink has a desired static surface tension, and for example, it is preferable to include at least one type of water-soluble solvent such as an alkanediol.
  • the content of the water-soluble solvent is not particularly limited as long as it can disperse or dissolve each component, but the lower limit of the content of the water-soluble solvent is 5% by mass or more based on the total amount of the water-based ink. It is preferably within the range of 10% by mass or more, more preferably within the range of 12% by mass or more.
  • the upper limit of the content of the water-soluble solvent is preferably within the range of 50% by mass or less, more preferably within the range of 45% by mass or less, and within the range of 40% by mass or less based on the total amount of the water-based ink. It is even more preferable.
  • the content of the water-soluble solvent is preferably in the range of 5% by mass or more and 50% by mass or less, more preferably in the range of 10% by mass or more and 45% by mass, and 12% by mass or more and 40% by mass or less. It is more preferable that the amount is within the range of % by mass or less.
  • the aqueous ink composition according to this embodiment may contain a coloring material. Although it is not essential for the ink composition according to the present embodiment to contain a coloring material, by containing a coloring material, it is possible to make a colored ink that forms a desired image pattern. It becomes possible to use white ink, metallic ink, etc. that can serve as a base layer.
  • the coloring material may be a dye or a pigment.
  • the pigment that can be used is not particularly limited, and includes organic pigments or inorganic pigments used in conventional aqueous ink compositions. These may be used alone or in combination of two or more. Note that the aqueous ink composition according to this embodiment does not need to contain a coloring material.
  • the dispersion stability of the pigment can be improved by using a dispersant or a dispersion aid (pigment derivative). Further, a pigment or dye may be included in the resin for use.
  • the pigment examples include inorganic pigments and organic pigments conventionally used in aqueous ink compositions. These may be used alone or in combination of two or more.
  • Specific organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine organic pigments, quinacridone organic pigments, perylene organic pigments, perinone organic pigments, azomethine organic pigments, and anthraquinone organic pigments.
  • Organic pigments (anthrone organic pigments), xanthene organic pigments, diketopyrrolopyrrole organic pigments, dioxazine organic pigments, nickel azo pigments, isoindolinone organic pigments, pyranthrone organic pigments, thioindigo organic pigments, condensed azo organic solid solution pigments such as benzimidazolone organic pigments, quinophthalone organic pigments, isoindoline organic pigments, quinacridone solid solution pigments, perylene solid solution pigments, and other pigments such as lake pigments and carbon black. It will be done.
  • Examples of organic pigments using color index (C.I.) numbers include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214, C. I.
  • dyes that can be used include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, and merocyanine. dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes such as indigoid, fulgide dyes, nickel complex dyes, and azulene dyes. can be mentioned.
  • inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, alumina, zinc white, lead sulfate, yellow lead, zinc yellow, red iron ( Examples include red iron oxide (III), cadmium red, ultramarine blue, navy blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and inorganic solid solution pigments.
  • the average dispersed particle size of the pigment is not particularly limited as long as the desired color can be developed. Although it varies depending on the type of pigment, in order to obtain good dispersion stability and sufficient coloring power, the lower limit of the average dispersed particle size of the pigment is preferably within the range of 10 nm or more, and 20 nm or more. It is more preferably within this range, and even more preferably within the range of 30 nm or more.
  • the upper limit of the average dispersed particle diameter of the pigment is preferably within the range of 500 nm or less, more preferably within the range of 400 nm or less, and even more preferably within the range of 350 nm or less.
  • the average dispersed particle size is 500 nm or less, even when the aqueous ink composition according to the present embodiment is inkjet-discharged, nozzle clogging of the inkjet head is unlikely to occur, and a homogeneous image with high reproducibility can be obtained. be able to.
  • the average dispersed particle size is 10 nm or more, the light resistance of the resulting recorded material can be made good.
  • the range of the average dispersed particle diameter of the pigment is preferably in the range of 10 nm or more and 500 nm or less, more preferably in the range of 20 nm or more and 400 nm or less, and even more preferably in the range of 30 nm or more and 350 nm or less. .
  • the average dispersed particle size of the pigment is the average particle size (D50) measured at 25°C using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000). ).
  • the ink composition according to this embodiment may contain a glitter pigment as a pigment.
  • the bright pigments include metal-containing bright pigments that are at least one of simple metals such as aluminum, silver, gold, nickel, chromium, tin, zinc, indium, titanium, and copper; metal compounds; alloys, and mixtures thereof;
  • pearlescent pigments having pearlescent luster or interference luster such as mica, fish scale foil, bismuth acid chloride, silicon dioxide, metal oxides, metallic compounds, and laminated layers thereof.
  • the aqueous ink composition according to the present embodiment contains a glittering pigment
  • the glittering pigment is preferably in the form of a plate (also expressed as a fine plate, a scale, etc.). Thereby, a more suitable metallic gloss can be imparted to the object.
  • the content of the coloring material is not particularly limited, but the total amount of the aqueous ink composition It is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and even more preferably 0.1% by mass or more.
  • the content of the coloring material is preferably 20.0% by mass or less, and 17.0% by mass or less based on the total amount of the aqueous ink composition. It is more preferable that the amount is 15.0% by mass or less, and even more preferably 15.0% by mass or less.
  • the content of the coloring material is preferably 0.05% by mass or more and 20.0% by mass or less, more preferably 0.08% by mass or more and 17.0% by mass or less based on the total amount of the aqueous ink composition.
  • the content is preferably 0.1% by mass or more and 15.0% by mass or less.
  • the content of the coloring material is within the range of 0.05% by mass or more or 20.0% by mass or less, the dispersion stability of the coloring material and the coloring power can be excellently balanced.
  • the aqueous ink composition according to this embodiment may contain a pigment dispersant together with a pigment.
  • the pigment dispersant refers to a resin or surfactant that has a function of improving the dispersibility of the pigment in the ink by adhering to a part of the surface of the pigment.
  • the pigment dispersant that can be used in the aqueous ink composition according to this embodiment is not particularly limited.
  • cationic, anionic, nonionic, amphoteric, silicone, fluorine, and other surfactants can be used.
  • surfactants polymer surfactants (polymer dispersants) such as those exemplified below are preferred.
  • a water-soluble polymer dispersant can be preferably used as the pigment dispersant that can be used in the aqueous ink composition according to the present embodiment.
  • Water-soluble polymer dispersants include, for example, polyester, polyacrylic, polyurethane, polyamine, and polycaptolactone main chains, and the side chains include amino groups, carboxyl groups, sulfo groups, and hydroxy groups. Examples include dispersants having polar groups such as.
  • (co)polymers of unsaturated carboxylic esters such as polyacrylic esters; copolymers of aromatic vinyl compounds such as styrene and ⁇ -methylstyrene and unsaturated carboxylic esters such as acrylic esters; (Partial) amine salts, (partial) ammonium salts and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic esters (co)polymers of and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (poly(lower alkyleneimine) and polyesters containing free carboxyl groups) Amides obtained by reaction and their bases); polyallylamine derivatives (selected from three types of compounds: polyallylamine and polyesters having free carboxylic est
  • water-soluble polymer dispersants include SMA1440, SMA2625, SMA17352, SMA3840, SMA1000, SMA2000, SMA3000 manufactured by Cray Valley, JONCRYL67, JONCRYL678, JONCRYL586 manufactured by BASF Japan, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL690, JONCRYL819, JONCRYL -JDX5050, EFKA4550, EFKA4560, EFKA4585, EFKA5220, EFKA6230, Dispex Ultra PX4575, SOLSPERSE20000, SOLSPERSE27000, SOLSPERSE4 manufactured by Lubrizol 0000, SOLSPERSE41000, SOLSPERSE41090, SOLSPERSE43000, SOLSPERSE44000, SOLSPERSE45000, SOLSPERSE46000, SOLSPERSE47000, SOLSPERSE53095, SOLSPERSE54
  • the aqueous ink composition according to this embodiment may contain a cationic or anionic compound. Although it is not essential for the aqueous ink composition according to this embodiment to contain a cationic compound, by containing a cationic or anionic compound, the aqueous ink composition according to this embodiment can be used as a receiving solution (pretreatment solution). Generally, the coloring material contained in colored ink is anionic, and by applying a receiving solution (pretreatment liquid) containing a cationic compound to the substrate before applying the colored ink to the substrate, The cationic compound makes it possible to aggregate the coloring material, thereby suppressing bleeding of the colored ink.
  • a receiving solution (pretreatment liquid) containing an anionic compound may be applied to the substrate before applying the colored ink to the substrate.
  • the anionic compound makes it possible to aggregate the coloring material, thereby suppressing bleeding of the colored ink.
  • cationic compounds include cationic resins and polyvalent metal salts (multivalent metal ions).
  • the cationic resin can be synthesized by a known method, or a commercially available product can be used.
  • commercially available products include APC-810, 815; D-6010, 6020, 6030, 6040, 6050, 6060, 6080, 6310, DEC-50, 53, 56, 65; FL-14, 42, 44LF, FQP-1264; RSL-18-22, 4071H, 4400, 8391, 8391H, HD70C, HF70D; WS-72 (manufactured by SNF), Arafix 100, 251S, 255, 255LOX (manufactured by Arakawa Chemical), DK-6810, 6853, 6885 ; WS-4010, 4011, 4020, 4024, 4027, 4030 (manufactured by Seiko PMC), Senka F-300; Papiogen P-105, P-113, P-271, P-316; Pitchnol QG5A; Miliogen P- 20; Unis
  • the cationic resin may exist in the aqueous ink composition in a dissolved state or in a dispersed state as a dispersible resin.
  • the metal salt examples include polyvalent metal salts containing an ion of a polyvalent metal with a valence of at least two or more and an anion.
  • polyvalent metal ions include calcium ions, magnesium ions, aluminum ions, titanium ions, iron (II) ions, iron (III) ions, cobalt ions, nickel ions, copper ions, zinc ions, barium ions, strontium ions, etc. can be mentioned.
  • one type selected from calcium ion, magnesium ion, nickel ion, zinc ion, and aluminum ion because it has a large interaction with the coloring material in the ink composition and is highly effective in suppressing bleeding and unevenness. It is preferable to contain the above.
  • the anion may be an inorganic anion or an organic anion.
  • organic anions include acetic acid, benzoic acid, salicylic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, dimethylolpropionic acid, pantothenic acid, succinic acid, maleic acid, glutaric acid, Mention may be made of the anions of suberic acid, trimellitic acid and methylmalonic acid.
  • specific examples of inorganic anions include chloride ions, bromide ions, nitrate ions, and sulfate ions.
  • the content of the cationic or anionic compound is not particularly limited, but the lower limit of the content of the cationic or anionic compound is 0.5% by mass or more based on the total amount of the aqueous ink composition. It is preferably within the range of 0.8% by mass or more, more preferably within the range of 1.0% by mass or more.
  • the content of the cationic or anionic compound is within the range of 0.5% by mass or more based on the total amount of the aqueous ink composition, it becomes possible to fix the coloring material more effectively and prevent bleeding of the colored ink. It can be suppressed more effectively.
  • the upper limit of the content of the cationic or anionic compound is preferably within the range of 9% by mass or less, more preferably within the range of 8% by mass or less, and 7% by mass based on the total amount of the aqueous ink composition. It is more preferable that it is within the following range.
  • the content of the cationic or anionic compound is within the range of 9% by mass or less based on the total amount of the aqueous ink composition, the storage stability and ejection stability of the aqueous ink composition are improved.
  • the content of the cationic or anionic compound is preferably in the range of 0.5% by mass or more and 9% by mass or less, and in the range of 0.8% by mass or more and 8% by mass or less based on the total amount of the aqueous ink composition. It is more preferably within the range of 1.0% by mass or more and 7% by mass or less.
  • the aqueous ink according to this embodiment may contain a leveling agent as a surfactant different from the emulsifier and pigment dispersant contained in the above-mentioned copolymer.
  • a leveling agent as a surfactant different from the emulsifier and pigment dispersant contained in the above-mentioned copolymer.
  • the surface tension of the aqueous ink composition can be controlled within an appropriate range.
  • Leveling agents include, but are not limited to, anionic surfactants, nonionic surfactants, silicone surfactants, and fluorine surfactants because of their excellent ability to adjust surface tension. Agents, acetylene glycol surfactants, and the like are preferably used.
  • Emar Latemul, Perex, Neoperex, Demol (all anionic surfactants; manufactured by Kao Corporation), Sunnol, Liporan, Ripon, Ripal (all anionic surfactants; manufactured by Lion Corporation) (manufactured by Kao Corporation), Neugen, Epan, Sorgen (all nonionic surfactants; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Emulgen, Amit, Emazol (all nonionic surfactants; manufactured by Kao Corporation), Naroacty , Emulmin, Sanonic (all nonionic surfactants; manufactured by Sanyo Chemical Industries, Ltd.), Surfynol 104, 82, 420, 440, 465, 485, TG, 2502, SE-F, 107L, Dynor 360, Dynor 604, Dynor 607 (all acetylene glycol surfactants; manufactured by Evonik), Dynor 960 (a blend of acetylene glycol and silicone surfactants;
  • the content of the leveling agent is not particularly limited, but the lower limit of the content of the leveling agent is preferably 0.30% by mass or more, and 0.40% by mass or more based on the total amount of the aqueous ink composition. It is more preferably within the range of 0.50% by mass or more, and even more preferably within the range of 0.50% by mass or more.
  • the upper limit of the content of the leveling agent is preferably within the range of 5.0% by mass or less, more preferably within the range of 4.0% by mass or less, and 3.0% by mass or less based on the total amount of the aqueous ink composition. % or less is more preferable.
  • the content of the leveling agent is preferably in the range of 0.30% by mass or more and 5.0% by mass or less, and 0.40% by mass or more and 4.0% by mass or less based on the total amount of the aqueous ink composition. It is more preferably within the range of 0.50% by mass or more and 3.0% by mass or less.
  • the aqueous ink composition may further contain conventionally known additives, if necessary.
  • additives include waxes, viscosity modifiers, pH modifiers, antioxidants, preservatives, antifungal agents, and the like.
  • the method for preparing the aqueous ink composition is not particularly limited.
  • a method of preparing a water-based ink composition by adding a self-dispersing pigment, a resin, a surfactant, and other components as necessary to a water-soluble solvent A method in which a pigment and a dispersant are added and dispersed, and then a resin, a surfactant, and other ingredients as necessary are added. Examples include a method of adding components and then dispersing the pigment.
  • the method of applying the aqueous ink composition according to the present embodiment onto the surface of the base material is not particularly limited, and examples thereof include an inkjet method, a gravure method, a flexo method, a spray method, a screen method, a coater method, etc. be able to.
  • the inkjet method is preferred. If the inkjet method is used, it is possible to form a desired image by discharging it onto an arbitrary location on a base material of a desired electronic image.
  • viscosity stability is particularly important. Since such aqueous ink compositions have high storage stability, viscosity stability can be increased, and as a result, ejection stability can also be improved.
  • the surface tension of the aqueous ink composition is not particularly limited, the upper limit of the surface tension at 25°C of the non-aqueous ink composition according to the present embodiment is preferably 40.0 mN/m or less, and 35.0 mN/m. The following is more preferable, and 32.0 mN/m or less is even more preferable.
  • the lower limit of the surface tension at 25° C. of the nonaqueous ink composition according to the present embodiment is preferably 17.0 mN/m or more, more preferably 18.0 mN/m or more, and even more preferably 19.0 mN/m or more. .
  • the range of surface tension at 25°C of the non-aqueous ink composition according to the present embodiment is preferably 17.0 mN/m or more and 40.0 mN/m or less, and 18.0 mN/m or more and 35.0 mN/m or less. More preferably, it is 19.0 mN/m or more and 32.0 mN/m or less.
  • the above water-based ink composition can be used as an overcoat, whether it is a colored ink, a metallic ink, etc., a receiving solution containing a cationic compound, or a clear ink that does not contain a coloring material. It may be ink.
  • the ink set according to this embodiment may be a combination of these ink compositions.
  • the ink set according to the present embodiment may be an aqueous ink composition as long as at least one aqueous ink composition contained in the ink set contains a copolymer containing the above-mentioned specific monomer as a constituent unit.
  • the aqueous ink composition A is an aqueous ink composition containing a copolymer containing the above specific monomer as a constituent unit
  • Ink composition B may be an aqueous ink composition different from the aqueous ink composition containing a copolymer containing the above-mentioned specific monomer as a constituent unit.
  • both the water-based ink composition A and the water-based ink composition B may be water-based ink compositions containing a copolymer containing the above-mentioned specific monomer as a constituent unit.
  • Examples of the ink set according to this embodiment include an ink set containing a colored ink composition containing a coloring material and a receiving solution (pretreatment liquid) containing a cationic compound, and a colored ink containing a coloring material.
  • Examples include an ink set that includes a composition, a receiving solution (pretreatment liquid) containing a cationic compound, and an overcoat ink, and an ink set that includes a colored ink composition containing a coloring material and an overcoat ink.
  • the ink set may also be an ink set that combines colored ink compositions containing coloring materials, such as yellow, magenta, cyan, black, and intermediate colors thereof (for example, orange ink, green ink, violet ink, blue
  • the ink set may be a combination of a plurality of ink compositions, such as a colored ink composition of a light color (for example, a light magenta ink, a light cyan ink, a light black ink).
  • an ink set including a white ink composition containing a white coloring material, a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition, and a white ink composition, and a white ink composition containing a white coloring material
  • the ink set may include a yellow ink composition, a magenta ink composition, a cyan ink composition, a black ink composition, and an intermediate color ink composition or a light color ink composition of yellow, magenta, cyan, or black.
  • an ink set including a metallic ink containing a glittering pigment, a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition, a metallic ink containing a glittering pigment, and a yellow ink composition.
  • the ink set may include a magenta ink composition, a cyan ink composition, a black ink composition, and an intermediate color ink composition or a light color ink composition of yellow, magenta, cyan, or black.
  • the recording method according to this embodiment is a recording method in which the above-mentioned aqueous ink composition containing a copolymer containing a specific monomer as a constituent unit is applied onto a substrate.
  • aqueous ink composition containing a copolymer containing a specific monomer as a constituent unit has high storage stability, so the aqueous ink composition can be coated on a substrate while maintaining high storage stability. It is possible to apply
  • aqueous ink composition containing a copolymer containing a specific monomer as a constituent unit onto the surface of the base material examples include an inkjet method, a gravure method, a flexographic method, and a spray method. method, screen method, coater method, etc. Among these, the inkjet method is preferred. If the inkjet method is used, it is possible to eject to any location on the base material.
  • the recording method according to the present embodiment may include a drying step of drying the aqueous ink composition applied to the surface of the base material. Thereby, the heating temperature during printing can be adjusted and the productivity of recorded matter can be improved.
  • Examples of methods for drying the aqueous ink composition applied to the surface of the substrate include methods for drying using a heating mechanism such as a preheater, platen heater, and afterheater provided in an inkjet recording device; It may be a blowing mechanism that blows hot air or room-temperature air, or a radiation irradiation mechanism that heats the surface of the recorded material using infrared rays or the like. Further, a plurality of these heating mechanisms may be combined.
  • a heating mechanism such as a preheater, platen heater, and afterheater provided in an inkjet recording device
  • It may be a blowing mechanism that blows hot air or room-temperature air, or a radiation irradiation mechanism that heats the surface of the recorded material using infrared rays or the like. Further, a plurality of these heating mechanisms may be combined.
  • the above water-based ink composition containing a copolymer containing a specific monomer as a constituent unit can form a coating film sufficiently even when dried at a relatively low temperature, resulting in recorded matter. It has high solvent resistance. Therefore, by drying at a low temperature, it is possible to produce recorded matter with high productivity while reducing energy load and load on the apparatus.
  • the surface of the recorded material it is preferable to dry the surface of the recorded material to a temperature of 120°C or lower, more preferably to dry the surface to a temperature of 100°C or lower, and dry the surface to a temperature of 80°C or lower. It is more preferable to dry it so that it becomes. Further, in the recording method according to the present embodiment, it is preferable to dry the surface of the recorded material to a temperature of 30°C or higher, more preferably to dry the surface to a temperature of 35°C or higher, and more preferably to a temperature of 40°C or higher. It is further preferable to dry it.
  • the surface of the recorded material it is preferable to dry the surface of the recorded material at a temperature of 30°C or more and 20°C or less, more preferably 35°C or more and 100°C or less, and 40°C or less. It is more preferable to dry at a temperature of 80° C. or lower.
  • the ejection method of the above-mentioned aqueous ink composition containing a copolymer containing a specific monomer as a constituent unit may be any method such as a piezo method, a thermal method, or an electrostatic method.
  • the above-mentioned recording method can also be defined as a method for producing a recorded matter in which the above-mentioned aqueous ink composition containing a copolymer containing a specific monomer as a constituent unit is applied onto a substrate.
  • Each layer constituting the recorded matter manufactured by the method for manufacturing a recorded matter of the above embodiment will be described. Specifically, it is a recorded matter in which the above-mentioned water-based ink composition containing a copolymer containing a specific monomer as a constituent unit, or the water-based ink composition included in the above-mentioned ink set, is applied onto a substrate.
  • the medium (recording medium) and the layer of the aqueous ink composition that constitute the recorded matter will be explained.
  • the base material (recording medium) included in the recorded matter according to this embodiment is not particularly limited, and may be a non-absorbent base material such as a resin base material, a metal plate, or glass, or a non-absorbent base material such as paper or cloth.
  • a non-absorbent base material such as a resin base material, a metal plate, or glass
  • a non-absorbent base material such as paper or cloth.
  • Various types of base materials can be used, such as absorbent base materials such as 100% absorbent base material, or surface coated base materials such as base materials provided with a receptive layer.
  • Non-absorbent base materials include resin base materials such as polyester resin, polypropylene synthetic paper, polypropylene resin, polyethylene resin, acrylic resin, styrene resin, polycarbonate resin, ABS resin, vinyl chloride resin, polyimide resin, etc. Examples include metal, metal foil coated paper, glass, synthetic rubber, and natural rubber.
  • absorbent substrate examples include cardboard, medium-quality paper, high-quality paper, synthetic paper, cotton, synthetic fabric, silk, hemp, fabric, nonwoven fabric, and leather.
  • Examples of the surface-coated base material include coated paper, art paper, cast paper, lightweight coated paper, lightly coated paper, and the like.
  • a layer of an aqueous ink composition is a layer formed by volatilization of the solvent (water or water-soluble organic solvent) contained in the above aqueous ink composition containing a copolymer containing a specific monomer as a constituent unit. It is.
  • the aqueous ink composition contains a coloring material, it becomes a decorative layer or a base layer for forming a desired image.
  • the above water-based ink composition containing a copolymer containing a specific monomer as a constituent unit is used as a receiving solution containing a cationic compound, a copolymer containing a specific monomer as a constituent unit is placed on a base material.
  • the above aqueous ink composition (receiving solution) containing a polymer is applied, and the above aqueous ink composition (colored ink) containing a copolymer containing a specific monomer as a constituent unit is applied thereon.
  • the above aqueous ink composition (receiving solution) containing a copolymer containing a specific monomer as a constituent unit may be applied onto a base material, and then a copolymer containing a specific monomer as a constituent unit may be applied.
  • the ink composition forming the recording layer of the recorded matter may be the above water-based ink composition containing a copolymer containing a specific monomer as a constituent unit, or the ink composition containing a specific monomer as a constituent unit.
  • the ink composition may be different from the above-mentioned aqueous ink composition containing the copolymer contained as a structural unit.
  • the apparatus according to the present embodiment is a storage container (ink This device is equipped with a storage mechanism.
  • the apparatus according to this embodiment is preferably an inkjet recording apparatus equipped with a container (ink storage mechanism) filled with the aqueous ink composition or the aqueous ink included in the ink set.
  • the storage container (ink storage mechanism) installed in the apparatus is not particularly limited, and examples thereof include containers such as an ink bottle, a pouch, a bag-in-box, and a drum. Further, these containers may be further housed in a cartridge or the like.
  • the material of the storage container (ink storage mechanism) is not particularly limited, and may be made of a conventionally known resin, or a material containing some metal materials (for example, an aluminum pouch with an aluminum vapor deposition layer). It may be.
  • this device includes a drying mechanism that dries the ink composition after ejecting the ink composition. This makes it possible to adjust the surface temperature of the recorded material during printing and effectively remove volatile components contained in each ink composition.
  • the drying mechanism is not particularly limited as long as it can dry the recording medium, but it may include a heater such as a pre-heater, platen heater, after-heater, radiation irradiation, or a blower mechanism (hot air, room temperature air, etc.). preferable. Further, a plurality of these heating mechanisms may be combined.
  • the ejection method in each ejection section may be any method such as a piezo method, a thermal method, or an electrostatic method.
  • Example 1 A mixture of 98.5 parts of cyclohexyl methacrylate and 1.50 parts of methacrylic acid was added to 41.0 parts of water and 2.0 parts of "Emulgen A-90 (manufactured by Kao Corporation; nonionic surfactant, solid content 100%)".
  • An emulsified monomer composition was prepared by adding 6.2 parts of Emar 20CM (manufactured by Kao Corporation; anionic surfactant, solid content 25%) into an aqueous solution and stirring.
  • the temperature was raised to 80°C, and while maintaining the temperature, 6.7 parts of 3% potassium persulfate and the remaining emulsified monomer composition were added dropwise over 4 hours to allow the polymerization reaction to proceed.
  • the pH was adjusted to 8 using a 10% ammonia aqueous solution, and the reaction was aged for 1 hour. Thereafter, the mixture was cooled to room temperature to obtain a polymer fine particle dispersion.
  • Example 2 A mixture of 92.6 parts of cyclohexyl methacrylate and 13.1 parts of 2-(dimethylamino)ethylbenzoate methacrylate was added to 40.0 parts of water (deionized water) with "Emulgen A-90 (manufactured by Kao Corporation; Nonion)". 2.0 parts of ⁇ type surfactant, solid content 100%'' and 6.2 parts of ⁇ Sanisol B-50 (manufactured by Kao Corporation; cationic type surfactant, solid content 50%)'' were added to an aqueous solution. An emulsified monomer composition was prepared by stirring.
  • Examples 3-5, 7, 8, 10-15, 19, 20 A polymer fine particle dispersion was obtained in the same manner as in Example 1 except that the monomer types and blending amounts were changed as shown in the table below.
  • Example 6 a polymer fine particle dispersion was obtained in the same manner as in Example 2, except that the monomer types and blending amounts were changed as shown in the table below.
  • Example 16 A mixture of 97.5 parts of cyclohexyl methacrylate, 1.50 parts of methacrylic acid, and 1 part of 2-(acryloylamino)-2-methyl-4-pentanone was added to 41.0 parts of water (deionized water) with "Emulgen A- 90 (manufactured by Kao Corporation; nonionic surfactant, solid content 100%)” and 6.2 parts of "Emar 20CM (manufactured by Kao Corporation; anionic surfactant, solid content 25%)” were dissolved.
  • An emulsified monomer composition was prepared by adding it to an aqueous solution and stirring.
  • the temperature was raised to 80°C, and while maintaining the temperature, 6.7 parts of 3% potassium persulfate and the remaining emulsified monomer composition were added dropwise over 4 hours to allow the polymerization reaction to proceed.
  • the pH was adjusted to 8 using a 10% ammonia aqueous solution, and the reaction was aged for 1 hour. Thereafter, the mixture was cooled to room temperature, and 1 part of adipic acid dihydrazide was added and stirred to obtain a polymer fine particle dispersion.
  • Example 17 100.0 parts by mass of diethylene glycol monobutyl ether was charged into a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the temperature was raised to 70°C under a nitrogen atmosphere.
  • Example 18 A mixture of 50.0 parts of cyclohexyl methacrylate, 48.5 parts of n-butyl methacrylate, and 1.50 parts of methacrylic acid was added to 41.0 parts of water (deionized water) with "Latemul PD-420 (manufactured by Kao Corporation; reactive type)".
  • An emulsified monomer composition was prepared by adding 5.0 parts of a surfactant (solid content: 100%) to an aqueous solution and stirring.
  • the temperature was raised to 80°C, and while maintaining the temperature, 6.7 parts of 3% potassium persulfate and the remaining emulsified monomer composition were added dropwise over 4 hours to allow the polymerization reaction to proceed.
  • the pH was adjusted to 8 using a 10% aqueous ammonia solution, and the reaction was aged for 1 hour. Thereafter, the mixture was cooled to room temperature to obtain a polymer fine particle dispersion.
  • an antifoaming agent "Surfynol 104PG" manufactured by Air Products
  • aqueous ink compositions of Examples 21, 23 to 25 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 21, 23 to 25 solid content concentration 30%), 25% by mass of 1,2-hexanediol, and 0.5% by mass of polysiloxane compound. % and the remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 30, 32 to 35 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 30, 32 to 35 solid content concentration 30%), 25% by mass of NN-diethylformamide, and 0.5% by mass of polysiloxane compound. % and the remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 36 to 40 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 36 to 40 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of N-N-diethylformamide.
  • An aqueous ink composition (colored ink) containing 0.5% by mass of a polysiloxane compound, and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 41, 43 to 45 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 41, 43 to 45 solid content concentration 30%), 25% by mass of 3-methoxy-1-butanol, and 0.5% by mass of polysiloxane compound.
  • An aqueous ink composition (colored ink) containing % by mass and a residual amount of water (deionized water) was produced.
  • aqueous ink composition 25% by mass of a polymer fine particle dispersion (Example 42, solid content concentration 30%), 25% by mass of 3-methoxy-1-butanol, 0.5% by mass of a polysiloxane compound, and the remainder of water (deionized water).
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 46 and 48 to 50 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 46, 48 to 50 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-methoxy-1-butanol.
  • Example 47 Preparation of aqueous ink composition of Example 47 25% by mass of polymer fine particle dispersion (Example 47, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methoxy-1-butanol, and 0.5% by mass of polysiloxane compound. % and the remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 51, 53 to 55 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 51, 53 to 55 solid content concentration 30%), 25% by mass of 2-pyrrolidone, 0.5% by mass of polysiloxane compound, An aqueous ink composition (colored ink) containing a residual amount of water (deionized water) was produced.
  • aqueous ink composition of Example 52 25% by mass of polymer fine particle dispersion (Example 52, solid content concentration 30%), 25% by mass of 2-pyrrolidone, 0.5% by mass of polysiloxane compound, and the remaining amount of water (deionized water).
  • An aqueous ink composition (receiving solution) was prepared.
  • aqueous ink compositions of Examples 56 and 58 to 60 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 56, 58 to 60 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 2-pyrrolidone.
  • an aqueous ink composition (colored ink) containing 0.5% by mass of a polysiloxane compound and a residual amount of water (deionized water) was produced.
  • Example 57 Preparation of aqueous ink composition of Example 57 25% by mass of polymer fine particle dispersion (Example 57, solid content concentration 30%), 20% by mass of 1,2-propanediol, 25% by mass of 2-pyrrolidone, 0.5% by mass of polysiloxane compound, and water. (Deionized water) An aqueous ink composition (receiving solution) containing the remaining amount was produced.
  • aqueous ink compositions of Examples 61, 63 to 65 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 61, 63 to 65 solid content concentration 30%), 25% by mass of 3-methyl-1,3-butanediol, and polysiloxane compound
  • An aqueous ink composition (colored ink) containing 0.5% by mass and a residual amount of water (deionized water) was produced.
  • Example 62 Preparation of aqueous ink composition of Example 62 25% by mass of polymer fine particle dispersion (Example 62, solid content concentration 30%), 25% by mass of 3-methyl-1,3-butanediol, 0.5% by mass of polysiloxane compound, and water (deionized water). ) remaining amount, and an aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 66 and 68 to 70 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 66, 68 to 70 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-methyl-1,3 -
  • aqueous ink composition of Example 67 25% by mass of polymer fine particle dispersion (Example 67, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methyl-1,3-butanediol, and 0% by mass of a polysiloxane compound.
  • An aqueous ink composition (receiving solution) containing .5% by mass and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 71, 73 to 75 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 71, 73 to 75 solid content concentration 30%), 25% by mass of 3-methoxy-N,N-dimethylpropanamide, and polysiloxane.
  • An aqueous ink composition (colored ink) containing 0.5% by mass of the compound and a residual amount of water (deionized water) was produced.
  • aqueous ink composition of Example 72 25% by mass of polymer fine particle dispersion (Example 72, solid content concentration 30%), 25% by mass of 3-methoxy-N,N-dimethylpropanamide, 0.5% by mass of polysiloxane compound, and water (desorbed).
  • An aqueous ink composition (receiving solution) containing the remaining amount of ionized water was produced.
  • aqueous ink compositions of Examples 76 and 78 to 80 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 76, 78 to 80 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-methoxy-N,N -
  • aqueous ink composition of Example 77 25% by mass of polymer fine particle dispersion (Example 77, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methoxy-N,N-dimethylpropanamide, and polysiloxane.
  • An aqueous ink composition (receiving solution) containing 0.5% by mass of the compound and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 81, 83 to 85 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 81, 83 to 85 solid content concentration 30%), 25% by mass of 3-butoxy-N,N-dimethylpropanamide, and polysiloxane.
  • An aqueous ink composition (colored ink) containing 0.5% by mass of the compound and a residual amount of water (deionized water) was produced.
  • Example 82 Preparation of aqueous ink composition of Example 82 25% by mass of polymer fine particle dispersion (Example 82, solid content concentration 30%), 25% by mass of 3-butoxy-N,N-dimethylpropanamide, 0.5% by mass of polysiloxane compound, and water (desorbed). An aqueous ink composition (receiving solution) containing the remaining amount of ionized water was produced.
  • aqueous ink compositions of Examples 86 and 88 to 90 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 86, 88 to 90 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-butoxy-N,N -
  • aqueous ink composition of Example 87 25% by mass of polymer fine particle dispersion (Example 87, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-butoxy-N,N-dimethylpropanamide, and polysiloxane.
  • An aqueous ink composition (receiving solution) containing 0.5% by mass of the compound and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 91, 93 to 95 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 91, 93-95 solid content concentration 30%), 25% by mass of Texanol, 0.5% by mass of polysiloxane compound, and water ( An aqueous ink composition (colored ink) containing the remaining amount of deionized water was produced.
  • Example 92 (Preparation of aqueous ink composition of Example 92) An aqueous solution containing 25% by mass of a polymer fine particle dispersion (Example 92, solid content concentration 30%), 25% by mass of Texanol, 0.5% by mass of a polysiloxane compound, and the remaining amount of water (deionized water). An ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 96, 98 to 100 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 96, 98 to 100 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of Texanol, and An aqueous ink composition (colored ink) containing 0.5% by mass of a siloxane compound and a residual amount of water (deionized water) was produced.
  • aqueous ink composition of Example 97 25% by mass of polymer fine particle dispersion (Example 97, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of Texanol, 0.5% by mass of polysiloxane compound, and water ( An aqueous ink composition (receiving solution) containing the remaining amount of deionized water was prepared.
  • aqueous ink compositions of Examples 101, 103 to 105 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 101, 103 to 105 solid content concentration 30%), 25% by mass of ⁇ -valerolactone, and 0.5% by mass of polysiloxane compound. , a residual amount of water (deionized water), and an aqueous ink composition (colored ink) was produced.
  • aqueous ink composition (Preparation of aqueous ink composition of Example 102) 25% by mass of polymer fine particle dispersion (Example 102, solid content concentration 30%), 25% by mass of ⁇ -valerolactone, 0.5% by mass of polysiloxane compound, remaining amount of water (deionized water), An aqueous ink composition (receiving solution) containing the following was produced.
  • aqueous ink compositions of Examples 106 and 108 to 110 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 106, 108 to 110 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of ⁇ -valerolactone.
  • An aqueous ink composition (colored ink) containing 0.5% by mass of a polysiloxane compound, and a residual amount of water (deionized water) was produced.
  • aqueous ink composition of Example 10 25% by mass of polymer fine particle dispersion (Example 107, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of ⁇ -valerolactone, 0.5% by mass of polysiloxane compound, An aqueous ink composition (receiving solution) containing a remaining amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 111, 113 to 115 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 111, 113 to 115 solid content concentration 30%), 25% by mass of N-methyl-epsilon-caprolactam, and 0.5% by mass of polysiloxane compound.
  • An aqueous ink composition (colored ink) containing % by mass and a residual amount of water (deionized water) was produced.
  • aqueous ink composition (Preparation of aqueous ink composition of Example 112) 25% by mass of a polymer fine particle dispersion (Example 112, solid content concentration 30%), 25% by mass of N-methyl-epsilon-caprolactam, 0.5% by mass of a polysiloxane compound, and the remainder of water (deionized water).
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 116 and 118 to 120 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 116, 118-120 solid content concentration 30%), 20% by mass of 1,2-propanediol, and N-methyl-epsilon-caprolactam.
  • aqueous ink composition of Example 117 25% by mass of polymer fine particle dispersion (Example 117, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of N-methyl-epsilon-caprolactam, and 0.5% by mass of a polysiloxane compound.
  • An aqueous ink composition (receiving solution) was produced, which contained % by mass and a residual amount of water (deionized water).
  • aqueous ink compositions of Examples 121, 123 to 125 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 121, 123 to 125 solid content concentration 30%), 25% by mass of 2-hydroxylethylmorpholine, and 0.5% by mass of polysiloxane compound. % and the remaining amount of water (deionized water).
  • aqueous ink composition (Preparation of aqueous ink composition of Example 122) 25% by mass of polymer fine particle dispersion (Example 122, solid content concentration 30%), 25% by mass of 2-hydroxylethylmorpholine, 0.5% by mass of polysiloxane compound, and remaining amount of water (deionized water)
  • aqueous ink compositions of Examples 126 and 128 to 130 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 126, 128 to 130 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 2-hydroxylethylmorpholine 9
  • An aqueous ink composition (colored ink) containing 0.5% by mass of a polysiloxane compound, and a remaining amount of water (deionized water) was produced.
  • Example 127 Preparation of aqueous ink composition of Example 127) 25% by mass of polymer fine particle dispersion (Example 127, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-hydroxylethylmorpholine, and 0.5% by mass of polysiloxane compound. % and the remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 131, 133 to 135 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 131, 133 to 135 solid content concentration 30%), 25% by mass of 2-hydroxylethylpyrrolidone, and 0.5% by mass of polysiloxane compound.
  • aqueous ink composition of Example 132 25% by mass of polymer fine particle dispersion (Example 132, solid content concentration 30%), 25% by mass of 2-hydroxylethylpyrrolidone, 0.5% by mass of polysiloxane compound, and the remaining amount of water (deionized water).
  • An aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 136 and 138 to 140 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 136, 138 to 140 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 2-hydroxylethylpyrrolidone. %, 0.5% by mass of a polysiloxane compound, and a remaining amount of water (deionized water).
  • Example 137 Preparation of aqueous ink composition of Example 137 25% by mass of polymer fine particle dispersion (Example 137, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-hydroxylethylpyrrolidone, and 0.5% by mass of polysiloxane compound. and a remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 141, 143 to 145 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 141, 143 to 145 solid content concentration 30%), 25% by mass of tripropylene glycol monomethyl ether, and 0.5% by mass of polysiloxane compound.
  • aqueous ink composition (Preparation of aqueous ink composition of Example 142) 25% by mass of polymer fine particle dispersion (Example 142, solid content concentration 30%), 25% by mass of tripropylene glycol monomethyl ether, 0.5% by mass of polysiloxane compound, and the remaining amount of water (deionized water).
  • An aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 146 and 148 to 150 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 146, 148-150 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of tripropylene glycol monomethyl ether. %, 0.5% by mass of a polysiloxane compound, and a remaining amount of water (deionized water).
  • Example 147 Preparation of aqueous ink composition of Example 147) 25% by mass of polymer fine particle dispersion (Example 147, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of tripropylene glycol monomethyl ether, and 0.5% by mass of polysiloxane compound. and a remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 151, 153 to 155 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 151, 153 to 155 solid content concentration 30%), 25% by mass of dipropylene glycol monomethyl ether, and 0.5% by mass of polysiloxane compound.
  • aqueous ink composition (Preparation of aqueous ink composition of Example 152) 25% by mass of polymer fine particle dispersion (Example 152, solid content concentration 30%), 25% by mass of dipropylene glycol monomethyl ether, 0.5% by mass of polysiloxane compound, and the remaining amount of water (deionized water).
  • An aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 156 and 158 to 160 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 156, 158-160 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of dipropylene glycol monomethyl ether. %, 0.5% by mass of a polysiloxane compound, and a remaining amount of water (deionized water).
  • Example 157 Preparation of aqueous ink composition of Example 157) 25% by mass of polymer fine particle dispersion (Example 157, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of dipropylene glycol monomethyl ether, and 0.5% by mass of polysiloxane compound. and a remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 161, 163 to 165 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 161, 163 to 165 solid content concentration 30%), 25% by mass of triethylene glycol monomethyl ether, and 0.5% by mass of polysiloxane compound.
  • An aqueous ink composition (colored ink) containing the remaining amount of water (deionized water) and the remaining amount of water (deionized water) was produced.
  • aqueous ink composition (Preparation of aqueous ink composition of Example 162) 25% by mass of polymer fine particle dispersion (Example 162, solid content concentration 30%), 25% by mass of triethylene glycol monomethyl ether, 0.5% by mass of polysiloxane compound, and the remaining amount of water (deionized water).
  • An aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 166 and 168 to 170 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 166, 168 to 170 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of triethylene glycol monomethyl ether. %, 0.5% by mass of a polysiloxane compound, and a remaining amount of water (deionized water).
  • Polymer fine particle dispersion (Example 167, solid content concentration 30%) 25% by mass, 1,2-propanediol 20% by mass, triethylene glycol monomethyl ether 9% by mass, and polysiloxane compound 0.5% by mass and a remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 171, 173 to 175 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 171, 173 to 175 solid content concentration 30%), 25% by mass of triethylene glycol monobutyl ether, and 0.5% by mass of polysiloxane compound.
  • Example 172 Preparation of aqueous ink composition of Example 172 25% by mass of polymer fine particle dispersion (Example 172, solid content concentration 30%), 20% by mass of 1,2-propanediol, 25% by mass of triethylene glycol monobutyl ether, and 0.5% by mass of polysiloxane compound. and a remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 176 and 178 to 180 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 176, 178-18 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of triethylene glycol monobutyl ether. %, 0.5% by mass of a polysiloxane compound, and a remaining amount of water (deionized water).
  • Example 177 Preparation of aqueous ink composition of Example 177) 25% by mass of polymer fine particle dispersion (Example 177, solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of triethylene glycol monobutyl ether, and 0.5% by mass of polysiloxane compound. and a remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 181 to 185 Preparation of aqueous ink compositions of Examples 181 to 185)
  • the content of the polymer fine particle dispersion was changed to 13% by mass, and water (deionized water) was adjusted so that the total content was 100% by mass.
  • Aqueous ink compositions were produced by changing the content ratio of .
  • aqueous ink compositions of Examples 186 and 188 20% by mass of pigment dispersion, 13% by mass of polymer fine particle dispersion (Examples 186 and 188 solid content concentration 30%), 30% by mass of organic solvent, 0.5% by mass of polysiloxane compound, and water (desorbed).
  • An aqueous ink composition (colored ink) containing the remaining amount of ionized water was produced.
  • the content of the organic solvent was as shown in the table below.
  • Example 187 Preparation of aqueous ink composition of Example 187) Aqueous polymeric particle dispersion (Example 187 solid content concentration 30%) containing 13% by mass, 30% by mass of organic solvent, 0.5% by mass of polysiloxane compound, and remaining amount of water (deionized water) An ink composition (receiving solution) was produced.
  • the content of the organic solvent was as shown in the table below.
  • aqueous ink composition of Example 189 Contains 25% by mass of polymer fine particle dispersion (Example 189, solid content concentration 30%), 30% by mass of organic solvent, 0.5% by mass of polysiloxane compound, and remaining amount of water (deionized water).
  • An aqueous ink composition (receiving solution) was produced.
  • the content of the organic solvent was as shown in the table below.
  • Storage stability The storage stability of the aqueous ink compositions of Examples and Comparative Examples was evaluated. Specifically, the aqueous ink composition was heated in an oven at 60° C. for one week, and the viscosity before and after heating was measured at a liquid temperature of 25° C., and evaluated based on the following evaluation criteria. The evaluation results are shown in the table below (denoted as "storage stability" in the table).
  • the intermittent ejection properties (ejection stability) of the aqueous ink compositions of Examples and Comparative Examples were evaluated. Specifically, the aqueous ink compositions of Examples and Comparative Examples were filled into ink cartridges (accommodating containers), and the ink cartridges (accommodating containers) were mounted on a serial type inkjet recording device equipped with a piezo-type inkjet head. Then, a nozzle check pattern was printed using the inkjet recording apparatus, and the same printing was performed after leaving the head still for 10 minutes without a head cap.
  • the presence or absence of nozzle chipping was checked before and after standing, and the same printing was repeated until nozzle chipping was less than 10% of the pattern before standing, and the ejection performance was evaluated based on the number of times of printing based on the following evaluation criteria.
  • the evaluation results are shown in the table below (denoted as "intermittent ejection property" in the table).
  • Evaluation criteria A 10% or less nozzle chipping in the first printing after standing still B: 10% or less nozzle chipping in the 2nd printing after standing still C: 10% or less nozzle chipping in the 3rd printing after standing still Nozzle chipping 10% or less in the 4th printing after standing still E: 11% or more nozzle chipping in the 4th printing after standing still (outside practical range)
  • blocking resistance The blocking properties of the aqueous ink compositions of Examples and Comparative Examples were evaluated. Specifically, the aqueous ink compositions of Examples and Comparative Examples were printed on a printing substrate (a polypropylene resin substrate (polyolefin resin substrate) whose surface was corona-treated) using an inkjet recording device. Print a solid image with a density of 100%, overlap the printed and non-printed surfaces of the printed material, apply a load of 3 kg/ cm2 for 18 hours at 50°C and 80% humidity, and then quickly peel it off. The gender was evaluated. The evaluation results are shown in the table below (in the table, it is written as "blocking resistance").
  • the aqueous ink compositions of Examples containing an acrylic resin and a copolymer containing a specific monomer as a constituent unit have high storage stability, and the resulting recorded material It can be seen that the solvent resistance is high.
  • the aqueous ink compositions of Examples 1 to 18 containing copolymers containing monomer A in a proportion of 50% by mass or more based on the total amount of the copolymer were compared with the ink composition of Example 19.
  • the solvent resistance of the resulting recorded matter was also improved.
  • aqueous ink compositions of Examples 1 to 19 containing monomer A having a side chain moiety SP value of 9.0 or more and 11.0 or less have a record that can be obtained even when compared with the ink composition of Example 20. Improved solvent resistance of products.

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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)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention fournit une composition d'encre aqueuse qui présente une stabilité de conservation élevée, et qui est telle que la résistance aux solvants d'un enregistrement qu'elle permet d'obtenir est élevée, y compris dans le cas d'une composition d'encre aqueuse comprenant une dispersion de microparticules polymériques en tant que résine de liant.　Plus précisément, l'invention concerne une composition d'encre aqueuse qui comprend une eau et une résine. Au moins une partie de la résine est comprise dans la composition de l'invention en tant que dispersion de microparticules polymériques. La résine comprend une résine acrylique qui comprend à son tour un copolymère contenant en tant qu'unités structurales les monomères (A) et (B) suivants.　Monomère (A) : monomère acrylique dans lequel la valeur SP d'une portion chaîne latérale calculée pour une portion de structure chimique définie par Ｒ２ dans la formule (1) est supérieure ou égale à ８,５ et inférieure ou égale à １３,０, ＣＨ２＝Ｃ（Ｒ１）－Ｒ２　・・・formule （１） (Ｒ１ consiste en un hydrogène ou en un groupe méthyle). Monomère (B) : monomère distinct du monomère (A), et possédant un groupe acide ou un groupe basique.
PCT/JP2023/023458 2022-06-30 2023-06-26 Composition d'encre aqueuse, procédé d'enregistrement, procédé de fabrication d'enregistrement, enregistrement, et dispositif d'enregistrement à jet d'encre WO2024004895A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004203996A (ja) * 2002-12-25 2004-07-22 Kao Corp 水系インク
JP2005272790A (ja) * 2003-04-07 2005-10-06 Seiko Epson Corp 水性インク組成物およびその製造方法
JP2007077371A (ja) * 2005-09-16 2007-03-29 Kao Corp インクジェット記録用水系インク
JP2010077218A (ja) * 2008-09-24 2010-04-08 Fujifilm Corp 水性インク組成物、インクセットおよび画像形成方法
JP2012201691A (ja) * 2011-03-23 2012-10-22 Toyo Ink Sc Holdings Co Ltd 水性インクジェット用インキ組成物
JP2015024508A (ja) * 2013-07-24 2015-02-05 コニカミノルタ株式会社 インクジェット記録方法
JP2019142057A (ja) * 2018-02-19 2019-08-29 株式会社リコー 画像形成装置、画像形成方法、インクおよび印刷物
JP2022085427A (ja) * 2020-11-27 2022-06-08 花王株式会社 水性インク

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004203996A (ja) * 2002-12-25 2004-07-22 Kao Corp 水系インク
JP2005272790A (ja) * 2003-04-07 2005-10-06 Seiko Epson Corp 水性インク組成物およびその製造方法
JP2007077371A (ja) * 2005-09-16 2007-03-29 Kao Corp インクジェット記録用水系インク
JP2010077218A (ja) * 2008-09-24 2010-04-08 Fujifilm Corp 水性インク組成物、インクセットおよび画像形成方法
JP2012201691A (ja) * 2011-03-23 2012-10-22 Toyo Ink Sc Holdings Co Ltd 水性インクジェット用インキ組成物
JP2015024508A (ja) * 2013-07-24 2015-02-05 コニカミノルタ株式会社 インクジェット記録方法
JP2019142057A (ja) * 2018-02-19 2019-08-29 株式会社リコー 画像形成装置、画像形成方法、インクおよび印刷物
JP2022085427A (ja) * 2020-11-27 2022-06-08 花王株式会社 水性インク

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