WO2024004896A1 - Aqueous ink composition, recording method, method for producing recorded matter, recorded matter, and inkjet recording device - Google Patents

Aqueous ink composition, recording method, method for producing recorded matter, recorded matter, and inkjet recording device Download PDF

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Publication number
WO2024004896A1
WO2024004896A1 PCT/JP2023/023459 JP2023023459W WO2024004896A1 WO 2024004896 A1 WO2024004896 A1 WO 2024004896A1 JP 2023023459 W JP2023023459 W JP 2023023459W WO 2024004896 A1 WO2024004896 A1 WO 2024004896A1
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Prior art keywords
mass
ink composition
aqueous ink
monomer
water
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PCT/JP2023/023459
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French (fr)
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 WO2024004896A1 publication Critical patent/WO2024004896A1/en

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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
    • C09D11/30—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 material, a recorded material, and an inkjet recording apparatus.
  • 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 resin emulsion refers to a state in which resin is dispersed in the ink composition as fine resin particles due to electrostatic repulsion. This is different from a molten resin in which the resin is dissolved or a colloidal dispersion that partially contains a dissolved resin.
  • 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 related to a composition containing a synthetic resin emulsion 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.
  • a water-soluble organic solvent that has high affinity with water. Since such water-soluble organic solvents with high affinity for water have a relatively high boiling point, a larger amount of heat is required to dry the aqueous ink composition. On the other hand, from the viewpoint of productivity, it is preferable to use an aqueous ink composition that dries suitably at as low a temperature as possible.
  • An object of the present invention is to provide an aqueous ink composition that provides recorded matter with high solvent resistance even when the aqueous ink composition is dried at low temperatures.
  • the present inventors have developed a copolymer containing an acrylic resin having a glass transition temperature (Tg) within a predetermined range and containing at least two types of monomers as constituent units.
  • Tg glass transition temperature
  • the inventors have discovered that the above-mentioned problems can be solved by using an aqueous ink composition containing the above-mentioned aqueous ink compositions, and have completed the present invention.
  • the present invention provides the following.
  • the resin contains an acrylic resin,
  • the acrylic resin contains a copolymer containing at least two types of monomers as constituent units,
  • the acrylic resin has a Tg of 0°C or more and 120°C or less.A water-based ink composition.
  • An ink set comprising the aqueous ink composition according to any one of (1) to (6).
  • 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 (6).
  • An inkjet recording device comprising an ink storage mechanism loaded with the aqueous ink composition according to any one of (1) to (6).
  • the aqueous ink composition according to this embodiment contains water, a water-soluble organic solvent, and a resin. At least a part of this resin is contained as a polymer fine particle dispersion, and the resin contains an acrylic resin having a Tg of 0°C or more and 120°C or less, and this acrylic resin contains at least two types. Contains a copolymer containing monomers as structural units.
  • the minimum film forming temperature is near the glass transition temperature (Tg) of the polymer fine particle dispersion contained in the aqueous ink composition.
  • the aqueous ink composition contains such an acrylic resin having a glass transition temperature (Tg) within a predetermined range and contains a copolymer containing at least two types of monomers as constituent units, when dried at a low temperature, However, a layer of the water-based ink composition with high solvent resistance can be formed on the coated surface.
  • Tg glass transition temperature
  • coalescents there is a method of lowering the minimum film forming temperature by incorporating a coalescent into the aqueous ink composition, but coalescents generally contain high boiling point organic solvents, and during drying, a large amount of The amount of heat required may make it impossible to achieve low-temperature drying properties.
  • 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 that is applied to the substrate prior to applying the colored ink 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 base material, etc., or an overcoat layer for forming an overcoat layer on the surface of a recorded material, etc. It may be an overcoat ink for other purposes, 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 having a Tg of 0° C. or more and 120° C. or less, and the acrylic resin contains a copolymer containing at least two types of monomers as constituent units.
  • the monomer constituting the copolymer is preferably a copolymer containing, for example, the following monomer A and monomer B as constituent units.
  • Monomer A A monomer having a partition coefficient (LogP) in water/1-octanol of 1.0 or more
  • Monomer B A monomer other than monomer A that has an acidic group or a basic group
  • the aqueous ink composition can further increase the solvent resistance of the obtained recorded material, and also improve the solvent resistance of the aqueous ink composition. It is also possible to increase storage stability.
  • the copolymer in a copolymer containing monomer A and monomer B as constituent units, it is more preferable that the copolymer further contains the following monomer C as a constituent unit.
  • Monomer C A monomer other than monomer A and monomer B whose homopolymer Tg is less than 60°C
  • monomer C which has a homopolymer Tg of less than 60°C, as a constituent unit in addition to monomer A and monomer B, it is possible to form a film satisfactorily even when drying at low temperatures. Therefore, the solvent resistance of the resulting recorded material can be further improved.
  • the acrylic resin refers to a resin that has an acrylic skeleton in at least one of its constituent monomers, and may also 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 water/1-octanol partition coefficient (LogP) of 1.0 or more.
  • Water/1-octanol partition coefficient (LogP) is an index of hydrophobicity, and "water/1-octanol partition coefficient (LogP)” is greater than or equal to a certain value (that is, the hydrophobicity is relatively high).
  • monomer A monomer
  • 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 this monomer A is preferably 1.2 or more, more preferably 1.7 or more, and 1.9. It is more preferable that it is above.
  • the water/1-octanol partition coefficient (LogP) of this monomer A is preferably 5.0 or less, more preferably 4.8 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 or more. More preferably, it is 4.8 or less.
  • this monomer A has a homopolymer Tg of 60° C. or higher.
  • the homopolymer of monomer A has a Tg of 60° C. or higher, it is possible to improve the abrasion resistance of the resulting recorded material.
  • the SP value of the side chain portion which is the SP value calculated for the chemical structure moiety defined by R 2 in the following formula (1), is 8.5 or more and 13.0 or less. .
  • 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 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 it will also be difficult to swell with solvents such as ethanol, making it possible to improve solvent resistance. becomes.
  • 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).
  • Monomer A includes cyclohexyl methacrylate (side chain portion SP value: 9.96, LogP: 3.179 ⁇ 0.252, Tg: 83°C), phenyl methacrylate (side chain portion SP value: 10.75, LogP: 2 .359 ⁇ 0.429, Tg: 110), methyl methacrylate (side chain moiety SP value: 10.26, LogP: 1.207 ⁇ 0.250, Tg: 105°C,), isobornyl acrylate (side chain moiety SP value: 9.42, LogP: 4.029 ⁇ 0.273, Tg: 97°C), isobornyl methacrylate (side chain moiety SP value: 9.42, LogP: 4.447 ⁇ 0.301, Tg: 180°C), ethyl methacrylate (side chain portion SP value: 9.88, LogP: 1.716 ⁇ 0.250, Tg: 65°C), tert-butyl acrylate (side chain portion SP value: 8.99, LogP: 2.062 ⁇ 0.238, Tg
  • Tg in parentheses means the Tg of the homopolymer of the monomer
  • LogP partition coefficient
  • 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 B 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 distribution coefficient (LogP) in water/1-octanol is within a predetermined range or higher, making it possible to further increase the solvent resistance of the resulting recorded material.
  • Monomer B is an acrylic monomer other than monomer A that has an acidic group or a basic group.
  • an acrylic monomer having an acidic group or a basic group electrostatic repulsion is imparted to the polymer fine particle dispersion, improving the dispersion stability of the polymer fine particle dispersion, thereby improving the storage stability of the aqueous ink composition. It becomes possible to improve sexual performance.
  • the acidic group or basic group of monomer B may be in the state of a neutralized salt by being neutralized even if it is as it is.
  • 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, ⁇ -carboxy-polycaprolactone ( 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. These monomers B may be used alone, or a plurality of monomers
  • 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 10.0% by mass or less.
  • Monomer C is a monomer other than monomer A and monomer B whose homopolymer Tg is less than 60°C.
  • monomer C which has a homopolymer Tg of less than 60°C, as a constituent unit in addition to monomer A and monomer B, it is possible to form a film sufficiently even when drying at a low temperature, and it is possible to obtain The solvent resistance of recorded matter can be further improved.
  • monomer B having a homopolymer Tg of 60°C or higher is contained, and monomer C having a homopolymer Tg lower than 60°C is further included to improve the abrasion resistance of the resulting recorded material. It is possible to further improve solvent resistance.
  • 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.
  • the monomer C has a homopolymer Tg of 50°C or less, it is more preferable that the homopolymer Tg is 45°C or less, and the monomer C has a homopolymer Tg of 40°C or less.
  • the following monomer C is more preferable.
  • the monomer C has a homopolymer Tg of -15°C or higher, more preferably a monomer C that has a Tg of -5°C or higher, and still more preferably a monomer C that has a Tg of 0°C or higher.
  • the homopolymer has a Tg of -15°C or more and 50°C or less, more preferably -5°C or more and 45°C or less, and monomer C that has a Tg of 0°C or more and 40°C or less. It is even more preferable that there be.
  • the monomer C may contain a monomer having two or more ethylenically unsaturated bonds, it is preferable that the monomer C is composed of only a monomer 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 monomer C which is a constituent monomer, is not particularly limited, but the lower limit of the content of monomer C is preferably 3% by mass or more, and 7% by mass or more based on the total amount of the copolymer.
  • the content is more preferably 10% by mass or more, and even more preferably 10% by mass or more.
  • the upper limit of the content of monomer C is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less based on the total amount of the copolymer. This makes it possible to relatively increase the content of monomer A in the copolymer, thereby making it possible to further improve the solvent resistance of the resulting recorded material.
  • the content range of monomer C is preferably 3% by mass or more and 45% by mass or less based on the total amount of the copolymer, more preferably 7% by mass or more and 40% by mass or less, and 10% by mass or more and 35% by mass. It is more preferable that it is the following.
  • the copolymer contained in the aqueous ink composition according to the present embodiment may or may not contain other monomers different from monomer A, monomer B, and monomer C as a constituent unit.
  • examples of other monomers include acrylic monomers that do not fall under Monomer A, Monomer B, and Monomer C, and monomers that have reactive groups such as ethylenically unsaturated multiple bonds that are different from acrylic monomers. Examples include styrene, vinylcyclohexane, t-butyl 4-ethynylcyclohexane, and the like. These other monomers may be used alone or in combination.
  • 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 upper limit of the content of other monomers is preferably 10% by mass or less, and preferably 5% by mass or less based on the total amount of the copolymer. More preferably, it is 1% by mass or less.
  • 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 monomers include, for example, 2-(acryloylamino)-2-methyl-4-pentanone (side chain moiety SP value: 12 .04, LogP: 0.037 ⁇ 0.287), acrylaldehyde (side chain moiety SP value: 15.47, LogP: 0.263 ⁇ 0.283), N-ethenylformamide (side chain moiety SP value: 19.72, LogP: 0.525 ⁇ 0.215), methyl ethenyl ketone (side chain moiety SP value: 10.91, LogP: 0.142 ⁇ 0.249), ethyl ethenyl ketone (side chain moiety SP Value: 10.34, LogP: 0.652 ⁇ 0.249), 2-(acetoacetyloxy)ethyl acrylate (side chain moiety SP value: 11.73, LogP: 0.331 ⁇ 0.356), methacrylic 2-(acetoacetyloxy)e
  • 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 aqueous ink composition according to the present embodiment contains an acrylic resin having a Tg of 0°C or more and 120°C or less, and this acrylic resin contains at least two types of monomers such as monomer A, monomer B, and monomer C. Contains a copolymer containing as a constituent unit. Thereby, even when drying at a low temperature, the solvent resistance of the resulting recorded material can be increased.
  • this copolymer is contained in the aqueous ink composition as a polymer fine particle dispersion.
  • This copolymer can be obtained from monomers by conventionally known radical polymerization methods such as emulsion polymerization and suspension polymerization. Among these, this copolymer is preferably an emulsion polymer.
  • ком ⁇ онент When obtaining a copolymer by polymerizing monomers by emulsion polymerization, other components such as an emulsifier, a polymerization initiator, a polymerization modifier, a crosslinking agent, a neutralizing agent, and a film-forming aid may be used as appropriate. .
  • 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 emulsifier used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, based on 100 parts by mass of the monomer.
  • 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 1 part by mass or more, based on 100 parts by mass of the monomer. is even more preferable.
  • 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 as appropriate, but it is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and 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 mass or more and 5 parts by mass or less, more preferably 0.03 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass 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).
  • a copolymer that does not contain a crosslinking agent as a polymer fine particle dispersion in an aqueous ink composition, it is possible to improve the dispersion stability of the copolymer, and as a result, the storage stability can be further improved. It becomes possible to improve the performance.
  • 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, for example, to neutralize acidic groups or basic groups derived from monomer B.
  • the copolymer contains a monomer B having an acidic group or a basic group as a constitutional unit, by neutralizing the acidic group or basic group derived from the monomer B (i.e., the copolymer is By including monomer B having an acidic group or a basic group as a structural unit), an aqueous ink composition that exhibits the effects of the present invention more effectively can be obtained.
  • 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 acrylic resin contained in the aqueous ink composition according to the present embodiment includes a copolymer containing at least two types of monomers such as monomer A, monomer B, and monomer C obtained in this manner as constituent units.
  • the Tg of the acrylic resin can be controlled by appropriately changing the types and contents of at least two types of monomers, such as monomer A, monomer B, and monomer C.
  • the Tg of the acrylic resin containing this copolymer is 0°C or more and 120°C or less. If the Tg of the acrylic resin is less than 0° C., the abrasion resistance of the resulting recorded matter will decrease. If the Tg of the acrylic resin exceeds 120° C., sufficient film formation will not be possible, and the solvent resistance of the resulting recorded product will decrease.
  • the Tg of the acrylic resin containing this copolymer is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 40°C or higher.
  • the Tg of the acrylic resin containing this copolymer is preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 80°C or lower.
  • the Tg of the acrylic resin containing the copolymer is preferably 20°C or more and 100°C or less, more preferably 30°C or more and 90°C or less, and even more preferably 40°C or more and 80°C or less. .
  • the arrangement of monomers contained in a copolymer containing at least two types of monomers as constituent units is a block copolymer with long continuous monomers of the same type, even if it is a random copolymer with no order in the arrangement of monomers. Although it may be a graft copolymer in which monomers are arranged in a branched manner, a random copolymer is preferable.
  • a random copolymer is preferable.
  • 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.
  • the weight average molecular weight of the polymer fine particle dispersion is preferably 2,000,000 or less, more preferably 1,750,000 or less, and even more preferably 1,500,000 or less from the viewpoint of storage stability of the aqueous ink composition.
  • 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, and 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. , can be measured using a polystyrene standard for calibration curves as a standard.
  • Copolymers containing at least two types of monomers as constituent units may be obtained by conventionally known polymerization methods, but commercially available resins containing copolymers containing two types of monomers as constituent units may be obtained. You can also get it by doing so.
  • the aqueous ink composition according to the present embodiment may contain a resin different from the copolymer containing at least two types of monomers 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 at least two types of monomers 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.
  • the content 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 based on the total amount of the aqueous ink composition, more preferably 17.5% by mass or less, and even more preferably 15% by mass or less.
  • the content range of the resin is preferably 0.05% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 17.5% by mass or less, based on the total amount of the aqueous ink composition. It is more preferably 0.5% by mass or more and 15% by mass or less, 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.
  • the "water-soluble solvent” mainly means a water-soluble organic solvent, and may also be a dispersion medium that disperses at least a part of the contained components.
  • 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, cyclounsaturated 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-d
  • Examples include morpholines and terpene solvents. These can be used alone or in combination of two or more. Among these, it is preferable to select a water-soluble solvent so that the aqueous ink has a desired static surface tension, and preferably contains at least one water-soluble solvent such as an alkanediol, for example.
  • 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 10% by mass or more and 45% by mass or less, based on the total amount of the water-based ink. It is more preferably within the range of 40% by mass or more.
  • 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.
  • 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. More preferably, the content is 0.1% by mass or more and 15.0% by mass or less. When the content of the coloring material is within the range of 0.05% by mass or more or 20% 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-based, polyacrylic-based, polyurethane-based, polyamine-based, polycaptolactone-based main chains, and side chains containing 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 alkylene imine) 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 or anionic compound, by containing a cationic or anionic compound, the aqueous ink composition according to this embodiment can be used.
  • the aqueous ink composition can be made into a receiving solution (pretreatment solution).
  • 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 polymer fine particle dispersion.
  • 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 0.1% 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 15% 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 15% 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 0.1% by mass or more and 15% by mass or less, and 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, and even 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 adjusters, antioxidants, preservatives, antifungal agents, antibacterial agents, antiviral agents, ultraviolet absorbers, light stabilizers, 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.
  • 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.
  • At least one aqueous ink composition included in the ink set contains a copolymer containing at least two types of monomers as constituent units, and an acrylic resin having a Tg within a predetermined range.
  • Any aqueous ink composition containing the following may be used.
  • the water-based ink composition A contains a copolymer containing the above-mentioned at least two types of monomers as constituent units, and has a Tg in a predetermined range.
  • An aqueous ink composition containing an acrylic resin wherein the aqueous ink composition B contains a copolymer containing the above-mentioned at least two types of monomers as constituent units, and the aqueous ink composition contains an acrylic resin having a Tg within a predetermined range.
  • the aqueous ink composition may be different from the one described above. Further, both the water-based ink composition A and the water-based ink composition B contain a copolymer containing the above-mentioned at least two types of monomers as constituent units, and are water-based ink compositions containing an acrylic resin having a Tg within a predetermined range. There may be. The same applies to ink sets containing three or more types of aqueous ink compositions.
  • 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, blue ink, violet).
  • 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 the present embodiment includes applying the above water-based ink composition containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin having a Tg within a predetermined range onto a substrate. This is a recording method.
  • the water-based ink composition contains a copolymer containing at least two types of monomers as constituent units and contains an acrylic resin with a Tg within a predetermined range
  • the water-based ink composition can be coated on a substrate in a state with high storage stability. It is possible to apply objects.
  • the method for applying the above aqueous ink composition onto the surface of the substrate 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, and the like. Among these, the inkjet method is preferred. With the inkjet method, 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 110°C or lower, more preferably to dry the surface to a temperature of 90°C or lower, and dry the surface to a temperature of 70°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 to a temperature of 30°C or higher and 110°C or lower, more preferably 35°C or higher and 90°C or lower, and 40°C or lower. It is more preferable to dry at a temperature of 70° C. or lower.
  • the inkjet discharge method is a piezo method. , thermal method, electrostatic method, etc. may be used.
  • the above-mentioned recording method is a recording method in which the above-mentioned water-based ink composition containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin having a Tg within a predetermined range is applied onto a substrate by an inkjet method. It can also be defined as a method of manufacturing a product.
  • the above aqueous ink composition containing a copolymer containing at least two types of monomers as constituent units and an acrylic resin having a Tg within a predetermined range, or the aqueous ink composition included in the above ink set. is the recorded material coated on the base material.
  • 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 the above, 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.
  • the layer of the aqueous ink composition is a layer containing a copolymer containing at least two types of monomers as constituent units, and a solvent (such as water or a water-soluble This layer is formed by the volatilization of organic solvents.
  • a solvent such as water or a water-soluble
  • 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 at least two types of monomers as constituent units and containing an acrylic resin having a Tg within a predetermined range is used as a receiving solution containing a cationic compound
  • the above water-based ink composition (receiving solution) containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin with a Tg within a predetermined range is applied onto a base material, and at least two
  • the above water-based ink composition (colored ink) containing a copolymer containing various types of monomers as constituent units and an acrylic resin having a Tg within a predetermined range may be coated on the base material, or at least two types of the above water-based ink composition may be coated on the base material.
  • the above water-based ink composition (receiving solution) containing a copolymer containing a monomer as a constituent unit and containing an acrylic resin with a Tg within a predetermined range is coated thereon, and at least two types of monomers as a constituent unit are applied thereon.
  • An ink composition (colored ink) different from the above-mentioned aqueous ink composition (colored ink) containing a copolymer containing a copolymer and an acrylic resin having a Tg within a predetermined range may be applied.
  • the ink composition forming the recording layer of the recorded matter contains the above water-based ink containing a copolymer containing at least two types of monomers as constituent units, and containing an acrylic resin having a Tg within a predetermined range.
  • the ink composition may be an ink composition different from the above water-based ink composition, which contains a copolymer containing at least two types of monomers as constituent units, and contains an acrylic resin having a Tg within a predetermined range. It's okay.
  • the apparatus according to the present embodiment contains a copolymer containing at least two types of monomers as constituent units, and is included in the above water-based ink composition or the above ink set containing an acrylic resin having a Tg within a predetermined range.
  • This device is equipped with a container filled with an ink composition.
  • the apparatus according to the present embodiment is preferably an inkjet recording apparatus equipped with a container filled with the aqueous ink composition described above or the aqueous ink composition included in the ink set described above.
  • the storage container installed in the apparatus according to the present embodiment 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 is not particularly limited, and may be made of conventionally known resin, or may be made of a material containing some metal material (for example, an aluminum pouch with an aluminum vapor deposition layer). .
  • this apparatus preferably includes a drying mechanism that dries the aqueous ink composition after coating the aqueous 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 aqueous 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.
  • 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 dispersion of fine polymer particles was obtained by cooling to room temperature.
  • Example 2 A mixture consisting of 74.1 parts of cyclohexyl methacrylate, 18.5 parts of n-butyl 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; nonionic surfactant, solid content 100%)” 2.0 parts and "Sanisol B-50 (manufactured by Kao Corporation; cationic surfactant, solid content 50%)” 6.2 parts An emulsified monomer composition was prepared by adding the monomer to an aqueous solution and stirring the mixture.
  • Examples 3-5, 7-10, 13, 15-17, 19-23 The fine polymer 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 18 In Example 2, the polymer fine particle dispersion was obtained in the same manner as in Example 1, except that the monomer species and blending amounts were changed as shown in the table below.
  • Example 11 A mixture of 69.0 parts of cyclohexyl methacrylate, 29.6 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% ammonia aqueous solution, and the reaction was aged for 1 hour. Thereafter, the dispersion of fine polymer particles was obtained by cooling to room temperature.
  • Example 12 100.0 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 14 A mixture of 69.0 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 the polymer fine particle dispersion.
  • Example 2 the polymer fine particle dispersion was obtained in the same manner as in Example 1, except that the monomer species and blending amounts were changed as shown in the table below.
  • an antifoaming agent "Surfynol 104PG" manufactured by Air Products
  • aqueous ink compositions of Examples 24 and 26 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 24, 26 solid content concentration 30%), 25% by mass of 1,2-hexanediol, 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 compositions of Examples 25 and 27 25% by mass of polymer fine particle dispersion (Examples 25, 27 solid content concentration 30%), 25% by mass of 1,2-hexanediol, 0.5% by mass of polysiloxane compound, and water (deionized water) remaining.
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 28 and 29 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 28 and 29 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 1,2-hexanediol.
  • 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 30 and 32 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 30, 32 solid content concentration 30%), 25% by mass of NN-diethylformamide, 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 compositions of Examples 31 and 33 25% by mass of polymer fine particle dispersion (Examples 31, 33 solid content concentration 30%), 25% by mass of N-N-diethylformamide, 0.5% by mass of polysiloxane compound, and water (deionized water) remaining.
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 34 and 36 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 34, 36 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 35 and 37 25% by mass of polymer fine particle dispersion (Examples 35, 37 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of NN-diethylformamide, and 0.5% by mass of 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 38 and 40 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 38 and 40 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 the remaining amount of water (deionized water) and the remaining amount of water (deionized water) was produced.
  • Aqueous ink composition containing 25% by mass of polymer fine particle dispersion (Examples 39, 41 solid content concentration 30%), 25% by mass of 3-methoxy-1-butanol, and remaining amount of water (deionized water) (receiving solution) was produced.
  • aqueous ink compositions of Examples 42 and 44 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 42, 44 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 3-methoxy-1-butanol. %, 0.5% by mass of a polysiloxane compound, and a remaining amount of water (deionized water).
  • aqueous ink compositions of Examples 43 and 45 25% by mass of polymer fine particle dispersion (Examples 43, 45 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methoxy-1-butanol, water (deionized water ) remaining amount, and an aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 46 and 48 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 46, 48 solid content concentration 30%), 25% by mass of 2-pyrrolidone, 0.5% by mass of polysiloxane compound, and water ( An aqueous ink composition (colored ink) containing the remaining amount of deionized water was produced.
  • Aqueous ink composition (receiving solution) containing 25% by mass of polymer fine particle dispersion (Examples 47, 49 solid content concentration 30%), 25% by mass of 2-pyrrolidone, and remaining amount of water (deionized water). was manufactured.
  • aqueous ink compositions of Examples 50 and 52 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 50, 52 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-pyrrolidone, 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 compositions of Examples 51 and 53 25% by mass of polymer fine particle dispersion (Examples 51, 53 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-pyrrolidone, and the remaining amount of water (deionized water).
  • An aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 54 and 56 20% by mass of a pigment dispersion, 25% by mass of a polymer fine particle dispersion (Examples 54 and 56 solid content concentration 30%), 25% by mass of 3-methyl-1,3-butanediol, and 0.0% by mass of a polysiloxane compound.
  • An aqueous ink composition (colored ink) containing 5% by mass and a remaining amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 55 and 57 An aqueous solution containing 25% by mass of polymer fine particle dispersion (Examples 55, 57 solid content concentration 30%), 25% by mass of 3-methyl-1,3-butanediol, and the remaining amount of water (deionized water). An ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 58 and 60 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 58 and 60 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-methyl-1,3-butane.
  • An aqueous ink composition (colored ink) containing 9% by mass of diol, 0.5% by mass of polysiloxane compound, and the remaining amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 59 and 61 25% by mass of polymer fine particle dispersion (Examples 59, 61 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methyl-1,3-butanediol, water ( An aqueous ink composition (receiving solution) containing the remaining amount of deionized water was prepared.
  • aqueous ink compositions of Examples 62 and 64 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 62 and 64 solid content concentration 30%), 25% by mass of 3-methoxy-N,N-dimethylpropanamide, and 0% by mass of polysiloxane compound.
  • An aqueous ink composition (colored ink) containing .5% by mass and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 63 and 65 Contains 25% by mass of polymer fine particle dispersion (Examples 63, 65 solid content concentration 30%), 25% by mass of 3-methoxy-N,N-dimethylpropanamide, and remaining amount of water (deionized water). An aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 66 and 68 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 66 and 68 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-methoxy-N,N-dimethyl
  • An aqueous ink composition (colored ink) containing 9% by mass of propanamide, 0.5% by mass of a polysiloxane compound, and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 67 and 69 25% by mass of polymer fine particle dispersion (Examples 67, 69 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methoxy-N,N-dimethylpropanamide, and water. (Deionized water) An aqueous ink composition (receiving solution) containing the remaining amount was produced.
  • aqueous ink compositions of Examples 70 and 72 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 70 and 72 solid content concentration 30%), 25% by mass of 3-butoxy-N,N-dimethylpropanamide, and 0% by mass of polysiloxane compound.
  • An aqueous ink composition (colored ink) containing .5% by mass and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 71 and 73 Contains 25% by mass of polymer fine particle dispersion (Examples 71, 73 solid content concentration 30%), 25% by mass of 3-butoxy-N,N-dimethylpropanamide, and the remaining amount of water (deionized water). An aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 74 and 76 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 74 and 76 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-butoxy-N,N-dimethyl
  • An aqueous ink composition (colored ink) containing 9% by mass of propanamide, 0.5% by mass of a polysiloxane compound, and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 75 and 77 25% by mass of polymer fine particle dispersion (Examples 75, 77 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-butoxy-N,N-dimethylpropanamide, and water. (Deionized water) An aqueous ink composition (receiving solution) containing the remaining amount was produced.
  • aqueous ink compositions of Examples 78 and 80 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 78 and 80 solid content concentration 30%), 25% by mass of Texanol, 0.5% by mass of polysiloxane compound, and water (deionized).
  • An aqueous ink composition (colored ink) containing the remaining amount of water) was produced.
  • aqueous ink compositions of Examples 82 and 84 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 82, 84 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of Texanol, polysiloxane compound
  • An aqueous ink composition (colored ink) containing 0.5% by mass and a residual amount of water (deionized water) was produced.
  • aqueous ink compositions of Examples 83 and 85 25% by mass of polymer fine particle dispersion (Examples 83, 85 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of Texanol, and the remaining amount of water (deionized water).
  • An aqueous ink composition (receiving solution) was prepared.
  • aqueous ink compositions of Examples 86 and 88 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 86 and 88 solid content concentration 30%), 25% by mass of ⁇ -valerolactone, 0.5% by mass of polysiloxane compound, and water. (deionized water) An aqueous ink composition (colored ink) containing the remaining amount.
  • aqueous ink compositions of Examples 87 and 89 An aqueous ink composition (receiving solution) containing 25% by mass of a polymer fine particle dispersion (Examples 87, 89 solid content concentration 30%), 25% by mass of ⁇ -valerolactone, and the remaining amount of water (deionized water). ) was manufactured.
  • aqueous ink compositions of Examples 90 and 92 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 90, 92 solid content concentration 30%), 20% by mass of 1,2-propanediol, 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 compositions of Examples 91 and 93 25% by mass of polymer fine particle dispersion (Examples 91, 93 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of ⁇ -valerolactone, and remaining amount of water (deionized water)
  • An aqueous ink composition (receiving solution) containing the following was produced.
  • aqueous ink compositions of Examples 94 and 96 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 94, 96 solid content concentration 30%), 25% by mass of N-methyl-epsilon-caprolactam, and 0.5% by mass of polysiloxane compound.
  • Aqueous ink composition containing 25% by mass of polymer fine particle dispersion (Examples 95, 97 solid content concentration 30%), 25% by mass of N-methyl-epsilon-caprolactam, and remaining amount of water (deionized water). (receiving solution) was produced.
  • aqueous ink compositions of Examples 98 and 100 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 98 and 100 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of N-methyl-epsilon-caprolactam. %, a polysiloxane compound of 0.5% by mass, and a residual amount of water (deionized water).
  • aqueous ink compositions of Examples 99 and 101 25% by mass of polymer fine particle dispersion (Examples 99, 101 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of N-methyl-epsilon-caprolactam, water (deionized water ) remaining amount, and an aqueous ink composition (receiving solution) was produced.
  • aqueous ink compositions of Examples 102 and 104 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 102, 104 solid content concentration 30%), 25% by mass of 2-hydroxylethylmorpholine, 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 ( A receiving solution) was prepared.
  • aqueous ink compositions of Examples 106 and 108 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 106 and 108 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 2-hydroxylethylmorpholine.
  • 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 107 and 109 25% by mass of polymer fine particle dispersion (Examples 107, 109 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-hydroxylethylmorpholine, and water (deionized water)
  • An aqueous ink composition (receiving solution) containing the remaining amount was produced.
  • aqueous ink compositions of Examples 110 and 112 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 110, 112 solid content concentration 30%), 25% by mass of 2-hydroxylethylpyrrolidone, and 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 compositions of Examples 111 and 113 An aqueous ink composition (accepted) containing 25% by mass of polymer fine particle dispersion (Examples 111, 113 solid content concentration 30%), 25% by mass of 2-hydroxylethylpyrrolidone, and the remaining amount of water (deionized water). solution) was produced.
  • aqueous ink compositions of Examples 114 and 116 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 114, 116 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 2-hydroxylethylpyrrolidone.
  • 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 115 and 117 25% by mass of polymer fine particle dispersion (Examples 115, 117 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-hydroxylethylpyrrolidone, and the remainder of water (deionized water).
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 118 and 120 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 118 and 120 solid content concentration 30%), 25% by mass of tripropylene glycol monomethyl ether, and 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 compositions of Examples 119 and 121 An aqueous ink composition (accepted) containing 25% by mass of polymer fine particle dispersion (Examples 119, 121 solid content concentration 30%), 25% by mass of tripropylene glycol monomethyl ether, and the remaining amount of water (deionized water). solution) was produced.
  • aqueous ink compositions of Examples 122 and 12 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 122, 124 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of tripropylene glycol monomethyl ether. , 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 123 and 125 25% by mass of polymer fine particle dispersion (Examples 123, 125 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of tripropylene glycol monomethyl ether, and the remainder of water (deionized water).
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 126 and 128 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 126 and 128 solid content concentration 30%), 25% by mass of dipropylene glycol monomethyl ether, and 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 compositions of Examples 127 and 129 An aqueous ink composition (accepted) containing 25% by mass of polymer fine particle dispersion (Examples 127, 129 solid content concentration 30%), 25% by mass of dipropylene glycol monomethyl ether, and the remaining amount of water (deionized water). solution) was produced.
  • aqueous ink compositions of Examples 130 and 132 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 130, 132 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of dipropylene glycol monomethyl ether.
  • 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 131 and 133 25% by mass of polymer fine particle dispersion (Examples 131, 133 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of dipropylene glycol monomethyl ether, and the remainder of water (deionized water).
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 134 and 136 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 134, 136 solid content concentration 30%), 25% by mass of triethylene glycol monomethyl ether, 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 compositions of Examples 135 and 137 An aqueous ink composition (accepted) containing 25% by mass of a polymer fine particle dispersion (Examples 135, 137 solid content concentration 30%), 25% by mass of triethylene glycol monomethyl ether, and the remaining amount of water (deionized water). solution) was produced.
  • aqueous ink compositions of Examples 138 and 140 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 138 and 140 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of triethylene glycol monomethyl ether. , 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 139 and 141 25% by mass of polymer fine particle dispersion (Examples 139, 141 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of triethylene glycol monomethyl ether, and water (deionized water) remaining.
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 142 and 144 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 142, 144 solid content concentration 30%), 25% by mass of triethylene glycol monobutyl ether, 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 compositions of Examples 143 and 145 An aqueous ink composition (accepted) containing 25% by mass of a polymer fine particle dispersion (Examples 143, 145 solid content concentration 30%), 25% by mass of triethylene glycol monobutyl ether, and the remaining amount of water (deionized water). solution) was produced.
  • aqueous ink compositions of Examples 146 and 1408 20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 146, 148 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of triethylene glycol monobutyl ether.
  • 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 147 and 149 25% by mass of polymer fine particle dispersion (Examples 147, 149 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of triethylene glycol monobutyl ether, and the remainder of water (deionized water).
  • An aqueous ink composition (receiving solution) was prepared comprising:
  • aqueous ink compositions of Examples 150 to 154 Preparation of aqueous ink compositions of Examples 150 to 154.
  • the content of the polymer fine particle dispersion was changed to 13% by mass, and water (deionized water) was added so that the total content was 100% by mass.
  • Aqueous ink compositions were manufactured by changing the content ratio.
  • the appearance of the coating film was examined using a Type II tester under the conditions of a weight of 1 kg (adhesive polyvinyl chloride film) and a weight of 200 g (corona-treated OPP), and a No. 3 cloth immersed in an ethanol aqueous solution with a mass concentration of 50%.
  • the appearance of the coating film was evaluated using the following evaluation criteria (coating film appearance index) (indicated as solvent resistance in the table).
  • Storage stability The storage stability of the aqueous ink compositions of Examples and Comparative Examples was evaluated. Specifically, the 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 ink compositions of Examples and Comparative Examples were evaluated for intermittent ejection performance (ejection stability). Specifically, an ink composition is filled into an ink cartridge (accommodation container), the ink cartridge (accommodation container) is mounted on a serial type inkjet recording device equipped with a piezo type inkjet head, and the inkjet recording device is used to print the inkjet recording device. , a nozzle check pattern was printed, the head was left standing for 10 minutes without a head cap, and then similar printing was performed.
  • 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)
  • MAA methacrylic acid.
  • DMMA 2-(dimethylamino)ethyl methacrylate.
  • CHMA cyclohexyl methacrylate.
  • PhMA phenyl methacrylate.
  • MMA is methyl methacrylate.
  • IBXMA is isobornyl methacrylate.
  • NMA is naphthalenyl methacrylate.
  • BMA is butyl methacrylate.
  • CHMA 2-(dimethylamino)ethyl methacrylate.
  • CHMA cyclohexyl methacrylate.
  • PhMA phenyl methacrylate.
  • MMA methyl methacrylate.
  • IBXMA is isobornyl methacrylate.
  • NMA is naphthalenyl methacrylate.
  • BMA is butyl methacrylate.
  • CHMA is cyclohexyl acrylate.
  • MA means methyl acrylate.
  • corona-treated OPP is a polypropylene resin base material (polyolefin resin base material) whose surface has been subjected to corona treatment.
  • any aqueous ink composition containing an acrylic resin with a glass transition temperature (Tg) of 0°C or more and 120°C or less and a copolymer containing at least two types of monomers as constituent units For example, it can be seen that even when dried at 60°C, 80°C, or 100°C, the obtained recorded matter has high solvent resistance.
  • Tg glass transition temperature
  • the aqueous ink compositions of Examples 1 to 14 containing acrylic monomer A having a water/1-octanol partition coefficient (LogP) of 1.0 or more are the aqueous ink compositions of Examples 15, 16, and 17. Even compared to the composition, a coating film with high solvent resistance could be formed.
  • Examples 1 to 14 containing acrylic monomer A with a water/1-octanol partition coefficient (LogP) of 4 or less have high solvent properties compared to the aqueous ink composition of Example 20. A coating film was formed.
  • the ink composition provides a recorded matter with low solvent resistance, and does not exhibit the effects of the present invention.
  • the aqueous ink composition of Comparative Example 1 containing a homopolymer of acrylic monomer had low solvent resistance at 60° C., and did not exhibit the effects of the present invention.
  • Comparative Example 4 that does not contain monomer B and Comparative Example 5 that does not contain monomer A have a decreased storage stability or a decreased solvent resistance of the obtained recorded material, and the effects of the present invention are not achieved. It has not become a thing.

Abstract

Provided is an aqueous ink composition which yields a recorded matter having high solvent resistance even if the aqueous ink composition is dried at a low temperature.　This aqueous ink composition contains water and a resin. At least a part of the resin is contained as a dispersion of polymer fine particles. The resin contains an acrylic resin. The acrylic resin contains a copolymer that contains at least two types of monomer as constituent units. The acrylic resin has a Tg value of 0-120ºC.

Description

水性インク組成物、記録方法、記録物の製造方法、記録物及びインクジェット記録装置Water-based ink composition, recording method, method for producing recorded matter, recorded matter and inkjet recording device
　本発明は、水性インク組成物、記録方法、記録物の製造方法、記録物及びインクジェット記録装置に関する。 The present invention relates to an aqueous ink composition, a recording method, a method for producing a recorded material, a recorded material, and an inkjet recording apparatus.
　インク組成物として、各種の色材を水、又は水と水溶性有機溶剤との混合液に溶解させた水性インクが広く用いられている。このような水を主成分とする水性インク組成物は、環境に対する影響が少なく、引火することがないため作業者に対して安全性が高い。 As 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. Such 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.
　このような水を主成分とする水性インク組成物にバインダー樹脂として、樹脂エマルジョンを使用することも従来行われている。樹脂エマルジョンとは、樹脂が静電反発力によって樹脂微粒子としてインク組成物中に分散している状態を示すものである。樹脂が溶解した状態の溶解樹脂や、一部溶解樹脂を含有するコロイダルディスパージョンとは異なる。バインダー樹脂として樹脂エマルジョンを含有することにより、分散安定性、吐出安定性等を好ましいものとすることができる。 It has also been conventional practice to use a resin emulsion as a binder resin in such aqueous ink compositions containing water as a main component. The resin emulsion refers to a state in which resin is dispersed in the ink composition as fine resin particles due to electrostatic repulsion. This is different from a molten resin in which the resin is dissolved or a colloidal dispersion that partially contains a dissolved resin. By containing a resin emulsion as the binder resin, dispersion stability, ejection stability, etc. can be made preferable.
　例えば、特許文献１には、スルホン酸基を有するラジカル重合性乳化剤を含有する乳化剤の存在下で、シリル基を有する不飽和単量体と、側鎖に６員環を有する不飽和単量体と、を、乳化重合させてなる、合成樹脂エマルジョンを含有する組成物に関する技術が記載されている。特許文献１には、この組成物は、インク受容層への速やかなインク透過性を維持しつつ、光沢を更に向上させ、特に発色性に優れたかつ塗液の凝集しない安定な皮膜を形成することができることが記載されている。 For example, in 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 related to a composition containing a synthetic resin emulsion 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.
特許第３７３０５６８号Patent No. 3730568
　水性インク組成物は、水との親和性の高い水溶性有機溶剤を選択することが一般的である。このような水との親和性の高い水溶性有機溶剤は、比較的高沸点であることから、水性インク組成物を乾燥させるのにはより多くの熱量が必要となる。一方、生産性の観点からはできるだけ低温で好適に乾燥する水性インク組成物であることが好ましい。 For water-based ink compositions, it is common to select a water-soluble organic solvent that has high affinity with water. Since such water-soluble organic solvents with high affinity for water have a relatively high boiling point, a larger amount of heat is required to dry the aqueous ink composition. On the other hand, from the viewpoint of productivity, it is preferable to use an aqueous ink composition that dries suitably at as low a temperature as possible.
　一方で、樹脂を含む水性インク組成物は、製膜時に所定の温度（最低造膜温度）以上の温度を加えることでインク組成物に含まれる樹脂が融着して耐溶剤性の有する塗膜を形成することが可能となる。特に、この樹脂が粒子状の高分子微粒子分散体である場合には、樹脂粒子同士の融着の度合いにより塗膜の状態は大きく変化する。 On the other hand, in water-based ink compositions containing resin, when a temperature higher than a predetermined temperature (minimum film-forming temperature) is applied during film formation, the resin contained in the ink composition fuses and forms a coating film with solvent resistance. It becomes possible to form. In particular, when the resin is a particulate polymer fine particle dispersion, the state of the coating film changes greatly depending on the degree of fusion between the resin particles.
　そして、最低造膜温度未満の温度で製膜した場合には、塗膜の製膜が不十分となり、得られる記録物の耐溶剤性に影響を及ぼすことが本発明者らの研究により明らかとなった。
このように本発明者らの見解によれば、高分子微粒子分散体を含有する水性インク組成物においては、低温乾燥性と耐溶剤性はトレードオフの関係にある。 The research of the present inventors has revealed that if the film is formed at a temperature lower than the minimum film forming temperature, the film formation will be insufficient, which will affect the solvent resistance of the resulting recorded material. became.
As described above, according to the inventors' opinion, in an aqueous ink composition containing a polymer fine particle dispersion, there is a trade-off relationship between low-temperature drying property and solvent resistance.
　本発明は、水性インク組成物を低温で乾燥させた場合であっても、得られる記録物の耐溶剤性の高い水性インク組成物を提供することを目的とする。 An object of the present invention is to provide an aqueous ink composition that provides recorded matter with high solvent resistance even when the aqueous ink composition is dried at low temperatures.
　本発明者らは、上記課題を解決するために鋭意検討をした結果、所定範囲のガラス転移温度（Ｔｇ）のアクリル系樹脂を含有し、少なくとも２種類のモノマーを構成単位として含む共重合体を含有する水性インク組成物であれば、上記課題を解決できることを見出し、本発明を完成するに至った。具体的には、本発明では、以下のようなものを提供する。 As a result of intensive studies to solve the above problems, the present inventors have developed a copolymer containing an acrylic resin having a glass transition temperature (Tg) within a predetermined range and containing at least two types of monomers as constituent units. The inventors have discovered that the above-mentioned problems can be solved by using an aqueous ink composition containing the above-mentioned aqueous ink compositions, and have completed the present invention. Specifically, the present invention provides the following.
　（１）水と、樹脂と、を含有する水性インク組成物であって、
　前記樹脂の少なくとも一部は、高分子微粒子分散体として含有し、
　前記樹脂は、アクリル系樹脂を含有し、
　前記アクリル系樹脂は、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、
　前記アクリル系樹脂のＴｇは、０℃以上１２０℃以下である
　水性インク組成物。 (1) An aqueous ink composition containing water and a resin,
At least a portion of the resin is contained as a polymer fine particle dispersion,
The resin contains an acrylic resin,
The acrylic resin contains a copolymer containing at least two types of monomers as constituent units,
The acrylic resin has a Tg of 0°C or more and 120°C or less.A water-based ink composition.
　（２）前記アクリル系樹脂は、以下のモノマーＡ、モノマーＢを構成単位として含む共重合体を含有する
　（１）に記載の水性インク組成物。
　モノマーＡ：水／１－オクタノールでの分配係数（ＬｏｇＰ）が１．０以上のアクリルモノマー
　モノマーＢ：モノマーＡ以外であって、酸性基または塩基性基を有するモノマー (2) The aqueous ink composition according to (1), wherein the acrylic resin contains a copolymer containing the following monomers A and B as constituent units.
Monomer A: an acrylic monomer with a water/1-octanol partition coefficient (LogP) of 1.0 or more Monomer B: a monomer other than monomer A that has an acidic group or a basic group
　（３）前記モノマーＡのホモポリマーのＴｇが６０℃以上である
　（２）に記載の水性インク組成物。 (3) The aqueous ink composition according to (2), wherein the homopolymer of monomer A has a Tg of 60° C. or higher.
　（４）前記アクリル系樹脂は、さらに以下のモノマーＣを構成単位として含む共重合体を含有する
　（３）に記載の水性インク組成物。
　モノマーＣ：モノマーＡ、モノマーＢ以外であって、ホモポリマーのＴｇが６０℃未満のモノマー (4) The aqueous ink composition according to (3), wherein the acrylic resin further contains a copolymer containing the following monomer C as a constituent unit.
Monomer C: A monomer other than Monomer A and Monomer B whose homopolymer Tg is less than 60°C
　（５）前記モノマーＡの水／１－オクタノールでの分配係数（ＬｏｇＰ）が１．９以上４．８以下である
　（２）から（４）のいずれかに記載の水性インク組成物。 (5) The aqueous ink composition according to any one of (2) to (4), wherein the monomer A has a water/1-octanol partition coefficient (LogP) of 1.9 or more and 4.8 or less.
　（６）前記アクリル系樹脂のＴｇは、４０℃以上８０℃以下である
　（１）から（５）のいずれかに記載の水性インク組成物。 (6) The aqueous ink composition according to any one of (1) to (5), wherein the acrylic resin has a Tg of 40°C or more and 80°C or less.
　（７）（１）から（６）のいずれかに記載の水性インク組成物を含む
　インクセット。 (7) An ink set comprising the aqueous ink composition according to any one of (1) to (6).
　（８）（１）から（６）のいずれかに記載の水性インク組成物をインクジェット吐出する
　記録方法。 (8) A recording method in which the aqueous ink composition according to any one of (1) to (6) is inkjet-discharged.
　（９）（１）から（６）のいずれかに記載の水性インク組成物をインクジェット吐出して記録物を得る
　記録物の製造方法。 (9) 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 (6).
　（１０）基材の表面に（１）から（６）のいずれかに記載の水性インク組成物が塗布された記録物。 (10) A recorded matter in which the aqueous ink composition according to any one of (1) to (6) is coated on the surface of a base material.
　（１１）（１）から（６）のいずれかに記載の水性インク組成物を搭載したインク貯蔵機構を備えた
　インクジェット記録装置。 (11) An inkjet recording device comprising an ink storage mechanism loaded with the aqueous ink composition according to any one of (1) to (6).
　本発明の水性インク組成物は、低温で乾燥させた場合であっても、得られる記録物の耐溶剤性が高い。 Even when the aqueous ink composition of the present invention is dried at low temperatures, the obtained recorded matter has high solvent resistance.
　以下、本発明の具体的な実施形態について、詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the purpose of the present invention. can do.
　≪１．水性インク組成物≫
　本実施の形態に係る水性インク組成物は、水と、水溶性有機溶剤と、樹脂と、を含有する。そして、この記樹脂の少なくとも一部は、高分子微粒子分散体として含有し、樹脂は、Ｔｇは、０℃以上１２０℃以下であるアクリル系樹脂を含有し、このアクリル系樹脂は、少なくとも２種類のモノマーを構成単位として含む共重合体を含有する。 ≪1. Water-based ink composition≫
The aqueous ink composition according to this embodiment contains water, a water-soluble organic solvent, and a resin. At least a part of this resin is contained as a polymer fine particle dispersion, and the resin contains an acrylic resin having a Tg of 0°C or more and 120°C or less, and this acrylic resin contains at least two types. Contains a copolymer containing monomers as structural units.
　最低造膜温度は、水性インク組成物に含まれる高分子微粒子分散体のガラス転移温度（Ｔｇ）付近となることが本発明者らの研究により明らかとなった。 Research by the present inventors has revealed that the minimum film forming temperature is near the glass transition temperature (Tg) of the polymer fine particle dispersion contained in the aqueous ink composition.
　このような所定範囲のガラス転移温度（Ｔｇ）のアクリル系樹脂を含有し、少なくとも２種類のモノマーを構成単位として含む共重合体を含有する水性インク組成物であれば、低温で乾燥させた場合であっても、その塗布表面に耐溶剤性の高い水性インク組成物の層を形成することができる。 If the aqueous ink composition contains such an acrylic resin having a glass transition temperature (Tg) within a predetermined range and contains a copolymer containing at least two types of monomers as constituent units, when dried at a low temperature, However, a layer of the water-based ink composition with high solvent resistance can be formed on the coated surface.
　例えば、水性インク組成物に造膜助剤を含有させて最低造膜温度を下げるような方法もあるが、造膜助剤は一般的に高沸点の有機溶剤が多く、乾燥の際に多くの熱量が必要となってしまい、低温乾燥性を実現できなくなることがある。 For example, there is a method of lowering the minimum film forming temperature by incorporating a coalescent into the aqueous ink composition, but coalescents generally contain high boiling point organic solvents, and during drying, a large amount of The amount of heat required may make it impossible to achieve low-temperature drying properties.
　なお、本実施の形態に係る水性インク組成物は、色材を含有する着色インクであってもよい。本明細書において「色材」とは、染料及び顔料を含むものであり、例えば、イエロー、マゼンタ、シアン、ブラック、及びこれらの中間色や淡色のような画像を形成する着色インクに含まれる染料又は顔料や、ホワイトインクに含まれる白色染料又は白色顔料や、メタリックインクに含まれる光輝性顔料をも含む概念として使用する。 Note that the aqueous ink composition according to this embodiment may be a colored ink containing a coloring material. In this specification, the term "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.
　この着色インクは、イエロー、マゼンタ、シアン、ブラック、及びこれらの中間色や淡色のような画像を形成する着色インクであってもよい。また、着色インクは、白色色材を含むホワイトインクであってもよく、光輝性顔料を含むメタリックインク等であってもよい。 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.
　また、本実施の形態に係る水性インク組成物は、基材に着色インクを塗布するのに先立ち、基材に塗布される受理溶液であってもよい。さらに、色材を含有しないクリアインクであってもよいし、基材等の表面にプライマー層を形成するためのプライマー剤であってもよいし、記録物等の表面にオーバーコート層を形成するためのオーバーコートインクであってもよく、塗料やコーティング剤と称されるものであってもよい。 Furthermore, the aqueous ink composition according to the present embodiment may be a receiving solution that is applied to the substrate prior to applying the colored ink 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 base material, etc., or an overcoat layer for forming an overcoat layer on the surface of a recorded material, etc. It may be an overcoat ink for other purposes, or it may be something called a paint or a coating agent.
　以下、本実施の形態に係るインク組成物に含まれる各成分について説明する。 Hereinafter, each component contained in the ink composition according to this embodiment will be explained.
　［樹脂］
　本実施の形態に係る水性インク組成物は、樹脂を含有する。この樹脂は、少なくとも一部が高分子微粒子分散体として含有する。本明細書において高分子微粒子分散体とは、樹脂が静電反発力によって樹脂微粒子としてインク組成物中に分散している樹脂エマルジョンや一部溶解樹脂を含有するコロイダルディスパージョンの状態となった樹脂を意味し、例えば、水性インク組成物中に溶解したような溶解性樹脂とは異なる。 [resin]
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. In this specification, 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.
　そして、この樹脂はＴｇが０℃以上１２０℃以下であるアクリル系樹脂を含有し、アクリル系樹脂は、少なくとも２種類のモノマーを構成単位として含む共重合体を含有する。 This resin contains an acrylic resin having a Tg of 0° C. or more and 120° C. or less, and the acrylic resin contains a copolymer containing at least two types of monomers as constituent units.
　本実施の形態に係る水性インク組成物において、共重合体を構成するモノマーは例えば以下のモノマーＡ、モノマーＢを構成単位として含む共重合体であることが好ましい。 In the aqueous ink composition according to the present embodiment, the monomer constituting the copolymer is preferably a copolymer containing, for example, the following monomer A and monomer B as constituent units.
　モノマーＡ：水／１－オクタノールでの分配係数（ＬｏｇＰ）が１．０以上のモノマー
　モノマーＢ：モノマーＡ以外であって、酸性基または塩基性基を有するモノマー Monomer A: A monomer having a partition coefficient (LogP) in water/1-octanol of 1.0 or more Monomer B: A monomer other than monomer A that has an acidic group or a basic group
　このようなモノマーＡ及びモノマーＢを構成単位として含む共重合体を含有することにより、水性インク組成物は、得られる記録物の耐溶剤性をさらに高くすることができるとともに、水性インク組成物の保存安定性をも高くすることが可能となる。 By containing such a copolymer containing monomer A and monomer B as structural units, the aqueous ink composition can further increase the solvent resistance of the obtained recorded material, and also improve the solvent resistance of the aqueous ink composition. It is also possible to increase storage stability.
　さらに、モノマーＡ、モノマーＢを構成単位として含む共重合体において、以下のモノマーＣを構成単位としてさらに含む共重合体であることがより好ましい。 Furthermore, in a copolymer containing monomer A and monomer B as constituent units, it is more preferable that the copolymer further contains the following monomer C as a constituent unit.
　モノマーＣ：モノマーＡ、モノマーＢ以外であって、ホモポリマーのＴｇが６０℃未満のモノマー Monomer C: A monomer other than monomer A and monomer B whose homopolymer Tg is less than 60°C
　このように、モノマーＡ、モノマーＢに加えてホモポリマーのＴｇが６０℃未満のモノマーＣを構成単位として含むことで、低温で乾燥させた場合であっても、十分に成膜することが可能となり、得られる記録物の耐溶剤性をさらに向上させることができる。 In this way, by including monomer C, which has a homopolymer Tg of less than 60°C, as a constituent unit in addition to monomer A and monomer B, it is possible to form a film satisfactorily even when drying at low temperatures. Therefore, the solvent resistance of the resulting recorded material can be further improved.
　なお、アクリル系樹脂とは、構成モノマーの少なくとも１つ以上にアクリル骨格を有する樹脂を意味し、例えば、アクリル骨格を有しないモノマーを含むものであってもよい。 Note that the acrylic resin refers to a resin that has an acrylic skeleton in at least one of its constituent monomers, and may also include, for example, a monomer that does not have an acrylic skeleton.
　また、本明細書では、構成モノマーとは、便宜上、重合体を構成する反応前の単量体であって、エチレン性不飽和多重結合等の反応基を有する重合性化合物を意味するものとして説明するが、実際には、モノマーを構成単位として含むときには、反応前の単量体の状態で含まれるものではなく、多重結合のうちの一つの結合は重合して失われて、共重合体を構成する重合後の単量体として含まれることとなる。 In addition, in this specification, for convenience, 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. However, in reality, 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.
　また、モノマーは、エチレン性不飽和多重結合等の反応基を有する単量体の重合性化合物であればよく、本明細書ではオリゴマーと称されるような分子量の大きな単量体であってもモノマーと称する。 In addition, 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.
　以下、この共重合体を構成してもよいモノマーＡ、モノマーＢ、モノマーＣ、及びその他のモノマーについて説明する。 Hereinafter, monomer A, monomer B, monomer C, and other monomers that may constitute this copolymer will be explained.
　（モノマーＡ）
　モノマーＡとは、水／１－オクタノールでの分配係数（ＬｏｇＰ）が１．０以上のアクリルモノマーである。 (Monomer A)
Monomer A is an acrylic monomer having a water/1-octanol partition coefficient (LogP) of 1.0 or more.
　「水／１－オクタノールでの分配係数（ＬｏｇＰ）」は、疎水性の指標であり、「水／１－オクタノールでの分配係数（ＬｏｇＰ）」が所定以上（すなわち、疎水性が相対的に高いモノマー）のモノマーＡを構成単位として含むことにより、エタノール等の溶剤に対して膨潤しづらい共重合体となる。このため、モノマーＡを構成単位として含む共重合体であれば、得られる記録物の耐溶剤性をさらに向上させることが可能となる。 "Water/1-octanol partition coefficient (LogP)" is an index of hydrophobicity, and "water/1-octanol partition coefficient (LogP)" is greater than or equal to a certain value (that is, the hydrophobicity is relatively high). By including monomer A (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.
　このようなモノマーＡの中でも、このモノマーＡの水／１－オクタノールでの分配係数（ＬｏｇＰ）は、１．２以上であることが好ましく、１．７以上であることがより好ましく、１．９以上であることがさらに好ましい。このモノマーＡの水／１－オクタノールでの分配係数（ＬｏｇＰ）は、５．０以下であることが好ましく、４．８以下であることがさらに好ましい。モノマーＡの水／１－オクタノールでの分配係数（ＬｏｇＰ）は、１．２以上５．０以下であることが好ましく、１．７以上４．８以下であることがより好ましく、１．９以上４．８以下であることがさらに好ましい。 Among such monomers A, the water/1-octanol partition coefficient (LogP) of this monomer A is preferably 1.2 or more, more preferably 1.7 or more, and 1.9. It is more preferable that it is above. The water/1-octanol partition coefficient (LogP) of this monomer A is preferably 5.0 or less, more preferably 4.8 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 or more. More preferably, it is 4.8 or less.
　また、このモノマーＡは、ホモポリマーのＴｇが６０℃以上であることが好ましい。モノマーＡのホモポリマーのＴｇが６０℃以上であることで、得られる記録物の耐擦性を向上させることが可能となる。 Furthermore, it is preferable that this monomer A has a homopolymer Tg of 60° C. or higher. When the homopolymer of monomer A has a Tg of 60° C. or higher, it is possible to improve the abrasion resistance of the resulting recorded material.
　また、このモノマーＡの中でも、下記式（１）のＲ２で定義される化学構造部分について計算されるＳＰ値である側鎖部分ＳＰ値が８．５以上１３．０以下であることが好ましい。 Moreover, among this monomer A, it is preferable that the SP value of the side chain portion, which is the SP value calculated for the chemical structure moiety defined by R 2 in the following formula (1), is 8.5 or more and 13.0 or less. .
　ＣＨ２＝Ｃ（Ｒ１）－Ｒ２　　　　・・・式（１）
（Ｒ１は水素又はメチル基である） CH 2 =C(R 1 )-R 2 ...Formula (1)
(R 1 is hydrogen or methyl group)
　ここで、側鎖部分ＳＰ値とは、式（１）の「－Ｒ２」部分のＳＰ値（ｓｏｌｕｂｉｌｉｔｙ　ｐａｒａｍｅｔｅｒ）を意味し、ＳＰ値と同様に「－Ｒ２」を構成する官能基を分解し、そのΔＥｏｈ（ｃａｌ／ｍｏｌ）の合計値をＡと定義し、そのΔＶ（ｃｍ３／ｍｏｌ）の合計値をＢと定義したときの√（Ａ／Ｂ）値を意味する。なお、ΔＥｏｈとΔＶは各置換基固有の数値であり、Ｆｅｄｏｒｓの数値を参考とした。例えば、ブチル（メタ）アクリレートである場合には、「－Ｒ２」は、「－ＣＯＯ－（ＣＨ２）３－ＣＨ３」となるので、以下の表１のΔＥｏｈとΔＶを使用して計算すると、側鎖部分ＳＰ値＝√（（１１２５＋１１８０×３＋４３００）／（３３．５＋１６．１×３＋１８．０））＝９．４８となる。 Here, 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 ΔEoh (cal/mol) is defined as A and the total value of ΔV (cm 3 /mol) is defined as B. Note that ΔEoh and ΔV are numerical values specific to each substituent, and the Fedors' numerical values were used as reference. For example, in the case of butyl (meth)acrylate, "-R 2 " becomes "-COO-(CH 2 ) 3 -CH 3 ", so calculate using ΔEoh and ΔV in Table 1 below. Then, the side chain portion SP value=√((1125+1180×3+4300)/(33.5+16.1×3+18.0))=9.48.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　共重合体を構成するモノマーＡの側鎖部分ＳＰ値を所定範囲とすることにより、得られる記録物の耐溶剤性を高くすること（その中でも耐エタノール性を高くすること）ができる。 By setting the SP value of the side chain portion of monomer A constituting the copolymer within a predetermined range, it is possible to increase the solvent resistance of the resulting recorded material (among others, to increase the ethanol resistance).
　高分子を含む塗膜の物性はしばしば塗膜に含まれる高分子の主鎖よりもむしろ高分子の側鎖部分によって大きく影響を受けることが本発明者らの研究により明らかとなった。式（１）の「－Ｒ２」部分のＳＰ値である側鎖部分ＳＰ値を所定範囲に制御されたモノマーを構成単位として含むことで、塗膜の物性に影響を与えることが可能となり、本発明の効果を奏する塗膜を形成することが可能となると考えられる。 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. By including as a constituent unit 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.
　そして、一般にＳＰ値は溶解度パラメータと呼ばれ、２つの成分のＳＰ値の差が小さいほど溶解度が高くなることが知られている。エタノールのＳＰ値は１２．７であるため、より遠ければ遠いほど塗膜としてはエタノールに対して耐溶剤性が高くなる。一方で、高分子微粒子分散体での塗膜形成では、水溶性溶媒によって微粒子同士が融着し樹脂鎖が拡散することで強固な塗膜となる。よって、水溶性溶媒に対する溶解性もある程度必要となる。そこでＳＰ値として以上の範囲とすることで、水溶性溶媒に対してある程度拡散し強固な塗膜となる一方でエタノール等の溶剤に関して膨潤しにくい塗膜となり、耐溶剤性を向上させることが可能となる。 In general, 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 it will also be difficult to swell with solvents such as ethanol, making it possible to improve solvent resistance. becomes.
　なお、側鎖部分ＳＰ値は、８．５以上であることが好ましく、８．８以上であることがより好ましく、９．０以上であることがさらに好ましい。側鎖部分ＳＰ値は、１３．０以下であることが好ましく、１２．０以下であることがより好ましく、１１．０以下であることがさらに好ましい。側鎖部分ＳＰ値は、８．５以上１３．０以下であることが好ましく、８．８以上１２．０以下であることがより好ましく、９．０以上１１．０以下であることがさらに好ましい。これにより、得られる記録物の耐溶剤性を高くすること（その中でも耐エタノール性を高くすること）ができる。 Note 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).
　モノマーＡとしては、シクロヘキシルメタクリレート（側鎖部分ＳＰ値：９．９６、ＬｏｇＰ：３．１７９±０．２５２、Ｔｇ：８３℃）、フェニルメタクリレート（側鎖部分ＳＰ値：１０．７５、ＬｏｇＰ：２．３５９±０．４２９、Ｔｇ：１１０）、メチルメタクリレート（側鎖部分ＳＰ値：１０．２６、ＬｏｇＰ：１．２０７±０．２５０、Ｔｇ：１０５℃、）、イソボルニルアクリレート（側鎖部分ＳＰ値：９．４２、ＬｏｇＰ：４．０２９±０．２７３、Ｔｇ：９７℃）、イソボルニルメタクリレート（側鎖部分ＳＰ値：９．４２、ＬｏｇＰ：４．４４７±０．３０１、Ｔｇ：１８０℃）、エチルメタクリレート（側鎖部分ＳＰ値：９．８８、ＬｏｇＰ：１．７１６±０．２５０、Ｔｇ：６５℃）、ｔｅｒｔ－ブチルアクリレート（側鎖部分ＳＰ値：８．９９、ＬｏｇＰ：２．０６２±０．２３８、Ｔｇ：１４℃）、ｔｅｒｔ－ブチルメタクリレート（側鎖部分ＳＰ値：８．９９、ＬｏｇＰ：２．４８１±０．２６１、Ｔｇ：１０７℃）、ジシクロペンタニルアクリレート（側鎖部分ＳＰ値：１０．３１、ＬｏｇＰ：３．９５７±０．２４４、Ｔｇ：１２０℃）、ジシクロペンタニルメタクリレート（側鎖部分ＳＰ値：１０．３１、ＬｏｇＰ：４．３７５±０．２６６、Ｔｇ：１７５℃）、２，２，２－トリフルオロエチルメタクリレート（側鎖部分ＳＰ値：１３．１５、ＬｏｇＰ：１．６１９±０．４１５、Ｔｇ：７２℃）、４－ｔｅｒｔ－ブチルシクロヘキシルアクリレート（側鎖部分ＳＰ値：９．０８、ＬｏｇＰ：４．５７０±０．２４３、Ｔｇ：８１℃）、ナフタレニルメタクリレート（側鎖部分ＳＰ値：９，８６、ＬｏｇＰ：４．８３１±０．２６０、Ｔｇ：１４３℃）、アダマンタンアクリレート（側鎖部分ＳＰ値：１０．３２、ＬｏｇＰ：３．７０２±０．２５８、Ｔｇ：２５０℃）、テトラヒドロフルフリルメタクリレート（側鎖部分ＳＰ値：１０．３７、ＬｏｇＰ：１．３９９±０．３４０、Ｔｇ：６０℃）、ｔｅｒｔ－ブチルシクロヘキシルメタクリレート（側鎖部分ＳＰ値：９．０８、ＬｏｇＰ：４．５７０±０．２４３、Ｔｇ：８１℃）等を挙げることができる。これらのモノマーＡは単独で使用しても良いし、複数のモノマーＡを組み合わせもよい。なお、括弧内の「Ｔｇ」とはそのモノマーのホモポリマーのＴｇを意味し、括弧内の「ＬｏｇＰ」とは、水／１－オクタノールでの分配係数（ＬｏｇＰ）を意味する。 Monomer A includes cyclohexyl methacrylate (side chain portion SP value: 9.96, LogP: 3.179±0.252, Tg: 83°C), phenyl methacrylate (side chain portion SP value: 10.75, LogP: 2 .359±0.429, Tg: 110), methyl methacrylate (side chain moiety SP value: 10.26, LogP: 1.207±0.250, Tg: 105°C,), isobornyl acrylate (side chain moiety SP value: 9.42, LogP: 4.029±0.273, Tg: 97°C), isobornyl methacrylate (side chain moiety SP value: 9.42, LogP: 4.447±0.301, Tg: 180°C), ethyl methacrylate (side chain portion SP value: 9.88, LogP: 1.716 ± 0.250, Tg: 65°C), tert-butyl acrylate (side chain portion SP value: 8.99, LogP: 2.062±0.238, Tg: 14°C), tert-butyl methacrylate (side chain moiety SP value: 8.99, LogP: 2.481±0.261, Tg: 107°C), dicyclopentanyl acrylate (Side chain moiety SP value: 10.31, LogP: 3.957±0.244, Tg: 120°C), dicyclopentanyl methacrylate (side chain moiety SP value: 10.31, LogP: 4.375±0 .266, Tg: 175°C), 2,2,2-trifluoroethyl methacrylate (side chain moiety SP value: 13.15, LogP: 1.619 ± 0.415, Tg: 72°C), 4-tert- Butyl cyclohexyl acrylate (side chain moiety SP value: 9.08, LogP: 4.570±0.243, Tg: 81°C), naphthalenyl methacrylate (side chain moiety SP value: 9.86, LogP: 4.831 ±0.260, Tg: 143℃), adamantane acrylate (side chain moiety SP value: 10.32, LogP: 3.702±0.258, Tg: 250℃), tetrahydrofurfuryl methacrylate (side chain moiety SP value :10.37, LogP: 1.399±0.340, Tg: 60°C), tert-butylcyclohexyl methacrylate (side chain moiety SP value: 9.08, LogP: 4.570±0.243, Tg: 81 °C), etc. These monomers A may be used alone, or a plurality of monomers A may be used in combination. Note that "Tg" in parentheses means the Tg of the homopolymer of the monomer, and "LogP" in parentheses means the partition coefficient (LogP) in water/1-octanol.
　なお、モノマーＡは２個以上のエチレン性不飽和結合を有するモノマーを含んでいてもよいが、モノマーＡは１つのエチレン性不飽和結合を有するモノマーのみから構成されることが好ましい。これにより樹脂の架橋点増加による塗膜の堅脆さが緩和し得られる記録物の耐溶剤性をさらに向上させることができる。 Although 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. As a result, 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.
　構成モノマーであるモノマーＡの含有量は、とくに限定されるものではないが、モノマーＢの含有量の下限は、共重合体全量中５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。これにより、水／１－オクタノールでの分配係数（ＬｏｇＰ）が所定以上の範囲にあるモノマーＡの含有量が増加するので、得られる記録物の耐溶剤性をさらに高くすることが可能となる。 The content of monomer A, which is a constituent monomer, is not particularly limited, but the lower limit of the content of monomer B 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 distribution coefficient (LogP) in water/1-octanol is within a predetermined range or higher, making it possible to further increase the solvent resistance of the resulting recorded material.
　（モノマーＢ）
　モノマーＢとは、モノマーＡ以外であって、酸性基または塩基性基を有するアクリルモノマーである。酸性基または塩基性基を有するアクリルモノマーを含むことにより、高分子微粒子分散体に静電反発力を付与して高分子微粒子分散体の分散安定性が向上するので、水性インク組成物の保存安定性を向上させることが可能となる。なお、モノマーＢの酸性基または塩基性基はそのままであっても中和されることで中和塩の状態になっていてもよい。 (Monomer B)
Monomer B is an acrylic monomer other than monomer A that has an acidic group or a basic group. By including an acrylic monomer having an acidic group or a basic group, electrostatic repulsion is imparted to the polymer fine particle dispersion, improving the dispersion stability of the polymer fine particle dispersion, thereby improving the storage stability of the aqueous ink composition. It becomes possible to improve sexual performance. In addition, the acidic group or basic group of monomer B may be in the state of a neutralized salt by being neutralized even if it is as it is.
　モノマーＢが備える酸性基とは、カルボキシル基、スルホン基、リン酸基等を挙げることができる。この中でもカルボキシル基であることが好ましい。 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.
　モノマーＢが備える塩基性基とは、アミノ基（－ＮＨ２、－ＮＨＲ、－ＮＲＲ‘）を挙げることができる。この中でも三級アミノ基（－ＮＲＲ‘）であることが好ましい。 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.
　モノマーＢの具体例としては、例えば、アクリル酸、メタクリル酸、２－アクリロイルオキシエチルコハク酸、フタル酸モノ－２－（メタクリロイルオキシ）エチル、フタル酸モノヒドロキシエチルアクリレート、ω－カルボキシ－ポリカプロラクトン（ｎ≒２）モノアクリレート、４－カルボキシスチレン、６－アクリルアミドヘキサン酸、メタクリル酸２－（ジメチルアミノ）エチル、アクリル酸２－（ジメチルアミノ）エチル、ジメチルアミノプロピルアクリルアミド、メタクリル酸２－アミノエチル、２－アミノエチルメタクリルアミド、Ｎ－(３－アミノプロピル)メタクリルアミド、メタクリル酸２－(ジイソプロピルアミノ)エチル、Ｎ－(２－ジメチルアミノエチル)メタクリルアミド等を挙げることができる。これらのモノマーＢは単独で使用しても良いし、複数のモノマーＢを組み合わせもよい。なお、これらのモノマーＢはそのままであっても中和塩の状態であってもよい。 Specific examples of monomer B include acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, mono-2-(methacryloyloxy)ethyl phthalate, monohydroxyethyl phthalate, ω-carboxy-polycaprolactone ( 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. These monomers B may be used alone, or a plurality of monomers B may be used in combination. Note that these monomers B may be used as they are or in the form of a neutralized salt.
　構成モノマーであるモノマーＢの含有量は、とくに限定されるものではないが、モノマーＢの含有量の下限は、共重合体全量中０．１質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、１．０質量％以上であることがさらに好ましい。これにより、高分子微粒子分散体の分散安定性がより効果的に向上するので、水性インク組成物の保存安定性をさらに向上させることが可能となる。モノマーＢの含有量の上限は、共重合体全量中２０．０質量％以下であることが好ましく、１５．０質量％以下であることがより好ましく、１０．０質量％以下であることがさらに好ましい。これにより、相対的に共重合体中のモノマーＡ、Ｃの含有量を増やすことが可能となるので、結果として得られる記録物の耐溶剤性をさらに向上させることが可能となる。モノマーＢの含有量の範囲は、共重合体全量中０．１質量％以上２０．０質量％以下であることが好ましく、０．５質量％以上１５．０質量％以下であることがより好ましく、１．０質量％以上１０．０質量％以下であることがさらに好ましい。 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. This makes it possible to relatively increase the content of monomers A and C in the copolymer, thereby making it possible to further improve the solvent resistance of the resulting recorded material. 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 10.0% by mass or less.
　（モノマーＣ）
　モノマーＣとは、モノマーＡ、モノマーＢ以外であって、ホモポリマーのＴｇが６０℃未満のモノマーである。 (Monomer C)
Monomer C is a monomer other than monomer A and monomer B whose homopolymer Tg is less than 60°C.
　モノマーＡ、モノマーＢに加えてホモポリマーのＴｇが６０℃未満のモノマーＣを構成単位として含むことで、低温で乾燥させた場合であっても、十分に成膜することが可能となり、得られる記録物の耐溶剤性をさらに向上させることができる。 By including monomer C, which has a homopolymer Tg of less than 60°C, as a constituent unit in addition to monomer A and monomer B, it is possible to form a film sufficiently even when drying at a low temperature, and it is possible to obtain The solvent resistance of recorded matter can be further improved.
　この中でも特にモノマーＢとしてホモポリマーのＴｇが６０℃以上であるモノマーＢを含有し、ホモポリマーのＴｇが６０℃未満のモノマーＣをさらに含有することで、得られる記録物の耐擦性を向上させつつ、耐溶剤性をさらに向上させることができる。 Among these, in particular, monomer B having a homopolymer Tg of 60°C or higher is contained, and monomer C having a homopolymer Tg lower than 60°C is further included to improve the abrasion resistance of the resulting recorded material. It is possible to further improve solvent resistance.
　モノマーＣとしては、ブチルメタクリレート（側鎖部分ＳＰ値：９．４８、ＬｏｇＰ：２．７３５±０．２５０、Ｔｇ：２０℃）、シクロヘキシルアクリレート（側鎖部分ＳＰ値：９．９６、ＬｏｇＰ：２．７６０±０．２２６、Ｔｇ：１９℃）、２－エチルヘキシルアクリレート（側鎖部分ＳＰ値：８．９８、ＬｏｇＰ：４．１９９±０．２２９、Ｔｇ：－７０℃）、ブチルアクリレート（側鎖部分ＳＰ値：９．４８、ＬｏｇＰ：２．３１７±０．２２４、Ｔｇ：－５４℃）、エチルアクリレート（側鎖部分ＳＰ値：９．８８、ＬｏｇＰ：１．２９８±０．２２３、Ｔｇ：－２０℃）、メチルアクリレート（側鎖部分ＳＰ値：１０．２６、ＬｏｇＰ：０．７８８±０．２２３、Ｔｇ：８℃）、ベンジルメタクリレート（側鎖部分ＳＰ値：１０．４９、ＬｏｇＰ：２．５２７±０．２５５、Ｔｇ：５４℃）、２－エチルヘキシルアクリレート（側鎖部分ＳＰ値：８．９８、ＬｏｇＰ：４．１９９±０．２２９、Ｔｇ：－７０℃）、イソブチルアクリレート（側鎖部分ＳＰ値：９．２４、ＬｏｇＰ：２．１６１±０．２２８、Ｔｇ：-２６℃）、イソブチルメタクリレート（側鎖部分ＳＰ値：９．２４、ＬｏｇＰ：２．５７９±０．２５４、Ｔｇ：４８℃）、イソデシルアクリレート（側鎖部分ＳＰ値：８．６６、ＬｏｇＰ：４．９０６±０．２３８、Ｔｇ：-６２℃）、イソデシルメタクリレート（側鎖部分ＳＰ値：８．６６、ＬｏｇＰ：５．３２４±０．２６１、Ｔｇ：－４１℃）、フェノキシエチルアクリレート（側鎖部分ＳＰ値：１０．４２、ＬｏｇＰ：２．３７１±０．２４６、Ｔｇ：-２２℃）、フェノキシエチルメタクリレート（側鎖部分ＳＰ値：１０．４２、ＬｏｇＰ：２．７９０±０．２６８、Ｔｇ：－３℃）、３，３，５－トリメチルシクロヘキシルアクリレート（側鎖部分ＳＰ値：９．１２、ＬｏｇＰ：４．２１２±０．２５４、Ｔｇ：５２℃）、環状トリメチロールプロパンホルマールアクリレート（側鎖部分ＳＰ値：９，９６、ＬｏｇＰ：１．０３２±０．３６１、Ｔｇ：２７℃）等を挙げることができる。これらのモノマーＣは単独で使用しても良いし、複数のモノマーＣを組み合わせもよい。なお括弧内の「側鎖部分ＳＰ値」とは、式（１）のＲ２で定義される化学構造部分について計算されるＳＰ値を意味し、括弧内の「ＬｏｇＰ」とは、水／１－オクタノールでの分配係数（ＬｏｇＰ）を意味し、括弧内の「Ｔｇ」とはそのモノマーのホモポリマーのＴｇを意味する。 As monomer C, butyl methacrylate (side chain portion SP value: 9.48, LogP: 2.735 ± 0.250, Tg: 20°C), cyclohexyl acrylate (side chain portion SP value: 9.96, LogP: 2 .760±0.226, Tg: 19°C), 2-ethylhexyl acrylate (side chain moiety SP value: 8.98, LogP: 4.199±0.229, Tg: -70°C), butyl acrylate (side chain Partial SP value: 9.48, LogP: 2.317±0.224, Tg: -54°C), Ethyl acrylate (side chain part SP value: 9.88, LogP: 1.298±0.223, Tg: -20℃), methyl acrylate (side chain portion SP value: 10.26, LogP: 0.788 ± 0.223, Tg: 8℃), benzyl methacrylate (side chain portion SP value: 10.49, LogP: 2 .527±0.255, Tg: 54°C), 2-ethylhexyl acrylate (side chain moiety SP value: 8.98, LogP: 4.199±0.229, Tg: -70°C), isobutyl acrylate (side chain Partial SP value: 9.24, LogP: 2.161 ± 0.228, Tg: -26°C), Isobutyl methacrylate (side chain part SP value: 9.24, LogP: 2.579 ± 0.254, Tg: 48℃), isodecyl acrylate (side chain moiety SP value: 8.66, LogP: 4.906 ± 0.238, Tg: -62℃), isodecyl methacrylate (side chain moiety SP value: 8.66, LogP : 5.324±0.261, Tg: -41°C), phenoxyethyl acrylate (side chain moiety SP value: 10.42, LogP: 2.371±0.246, Tg: -22°C), phenoxyethyl methacrylate (Side chain moiety SP value: 10.42, LogP: 2.790±0.268, Tg: -3°C), 3,3,5-trimethylcyclohexyl acrylate (Side chain moiety SP value: 9.12, LogP: 4.212±0.254, Tg: 52°C), cyclic trimethylolpropane formal acrylate (side chain moiety SP value: 9,96, LogP: 1.032±0.361, Tg: 27°C), etc. Can be done. These monomers C may be used alone, or a plurality of monomers C may be used in combination. 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.
　このようなモノマーＣの中でも、ホモポリマーのＴｇが５０℃以下のモノマーＣであることが好ましく、ホモポリマーのＴｇが４５℃以下のモノマーＣであることがより好ましく、ホモポリマーのＴｇが４０℃以下のモノマーＣであることがさらに好ましい。また、ホモポリマーのＴｇが－１５℃以上のモノマーＣであることが好ましく、－５℃以上のモノマーＣであることがより好ましく、０℃以上のモノマーＣであることがさらに好ましい。また、ホモポリマーのＴｇが－１５℃以上５０℃以下のモノマーＣであることが好ましく、－５℃以上４５℃以下のモノマーＣであることがより好ましく、０℃以上４０℃以下のモノマーＣであることがさらに好ましい。 Among such monomers C, it is preferable that the monomer C has a homopolymer Tg of 50°C or less, it is more preferable that the homopolymer Tg is 45°C or less, and the monomer C has a homopolymer Tg of 40°C or less. The following monomer C is more preferable. Further, it is preferable that the monomer C has a homopolymer Tg of -15°C or higher, more preferably a monomer C that has a Tg of -5°C or higher, and still more preferably a monomer C that has a Tg of 0°C or higher. Further, it is preferable that the homopolymer has a Tg of -15°C or more and 50°C or less, more preferably -5°C or more and 45°C or less, and monomer C that has a Tg of 0°C or more and 40°C or less. It is even more preferable that there be.
　なお、モノマーＣは２個以上のエチレン性不飽和結合を有するモノマーを含んでいてもよいが、モノマーＣは１つのエチレン性不飽和結合を有するモノマーのみから構成されることが好ましい。これにより樹脂の架橋点増加による塗膜の堅脆さが緩和し得られる記録物の耐溶剤性をさらに向上させることができる。 Although the monomer C may contain a monomer having two or more ethylenically unsaturated bonds, it is preferable that the monomer C is composed of only a monomer having one ethylenically unsaturated bond. As a result, 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.
　構成モノマーであるモノマーＣの含有量は、とくに限定されるものではないが、モノマーＣの含有量の下限は、共重合体全量中３質量％以上であることが好ましく、７質量％以上であることがより好ましく、１０質量％以上であることがさらに好ましい。これにより、得られる記録物の耐溶剤性をさらに向上させることができる。モノマーＣの含有量の上限は、共重合体全量中４５質量％以下であることが好ましく、４０質量％以下であることがより好ましく、３５質量％以下であることがさらに好ましい。これにより、相対的に共重合体中のモノマーＡの含有量を増やすことが可能となるので、得られる記録物の耐溶剤性をさらに向上させることが可能となる。モノマーＣの含有量の範囲は、共重合体全量中３質量％以上４５質量％以下であることが好ましく、７質量％以上４０質量％以下であることがより好ましく、１０質量％以上３５質量％以下であることがさらに好ましい。 The content of monomer C, which is a constituent monomer, is not particularly limited, but the lower limit of the content of monomer C is preferably 3% by mass or more, and 7% by mass or more based on the total amount of the copolymer. The content is more preferably 10% by mass or more, and even more preferably 10% by mass or more. Thereby, the solvent resistance of the resulting recorded material can be further improved. The upper limit of the content of monomer C is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less based on the total amount of the copolymer. This makes it possible to relatively increase the content of monomer A in the copolymer, thereby making it possible to further improve the solvent resistance of the resulting recorded material. The content range of monomer C is preferably 3% by mass or more and 45% by mass or less based on the total amount of the copolymer, more preferably 7% by mass or more and 40% by mass or less, and 10% by mass or more and 35% by mass. It is more preferable that it is the following.
　（その他のモノマー）
　本実施の形態に係る水性インク組成物に含まれる共重合体は、モノマーＡ、モノマーＢ、モノマーＣとは異なるその他のモノマーを構成単位として含んでいてもよいし、含んでいなくともよい。その他のモノマーとしては、モノマーＡ、モノマーＢ、モノマーＣに該当しないアクリルモノマーや、アクリルモノマーとは異なるエチレン性不飽和多重結合等の反応基を有するモノマーを挙げることができる。例えばスチレン、ビニルシクロヘキサン、ｔ－ブチル４エチニルシクロヘキサン等を挙げることができる。これらのその他のモノマーは単独で使用しても良いし、複数のモノマーを組み合わせもよい。 (Other monomers)
The copolymer contained in the aqueous ink composition according to the present embodiment may or may not contain other monomers different from monomer A, monomer B, and monomer C as a constituent unit. Examples of other monomers include acrylic monomers that do not fall under Monomer A, Monomer B, and Monomer C, and monomers that have reactive groups such as ethylenically unsaturated multiple bonds that are different from acrylic monomers. Examples include styrene, vinylcyclohexane, t-butyl 4-ethynylcyclohexane, and the like. These other monomers may be used alone or in combination.
　なお、その他のモノマーは２個以上のエチレン性不飽和結合を有するモノマーを含んでいてもよいが、その他のモノマーは１つのエチレン性不飽和結合を有するモノマーのみから構成されることが好ましい。これにより樹脂の架橋点増加による塗膜の堅脆さが緩和し得られる記録物の耐溶剤性をさらに向上させることができる。 Note that 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. As a result, 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.
　その他のモノマーの含有量は、とくに限定されるものではないが、その他のモノマーの含有量の上限は、共重合体全量中１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、１質量％以下であることがさらに好ましい。 The content of other monomers is not particularly limited, but the upper limit of the content of other monomers is preferably 10% by mass or less, and preferably 5% by mass or less based on the total amount of the copolymer. More preferably, it is 1% by mass or less.
　例えば、樹脂構造中にカルボニル基含むモノマーを構成単位として含む重合体に対して、そのカルボニル基と反応しうる官能基を有する化合物を架橋剤として添加することで、重合体を含む樹脂に架橋構造を導入することができる。このため、このようなカルボニル基を含むモノマーを構成単位として含む重合体を含有する樹脂組成物を使用することで、得られる塗膜の耐摩擦性を向上させることができる。 For example, by adding a compound having a functional group that can react with the carbonyl group as a crosslinking agent to a polymer containing a monomer containing a carbonyl group as a constituent unit in the resin structure, the resin containing the polymer has a crosslinked structure. can be introduced. Therefore, by using a 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.
　このようなカルボニル基を含むモノマーのうち、カルボニル基含有１官能エチレン性不飽和単量体としては、例えば、２－（アクリロイルアミノ）－２－メチル－４－ペンタノン（側鎖部分ＳＰ値：１２．０４、ＬｏｇＰ：０．０３７±０．２８７）、アクリルアルデヒド（側鎖部分ＳＰ値：１５．４７、ＬｏｇＰ：０．２６３±０．２８３）、Ｎ－エテニルホルムアミド（側鎖部分ＳＰ値：１９．７２、ＬｏｇＰ：０．５２５±０．２１５）、メチルエテニルケトン（側鎖部分ＳＰ値：１０．９１、ＬｏｇＰ：０．１４２±０．２４９）、エチルエテニルケトン（側鎖部分ＳＰ値：１０．３４、ＬｏｇＰ：０．６５２±０．２４９）、アクリル酸２－（アセトアセチルオキシ)エチル（側鎖部分ＳＰ値：１１．７３、ＬｏｇＰ：０．３３１±０．３５６）、メタクリル酸2-(アセトアセチルオキシ)エチル（側鎖部分ＳＰ値：１１．７３、ＬｏｇＰ：０．７５０±０．３８５）、アクリル酸2-(アセトアセチルオキシ)プロピル（側鎖部分ＳＰ値：１１．４３、ＬｏｇＰ：０．６３５±０．３５０）、アクリル酸２－（アセトアセチルオキシ）プロピル（側鎖部分ＳＰ値：１１．４３、ＬｏｇＰ：１．０５４±０．３７８）、などが挙げられる。しかしながら、これらのモノマーは、「水／１－オクタノールでの分配係数（ＬｏｇＰ）」が０～１．１であり、相対的に親水性が高いモノマーである。このようにカルボニル基を含むモノマーを構成単位として含む重合体を含有する樹脂組成物であると、得られる塗膜の耐溶剤性が相対的に低下する傾向がある。このため、本実施の形態に係る樹脂は、カルボニル基を含むモノマーを構成単位として含む重合体を含有してもよいが、特に架橋剤を添加して重合体を含む樹脂に架橋構造を導入するのでなければ、カルボニル基を含むモノマーを構成単位として含む重合体を含有しないことが好ましい。 Among such carbonyl group-containing monomers, carbonyl group-containing monofunctional ethylenically unsaturated monomers include, for example, 2-(acryloylamino)-2-methyl-4-pentanone (side chain moiety SP value: 12 .04, LogP: 0.037±0.287), acrylaldehyde (side chain moiety SP value: 15.47, LogP: 0.263±0.283), N-ethenylformamide (side chain moiety SP value: 19.72, LogP: 0.525±0.215), methyl ethenyl ketone (side chain moiety SP value: 10.91, LogP: 0.142±0.249), ethyl ethenyl ketone (side chain moiety SP Value: 10.34, LogP: 0.652±0.249), 2-(acetoacetyloxy)ethyl acrylate (side chain moiety SP value: 11.73, LogP: 0.331±0.356), methacrylic 2-(acetoacetyloxy)ethyl acid (side chain moiety SP value: 11.73, LogP: 0.750±0.385), 2-(acetoacetyloxy)propyl acrylate (side chain moiety SP value: 11. 43, LogP: 0.635±0.350), 2-(acetoacetyloxy)propyl acrylate (side chain moiety SP value: 11.43, LogP: 1.054±0.378), and the like. However, these monomers have a "water/1-octanol partition coefficient (LogP)" of 0 to 1.1, and are relatively highly hydrophilic monomers. In this way, when the resin composition contains a polymer containing a monomer containing a carbonyl group as a constitutional unit, the solvent resistance of the resulting coating film tends to be relatively reduced. Therefore, 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.
　［共重合体］
　本実施の形態に係る水性インク組成物は、Ｔｇが０℃以上１２０℃以下であるアクリル系樹脂を含有し、このアクリル系樹脂は、モノマーＡ、モノマーＢ、モノマーＣなどの少なくとも２種類のモノマーを構成単位として含む共重合体を含有する。これにより、低温で乾燥させた場合であっても、得られる記録物の耐溶剤性を高くすることができる。 [Copolymer]
The aqueous ink composition according to the present embodiment contains an acrylic resin having a Tg of 0°C or more and 120°C or less, and this acrylic resin contains at least two types of monomers such as monomer A, monomer B, and monomer C. Contains a copolymer containing as a constituent unit. Thereby, even when drying at a low temperature, the solvent resistance of the resulting recorded material can be increased.
　そして、この共重合体の少なくとも一部は、水性インク組成部中に高分子微粒子分散体として含有するものである。この共重合体は、モノマーを乳化重合法、懸濁重合法等の従来公知のラジカル重合法により得ることができる。なかでもこの共重合体は、乳化重合物であることが好ましい。 At least a portion of this copolymer is contained in the aqueous ink composition as a polymer fine particle dispersion. This copolymer can be obtained from monomers by conventionally known radical polymerization methods such as emulsion polymerization and suspension polymerization. Among these, this copolymer is preferably an emulsion polymer.
　モノマーを乳化重合法により重合して共重合体を得る場合には、乳化剤、重合開始剤、重合調整剤、架橋剤、中和剤、造膜助剤等の他の成分を適宜用いてもよい。 When obtaining a copolymer by polymerizing monomers by emulsion polymerization, other components such as an emulsifier, a polymerization initiator, a polymerization modifier, a crosslinking agent, a neutralizing agent, and a film-forming aid may be used as appropriate. .
　モノマーを乳化重合法により重合して共重合体を得る場合には、例えば、各成分を混合し、昇温する方法や、各成分の一部を混合し、昇温し、重合した後に残りの単量体成分を添加して重合する方法やモノマー以外の成分を混合して昇温した後にモノマー成分を添加して重合する方法が挙げられる。 When obtaining a copolymer by polymerizing monomers by emulsion polymerization, for example, there are methods such as mixing each component and raising the temperature, or mixing a part of each component, raising the temperature, polymerizing, and then adding the remaining Examples include a method in which monomer components are added and polymerized, and a method in which components other than monomers are mixed and heated, and then monomer components are added and polymerized.
　乳化剤としては、アニオン型、カチオン型、およびノニオン型の界面活性剤を挙げることができる。この中でも構造中に多重結合を有しない非反応性の乳化剤を使用すること（すなわち、高分子微粒子分散体として含有する樹脂は、非反応性の乳化剤を含むこと）が好ましい。非反応性の乳化剤を使用して得られた共重合体を高分子微粒子分散体として水性インク組成物中に分散させることにより、共重合体の分散安定性を向上させることが可能となって、結果として保存安定性をさらに向上させることが可能となる。 Examples of emulsifiers include anionic, cationic, and nonionic surfactants. Among these, it is preferable to use 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). By dispersing a copolymer obtained using a non-reactive emulsifier in an aqueous ink composition as a polymer fine particle dispersion, it is possible to improve the dispersion stability of the copolymer. As a result, it becomes possible to further improve storage stability.
　非反応性の乳化剤としては、例えば、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム、テトラデシル硫酸ナトリウム等のアルキル硫酸ナトリウム、ラウリル硫酸アンモニウム、ジフェニルエーテルスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル等を挙げられ、具体的には、「アデカプルロニックＬ－３１」、「アデカプルロニックＰ－８５」、「アデカプルロニックＦ－１０８」、「アデカトールＬＢ－８３」、「アデカトールＳＯ－１４５」、「アデカホープＹＥＳ－２５」、「アデカミン４ＭＡＣ－３０」、「アデカミン４ＭＴ－５０」、「アデカコールＴＳ－２３０Ｅ」、「アデカコールＰＳ－８１０Ｅ」〔以上、アデカ社製〕、「エマルゲン　１２０」、「エマルゲン　１４７」、「エマルゲン　１０９Ｐ」、「エマルゲン　２１０Ｐ」、「エマルゲン　３０６Ｐ」、「エマルゲン　４０９ＰＶ」、「エマルゲン　４２０」、「エマルゲン　７０９」、「エマルゲン　１１０８」、「エマルゲン　１１１８Ｓ－７０」、「エマルゲン　１１５０Ｓ－６０」、「エマルゲン　１１３５Ｓ－７０」、「エマルゲン　４０８５」、「エマルゲン　２０２０Ｇ－ＨＡ」、「エマルゲン　Ａ－６０」、「エマルゲン　Ａ－９０」、「エマルゲン　Ａ－５００」、「エマルゲン　ＬＳ－１１０」、「エマルゲン　Ｇ２Ｅ－４」、「エマール　２ＦＧ」、「エマール　２０ＣＭ」、「エマール　２７０Ｊ」、「ラテムル　ＡＤ－２５」、「ラムテルＥ－１０００Ａ」、「アセタミン　２４」、「コータミン　６０Ｗ」、「サニゾール　Ｃ」「エマノーン　１１１２」〔以上、花王社製〕、等の市販品を挙げることができる。これらは１種類で使用しても、２種類以上を混合して使用してもよい。 Examples of 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. Specifically, "Adeka Pluronic L-31", "Adeka Pluronic P-85", "Adeka Pluronic F-108", "Adekatol LB-83", "Adekatol SO-145", "Adeka Hope YES-" 25'', ``Adekamin 4MAC-30'', ``Adekamin 4MT-50'', ``Adekacol TS-230E'', ``Adekacol PS-810E'' [all manufactured by Adeka Corporation], ``Emulgen 120'', ``Emulgen 147'', ``Emulgen 109P”, “Emulgen 210P”, “Emulgen 306P”, “Emulgen 409PV”, “Emulgen 420”, “Emulgen 709”, “Emulgen 1108”, “Emulgen 1118S-70”, “Emulgen 1150S-60”, “Emulgen 1135S -70”, “Emulgen 4085”, “Emulgen 2020G-HA”, “Emulgen A-60”, “Emulgen A-90”, “Emulgen A-500”, “Emulgen LS-110”, “Emulgen G2E-4” , "Emar 2FG", "Emar 20CM", "Emar 270J", "Latemul AD-25", "Ramtel E-1000A", "Acetamine 24", "Cortamine 60W", "Sanisol C", "Emanon 1112" [and above] , manufactured by Kao Corporation], and other commercially available products. These may be used alone or in combination of two or more.
　反応性の乳化剤としては、具体的には、「アデカリアソープＳＥ－２０Ｎ」、「アデカリアソープＳＥ－１０Ｎ」、「アデカリアソープＰＰ－７０」、「アデカリアソープＰＰ－７１０」、「アデカリアソープＳＲ－１０」、「アデカリアソープＳＲ－２０」〔以上、アデカ社製〕、「エレミノールＪＳ－２」、「エレミノールＲＳ－３０」〔以上、三洋化成工業社製〕、「ラテムルＳ－１８０Ａ」、「ラテムルＳ－１８０」、「ラテムルＰＤ－１０４」〔以上、花王社製〕、「アクアロンＢＣ－０５」、「アクアロンＢＣ－１０」、「アクアロンＢＣ－２０」、「アクアロンＨＳ－０５」、「アクアロンＨＳ－１０」、「アクアロンＨＳ－２０」、「ニューフロンティアＳ－５１０」、「アクアロンＫＨ－０５」、「アクアロンＫＨ－１０」〔以上、第一工業製薬社製〕、「フォスフィノ－ルＴＸ」〔東邦化学工業社製〕「アデカリアソープＮＥ－１０」、「アデカリアソープＮＥ－２０」、「アデカリアソープＮＥ－３０」、「アデカリアソープＮＥ－４０」、「アデカリアソープＥＲ－１０」、「アデカリアソープＥＲ－２０」、「アデカリアソープＥＲ－３０」、「アデカリアソープＥＲ－４０」、〔以上、アデカ社製〕、「アクアロンＲＮ－１０」、「アクアロンＲＮ－２０」、「アクアロンＲＮ－３０」、「アクアロンＲＮ－５０」〔以上、第一工業製薬社製〕等の市販品が挙げられる。 Specifically, 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''. ", "Aqualon HS-10", "Aqualon HS-20", "New Frontier S-510", "Aqualon KH-05", "Aqualon KH-10" [all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], "Fosphino ``Adecaria Soap NE-10'', ``Adecaria Soap NE-20'', ``Adecaria Soap NE-30'', ``Adecaria Soap NE-40'', ``Adecaria Soap ER-10'', ``Adecaria Soap ER-20'', ``Adecaria Soap ER-30'', ``Adekaria Soap ER-40'', [all manufactured by Adeka], ``Aqualon RN-10'', ``Aqualon'' Examples include commercially available products such as "RN-20", "Aqualon RN-30", and "Aqualon RN-50" (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
　乳化剤の使用量は、モノマー１００質量部に対して、０．１質量部以上であることが好ましく、０．５質量部以上であることがより好ましく、１質量部以上であることがさらに好ましい。乳化剤の使用量は、モノマー１００質量部に対して、２０質量部以下であることが好ましく、１５質量部以下であることがより好ましく、１０質量部以下であることがさらに好ましい。乳化剤の使用量は、モノマー１００質量部に対して、０．１質量部以上２０質量部以下であることが好ましく、０．５質量部以上であることがより好ましく、１質量部以上であることがさらに好ましい。 The amount of emulsifier used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, based on 100 parts by mass of the monomer. 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 1 part by mass or more, based on 100 parts by mass of the monomer. is even more preferable.
　重合開始剤としては、例えば、アルキルパーオキサイド、ｔ－ブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、ｐ－メタンヒドロパーオキサイド、ラウロイルパーオキサイド、３，５，５－トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ベンゾイルパーオキサイド、ジクロルベンゾイルパーオキサイド、ジクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、３，３，５－トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、ジ－イソブチルパーオキシジカーボネート、ジ－２－エチルヘキシルパーオキシジカーボネート、ｔ－ブチルパーオキシイソブチレート等の有機過酸化物、２，２′－アゾビスイソブチロニトリル、ジメチル－２，２′－アゾビスイソブチレート、２，２′－アゾビス（２，４－ジメチルバレロニトリル）、２，２′－アゾビス（２－メチルブチロニトリル）、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、４，４′－アゾビス－４－シアノバレリックアシッドのアンモニウム（アミン）塩、２，２′－アゾビス（２－メチルアミドオキシム）ジヒドロクロライド、２，２′－アゾビス（２－メチルブタンアミドオキシム）ジヒドロクロライドテトラヒドレート、２，２′－アゾビス｛２－メチル－Ｎ－〔１，１－ビス（ヒドロキシメチル）－２－ヒドロキシエチル〕－プロピオンアミド｝、２，２′－アゾビス〔２－メチル－Ｎ－（２－ヒドロキシエチル）－プロピオンアミド〕、各種レドックス系触媒（この場合酸化剤としては、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム、過酸化水素、ｔ－ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、キュメンハイドロパーオキサイド、ｐ－メタンハイドロパーオキサイド等が、還元剤としては亜硫酸ナトリウム、酸性亜硫酸ナトリウム、ロンガリット、アスコルビン酸等が用いられる。）等が挙げられる。これらの重合開始剤は単独であるいは２種以上併せて用いられる。 Examples of the polymerization initiator include alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and octanoyl peroxide. oxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5 - Organic peroxides such as trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butylperoxyisobutyrate, etc. Oxide, 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, ammonium (amine) salt of 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (2-Methylamidoxime) dihydrochloride, 2,2'-azobis(2-methylbutanamidoxime) dihydrochloride tetrahydrate, 2,2'-azobis{2-methyl-N-[1,1-bis( hydroxymethyl)-2-hydroxyethyl]-propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], various redox catalysts (in this case, the oxidizing agent is Ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p-methane hydroperoxide, etc., and reducing agents include sodium sulfite and acidic sodium sulfite. , Rongalit, ascorbic acid, etc.). These polymerization initiators may be used alone or in combination of two or more.
　重合開始剤の使用量は、適宜調整されればよいが、モノマー１００質量部に対して、０．０１質量部以上であることが好ましく、０．０３質量部以上であることがより好ましく、０．０５質量部以上であることがさらに好ましい。重合開始剤の使用量は、モノマー１００質量部に対して、５質量部以下であることが好ましく、３質量部以下であることがより好ましく、１質量部以下であることがさらに好ましい。重合開始剤の使用量は、モノマー１００質量部に対して、０．０１質量部以上５質量部以下であることが好ましく、０．０３質量部以上３質量部以下であることがより好ましく、０．０５質量部以上１質量部以下であることがさらに好ましい。 The amount of the polymerization initiator used may be adjusted as appropriate, but it is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and 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 mass or more and 5 parts by mass or less, more preferably 0.03 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the monomer. More preferably, the amount is .05 parts by mass or more and 1 part by mass or less.
　重合調整剤としては、例えば、メタノール、エタノール、プロパノール、ブタノー
ル等のアルコール；アセトアルデヒド、プロピオンアルデヒド、ｎ－ブチルアルデヒド、フルフラール、ベンズアルデヒド等のアルデヒド類；ｎ－ドデシルメルカプタン、チオグリコール酸、チオグリコール酸オクチル、チオグリセロール等のメルカプタン類等が挙げられる。これらは単独でもしくは２種以上併せて用いられる。 Examples of polymerization regulators 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.
　重合調整剤の使用量は、適宜調整されればよいが、モノマー１００質量部に対して、０．０１質量部以上であることが好ましく、０．０５質量部以上であることがより好ましく、０．１質量部以上であることがさらに好ましい。重合調整剤の使用量は、モノマー１００質量部に対して、１０質量部以下であることが好ましく、５質量部以下であることがより好ましく、３質量部以下であることがさらに好ましい。重合調整剤の使用量は、モノマー１００質量部に対して、０．０１質量部以上１０質量部以下であることが好ましく、０．０５質量部以上５質量部以下であることがより好ましく、０．１質量部以上３質量部以下であることがさらに好ましい。 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.
　架橋剤は使用してもよいが、使用しないこと（すなわち、高分子微粒子分散体として含有する樹脂は、架橋剤を含有しないこと）が好ましい。架橋剤を含有しない共重合体を高分子微粒子分散体として水性インク組成物中に分散させることにより、共重合体の分散安定性を向上させることが可能となって、結果として保存安定性をさらに向上させることが可能となる。 Although 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). By dispersing a copolymer that does not contain a crosslinking agent as a polymer fine particle dispersion in an aqueous ink composition, it is possible to improve the dispersion stability of the copolymer, and as a result, the storage stability can be further improved. It becomes possible to improve the performance.
　架橋剤を含有する場合、架橋剤としては、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジドなどの脂肪族ジヒドラジドの他、炭酸ポリヒドラジド、脂肪族、脂環族、芳香族ビスセミカルバジド、芳香族ジカルボン酸ジヒドラジド、ポリアクリル酸のポリヒドラジド、芳香族炭化水素のジヒドラジド、ヒドラジン－ピリジン誘導体およびマレイン酸ジヒドラジドなどの不飽和ジカルボン酸のジヒドラジドなどが挙げられる。 When containing 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.
　架橋剤の使用量は、適宜調整されればよいが、モノマー１００質量部に対して、２質量部未満であることが好ましく、１質量部未満であることがより好ましく、０．５質量部未満であることがさらに好ましい。 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
　中和剤は、例えば、モノマーＢに由来する酸性基または塩基性基を中和するのに使用される。共重合体が酸性基または塩基性基を有するモノマーＢを構成単位として含む場合、モノマーＢに由来する酸性基または塩基性基を中和することで（すなわち、共重合体は、中和された酸性基または塩基性基を有するモノマーＢを構成単位として含むことで）、本発明の効果をより効果的に奏する水性インク組成物となる。 The neutralizing agent is used, for example, to neutralize acidic groups or basic groups derived from monomer B. When the copolymer contains a monomer B having an acidic group or a basic group as a constitutional unit, by neutralizing the acidic group or basic group derived from the monomer B (i.e., the copolymer is By including monomer B having an acidic group or a basic group as a structural unit), an aqueous ink composition that exhibits the effects of the present invention more effectively can be obtained.
　モノマーＢに由来する塩基性基を中和する酸としては、塩酸、硝酸、リン酸、硫酸等の無機酸や、ギ酸、酢酸、プロピオン酸、安息香酸、こはく酸、酪酸、フマル酸、パラトルエンスルホン酸、クエン酸、シュウ酸等の有機酸等を挙げることができる。このなかでも低温乾燥時の耐溶剤性の観点から安息香酸を使用することが好ましい。 Examples of 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. Among these, benzoic acid is preferably used from the viewpoint of solvent resistance during low temperature drying.
　モノマーＢに由来する酸性基を中和する塩基としては、アルカリ金属水酸化物、アルカリ土類金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩等の無機塩基や、アンモニア、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、エタノールアミン、イソプロピルアミン、プロパノールアミン、２－メチル－２－アミノプロパノール、ジエタノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ－メチルジエタノールアミン、ジメチルアミン、トリエチルアミンジブチルアミン、Ｎ，Ｎ－ジエチルエタノールアミン、Ｎ，Ｎ－ジブチルアミノエタノール、Ｎ－（β－アミノエチル）エタノールアミン、Ｎ－メチルエタノールアミン、２－エチルアミノエタノール、モノ－ｎ－ブチルエタノールアミン、モノ－ｎ－ブチルジエタノールアミン、ｎ－ターシャリーブチルジエタノールアミン、３－メチル－２－オキサゾリジノン、ｎ－（２－ヒドロキシエチル）モルフォリン、アミノメチルプロパンジオール、アミノエチルプロパンジオール、２－（ジメチルアミノメチル）－２－プロパノール、トリ（ヒドロキシメチル）アミノメタン、ＤＬ－２－アミノ－１－ブタノール、３－アミノ－４－オクタノール、トリエタノールアミントリス（２－ヒドロキシエチル）アミン、等のアミン類が挙げられる。このなかでも低温乾燥時の耐溶剤性の観点からアンモニア、Ｎ，Ｎ－ジメチルエタノールアミンを使用することが好ましい。 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. , ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, isopropylamine, propanolamine, 2-methyl-2-aminopropanol, diethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine, dimethylamine, Triethylamine dibutylamine, N,N-diethylethanolamine, N,N-dibutylaminoethanol, N-(β-aminoethyl)ethanolamine, N-methylethanolamine, 2-ethylaminoethanol, mono-n-butylethanolamine , mono-n-butyldiethanolamine, n-tert-butyldiethanolamine, 3-methyl-2-oxazolidinone, n-(2-hydroxyethyl)morpholine, aminomethylpropanediol, aminoethylpropanediol, 2-(dimethylaminomethyl )-2-propanol, tri(hydroxymethyl)aminomethane, DL-2-amino-1-butanol, 3-amino-4-octanol, triethanolamine tris(2-hydroxyethyl)amine, etc. It will be done. Among these, ammonia and N,N-dimethylethanolamine are preferably used from the viewpoint of solvent resistance during low temperature drying.
　本実施の形態に係る水性インク組成物に含有されるアクリル樹脂は、このようにして得られたモノマーＡ、モノマーＢ、モノマーＣなどの少なくとも２種類のモノマーを構成単位として含む共重合体を含む、モノマーＡ、モノマーＢ、モノマーＣなどの少なくとも２種類のモノマーの種類や含有量を適宜変更することで、アクリル樹脂のＴｇを制御することができる。 The acrylic resin contained in the aqueous ink composition according to the present embodiment includes a copolymer containing at least two types of monomers such as monomer A, monomer B, and monomer C obtained in this manner as constituent units. The Tg of the acrylic resin can be controlled by appropriately changing the types and contents of at least two types of monomers, such as monomer A, monomer B, and monomer C.
　この共重合体を含有するアクリル系樹脂のＴｇは、０℃以上１２０℃以下である。アクリル系樹脂のＴｇが０℃未満であると、得られる記録物の耐擦性が低下する。アクリル系樹脂のＴｇが１２０℃超であると、十分に成膜することができなくなり、得られる記録物の耐溶剤性が低下する。 The Tg of the acrylic resin containing this copolymer is 0°C or more and 120°C or less. If the Tg of the acrylic resin is less than 0° C., the abrasion resistance of the resulting recorded matter will decrease. If the Tg of the acrylic resin exceeds 120° C., sufficient film formation will not be possible, and the solvent resistance of the resulting recorded product will decrease.
　なお、この共重合体を含有するアクリル系樹脂のＴｇは、２０℃以上であることが好ましく、３０℃以上であることがより好ましく、４０℃以上であることがさらに好ましい。この共重合体を含有するアクリル系樹脂のＴｇは、１００℃以下であることが好ましく、９０℃以下であることがより好ましく、８０℃以下であることがさらに好ましい。共重合体を含有するアクリル系樹脂のＴｇは、２０℃以上１００℃以下であることが好ましく、３０℃以上９０℃以下であることがより好ましく、４０℃以上８０℃以下であることがさらに好ましい。 Note that the Tg of the acrylic resin containing this copolymer is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 40°C or higher. The Tg of the acrylic resin containing this copolymer is preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 80°C or lower. The Tg of the acrylic resin containing the copolymer is preferably 20°C or more and 100°C or less, more preferably 30°C or more and 90°C or less, and even more preferably 40°C or more and 80°C or less. .
　少なくとも２種類のモノマーを構成単位として含む共重合体に含まれるモノマーの配列は、モノマーの配列に秩序のないランダム共重合体であっても、同種の単量体が長く連続したブロック共重合体であっても、枝状にモノマーが配列したグラフト共重合体であってもよいが、ランダム共重合体であることが好ましい。少なくとも２種類のモノマーを構成単位として含むランダム共重合体を高分子微粒子分散体として水性インク組成物中に分散させることにより、共重合体の分散安定性を向上させることが可能となって、水性インク組成物をインクジェット方式により基材の表面に吐出する場合には、吐出安定性を高めることが可能となる。 The arrangement of monomers contained in a copolymer containing at least two types of monomers as constituent units is a block copolymer with long continuous monomers of the same type, even if it is a random copolymer with no order in the arrangement of monomers. Although it may be a graft copolymer in which monomers are arranged in a branched manner, a random copolymer is preferable. By dispersing a random copolymer containing at least two types of monomers as constituent units into an aqueous ink composition as a polymer fine particle dispersion, it is possible to improve the dispersion stability of the copolymer, and it is possible to improve the dispersion stability of the copolymer. When the ink composition is ejected onto the surface of the base material by an inkjet method, ejection stability can be improved.
　樹脂が高分子微粒子分散体として含有する場合、高分子微粒子分散体の平均粒子径は、インク組成物中での分散安定性と、インクジェット吐出性の観点から、１０ｎｍ以上が好ましく、２０ｎｍ以上がより好ましく、３０ｎｍ以上がさらに好ましい。高分子微粒子分散体の平均粒子径は、インク組成物中での分散安定性と、インクジェット吐出性の観点から、５００ｎｍ以下が好ましく、３５０ｎｍ以下がより好ましく、２５０ｎｍ以下がさらに好ましい。高分子微粒子分散体の平均粒子径は、１０ｎｍ以上５００ｎｍ以下が好ましく、２０ｎｍ以上３５０ｎｍ以下がより好ましく、３０ｎｍ以上２５０ｎｍ以下がさらに好ましい。なお、高分子微粒子分散体の平均粒子径は、測定温度２５℃にて濃厚系粒径アナライザー（大塚電子（株）製、型式：ＦＰＡＲ－１０００）を用いて測定することができる。 When the resin is contained as a polymer fine particle dispersion, 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.
　高分子微粒子分散体の重量平均分子量は、耐溶剤性の観点から、５０００以上が好ましく、１００００以上がより好ましく、１０００００以上がさらに好ましい。高分子微粒子分散体の重量平均分子量は、水性インク組成物の保存安定性の観点から、２００００００以下が好ましく、１７５００００以下がより好ましく、１５０００００以下がより好ましい。高分子微粒子分散体の重量平均分子量は、５０００以上２００００００以下が好ましく、１００００以上１７５００００以下がより好ましく、１０００００以上１５０００００以下がさらに好ましい。なお、本実施形態において樹脂の分子量は、重量平均分子量Ｍｗを示すものであり、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定された値であり、東ソー（株）製の「ＨＬＣ－８１２０ＧＰＣ」にて、校正曲線用ポリスチレンスタンダードを標準にして測定することができる。 From the viewpoint of solvent resistance, 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. The weight average molecular weight of the polymer fine particle dispersion is preferably 2,000,000 or less, more preferably 1,750,000 or less, and even more preferably 1,500,000 or less from the viewpoint of storage stability of the aqueous ink composition. 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, and even more preferably 100,000 or more and 1,500,000 or less. In this embodiment, 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. , can be measured using a polystyrene standard for calibration curves as a standard.
　少なくとも２種類のモノマーを構成単位として含む共重合体は、従来公知の重合方法により得てもよいが、市販の樹脂のうち、２種類のモノマーを構成単位として含む共重合体を含むものを入手して得てもよい。 Copolymers containing at least two types of monomers as constituent units may be obtained by conventionally known polymerization methods, but commercially available resins containing copolymers containing two types of monomers as constituent units may be obtained. You can also get it by doing so.
　また、本実施の形態に係る水性インク組成物は、少なくとも２種類のモノマーを構成単位として含む共重合体とは異なる樹脂を含有してもよい。樹脂としては、具体的には、上記の共重合体とは異なるアクリル系樹脂（スチレン－アクリル系樹脂等のような共重合体も含む）、ポリウレタン系樹脂、ポリエステル系樹脂、塩化ビニル系樹脂、酢酸ビニル系樹脂、ポリエーテル系樹脂、塩化ビニル酢酸ビニル共重合樹脂、ポリエチレン系樹脂、アクリルアミド系樹脂、エポキシ系樹脂、ポリカーボネート系樹脂、シリコーン系樹脂、ポリスチレン系樹脂からなる群より選択される１つ以上の樹脂あるいは共重合樹脂を含むものあるいはこれらの混合物を含むものを用いることができる。 Furthermore, the aqueous ink composition according to the present embodiment may contain a resin different from the copolymer containing at least two types of monomers as constituent units. Specifically, 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.
　市販の高分子微粒子分散体としては、例えば、アクリットＷＥＭ－０３１Ｕ、ＷＥＭ－２００Ｕ、ＷＥＭ－３２１、ＷＥＭ－３０００、ＷＥＭ－２０２Ｕ、ＷＥＭ－３００８、（大成ファインケミカル（株）製、アクリル－ウレタン樹脂エマルジョン）、アクリットＵＷ－５５０ＣＳ、ＵＷ－２２３ＳＸ、ＡＫＷ１０７、ＲＫＷ－５００（大成ファインケミカル（株）製、アクリル樹脂エマルジョン）、ＬＵＢＲＩＪＥＴ　Ｎ２４０（ルーブリゾール製、アクリル樹脂エマルジョン）、スーパーフレックス１５０、２１０、４７０、５００Ｍ、６２０、６５０、Ｅ２０００、Ｅ４８００、Ｒ５００２（第一工業製薬（株）製、ウレタン樹脂エマルジョン）、ビニブラン７０１ＦＥ３５、７０１ＦＥ５０、７０１ＦＥ６５、７００、７０１、７１１、７３７、７４７（日信化学（株）製、塩化ビニル－アクリル樹脂エマルジョン）、ビニブラン２７０６、２６８５（日信化学（株）製、アクリル樹脂エマルジョン）、モビニール７４３Ｎ、６５２０、６６００、６８２０、７４７０、７７２０、（ジャパンコーティングレジン社製、アクリル樹脂エマルジョン）、ＰＲＩＭＡＬ　ＡＣ-２６１Ｐ、　ＡＣ-８１８（ダウ・ケミカル社製　アクリル樹脂エマルジョン）、ＪＥ－１０５６（星光ＰＭＣ社製　アクリル樹脂エマルジョン）、ＮｅｏＣｒｙｌ　ＸＫ－１９０（ＤＳＭ　Ｃｏａｔｉｎｇ　Ｒｅｓｉｎ社製　アクリル樹脂エマルジョン）、ＮｅｏＣｒｙｌ　Ａ２０９１、Ａ２０９２、Ａ６３９、Ａ６５５、Ａ６６２（ＤＳＭ　Ｃｏａｔｉｎｇ　Ｒｅｓｉｎ社製　スチレン－アクリル樹脂エマルジョン）、ＱＥ－１０４２、ＫＥ－１０６２（星光ＰＭＣ社製　スチレン－アクリル樹脂エマルジョン）、ＪＯＮＣＲＹＬ７１９９、ＰＤＸ－７６３０Ａ（ＢＡＳＦジャパン社製　スチレン－アクリル樹脂エマルジョン）、シャリーヌＲ１７０ＢＸ（日信化学工業社製　シリコーン－アクリル樹脂エマルジョン）、タケラックＷ－６０１０（三井化学社製　ウレタン樹脂エマルジョン）、エリーテル ＫＡ-５０７１Ｓ（ユニチカ社製　ポリエステル樹脂エマルジョン）、ポリゾールＡＰ-１３５０（昭和電工社製　アクリル樹脂エマルジョン）等を例示することができるが、これらに限定されるものではない。 Commercially available 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 (manufactured by Nissin Chemical Co., Ltd.), Vinyl chloride-acrylic resin emulsion), Vinyblan 2706, 2685 (Nissin Chemical Co., Ltd., acrylic resin emulsion), Movinyl 743N, 6520, 6600, 6820, 7470, 7720, (Japan Coating Resin Co., Ltd., acrylic resin emulsion) , PRIMAL AC-261P, AC-818 (acrylic resin emulsion manufactured by Dow Chemical), JE-1056 (acrylic resin emulsion manufactured by Seiko PMC), NeoCryl XK-190 (acrylic resin emulsion manufactured by DSM Coating Resin), Neo Cryl A2091 , A2092, A639, A655, A662 (DSM Coating Resin, styrene-acrylic resin emulsion), QE-1042, KE-1062 (Seiko PMC, styrene-acrylic resin emulsion), JONCRYL7199, PDX-7630A (BASF Jaguar) Manufactured by Pan Company styrene-acrylic resin emulsion), Chaline R170BX (Silicone-acrylic resin emulsion manufactured by Nissin Chemical Industries, Ltd.), Takelac W-6010 (urethane resin emulsion manufactured by Mitsui Chemicals), ELITEL KA-5071S (polyester resin emulsion manufactured by Unitika), Examples include Polysol AP-1350 (acrylic resin emulsion manufactured by Showa Denko K.K.), but are not limited thereto.
　少なくとも２種類のモノマーを構成単位として含む共重合体を含む樹脂の含有量は、特に限定されるものではないが、樹脂の含有量の下限は、水性インク組成物全量中０．０５質量％以上であることが好ましく、０．１質量％以上であることがより好ましく、０．５質量％以上であることがさらに好ましく、１質量％以上がさらになお好ましい。樹脂の含有量の上限は、水性インク組成物全量中２０質量％以下であることが好ましく、中でも、１７．５質量％以下であることがより好ましく、１５質量％以下であることがさらに好ましい。樹脂の含有量の範囲は、水性インク組成物全量中０．０５質量％以上２０質量％以下であることが好ましく、０．１質量％以上１７．５質量％以下であることがより好ましく、更に０．５質量％以上１５質量％以下であることがさらに好ましく、１質量％以上１５質量％以下がさらになお好ましい。 The content of the resin containing the copolymer containing at least two types of monomers 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. The content 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 based on the total amount of the aqueous ink composition, more preferably 17.5% by mass or less, and even more preferably 15% by mass or less. The content range of the resin is preferably 0.05% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 17.5% by mass or less, based on the total amount of the aqueous ink composition. It is more preferably 0.5% by mass or more and 15% by mass or less, even more preferably 1% by mass or more and 15% by mass or less.
　［水］
　本実施の形態に係る水性インク組成物は、水を含有する。水としては、種々のイオンを含有するものではなく、脱イオン水を使用することが好ましい。水の含有量としては、各成分を分散又は溶解可能なものであれば特に限定されるものではないが、水の含有量の下限は、水性インク組成物全量中３０質量％以上の範囲内であることが好ましく、４５質量％以上の範囲内であることがより好ましく、５０質量％以上の範囲内であることがさらに好ましい。水の含有量の上限は、水性インク組成物全量中８５質量％以下の範囲内であることが好ましく、８０質量％以下の範囲内であることがより好ましく、７５質量％以下の範囲内であることがさらに好ましい。水の含有量の範囲は、水性インク組成物全量中３０質量％以上８５質量％以下の範囲内であることが好ましく、４５質量％以上８０質量％以下の範囲内であることがより好ましく、５０質量％以上７５質量％以下の範囲内であることがさらに好ましい。 [water]
The aqueous ink composition according to this embodiment contains water. As 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.
　［水溶性溶媒］
　本実施の形態に係る水性インクは、水溶性溶媒を含有してもよい。溶媒は、色材等を分散又は溶解することができるものである。なお、本明細書において「水溶性溶媒」とは、主に水溶性有機溶媒を意味し、また含有成分の少なくとも一部を分散する分散媒であってもよい。 [Water-soluble solvent]
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. In addition, in this specification, the "water-soluble solvent" mainly means a water-soluble organic solvent, and may also be a dispersion medium that disperses at least a part of the contained components.
　水溶性溶媒としては、メチルアルコール、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、ｓｅｃ－ブチルアルコール、ｔｅｒｔ－ブチルアルコール、イソブチルアルコール、ｎ－ペンタノール等の炭素数１～５のアルキルアルコール類；３－メトキシ－１－ブタノール、３－メトキシ－３－メチル－１－ブタノール、３－メトキシ－１－プロパノール、１－メトキシ－２－プロパノール、３－メトキシ－ｎ－ブタノール等の１価のアルコール類；ホルムアミド、アセトアミド、プロパンアミド、ブタンアミド、イソブチルアミド、ペンタンアミド、Ｎ－メチルホルムアミド、Ｎ－メチルアセトアミド、Ｎ－メチルプロパンアミド、Ｎ－メチルブタンアミド、Ｎ－メチルイソブチルアミド、Ｎ－メチルペンタンアミド、Ｎ－エチルホルムアミド、Ｎ－エチルアセトアミド、Ｎ－エチルプロパンアミド、Ｎ－エチルブタンアミド、Ｎ－エチルイソブチルアミド、Ｎ－エチルペンタンアミド、Ｎ－プロピルホルムアミド、Ｎ－プロピルアセトアミド、Ｎ－プロピルプロパンアミド、Ｎ－プロピルブタンアミド、Ｎ－プロピルイソブチルアミド、Ｎ－プロピルペンタンアミド、Ｎ－イソプロピルホルムアミド、Ｎ－イソプロピルアセトアミド、Ｎ－イソプロピルプロパンアミド、Ｎ－イソプロピルブタンアミド、Ｎ－イソプロピルイソブチルアミド、Ｎ－イソプロピルペンタンアミド、Ｎ－ブチルホルムアミド、Ｎ－ブチルアセトアミド、Ｎ－ブチルプロパンアミド、Ｎ－ブチルブタンアミド、Ｎ－ブチルイソブチルアミド、Ｎ－ブチルペンタンアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルプロパンアミド、Ｎ，Ｎ－ジメチルブタンアミド、Ｎ，Ｎ－ジメチルイソブチルアミド、Ｎ，Ｎ－ジメチルペンタンアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジエチルプロパンアミド、Ｎ，Ｎ－ジエチルブタンアミド、Ｎ，Ｎ－ジエチルイソブチルアミド、Ｎ，Ｎ－ジエチルペンタンアミド、Ｎ，Ｎ－ジプロピルホルムアミド、Ｎ，Ｎ－ジプロピルアセトアミド、Ｎ，Ｎ－ジプロピルプロパンアミド、Ｎ，Ｎ－ジプロピルブタンアミド、Ｎ，Ｎ－ジプロピルイソブチルアミド、Ｎ，Ｎ－ジプロピルペンタンアミド、Ｎ，Ｎ－ジイソプロピルホルムアミド、Ｎ，Ｎ－ジイソプロピルアセトアミド、Ｎ，Ｎ－ジイソプロピルプロパンアミド、Ｎ，Ｎ－ジイソプロピルブタンアミド、Ｎ，Ｎ－ジイソプロピルイソブチルアミド、Ｎ，Ｎ－ジイソプロピルペンタンアミド、Ｎ，Ｎ－ジブチルホルムアミド、Ｎ，Ｎ－ジブチルアセトアミド、Ｎ，Ｎ－ジブチルプロパンアミド、Ｎ，Ｎ－ジブチルブタンアミド、Ｎ，Ｎ－ジブチルイソブチルアミド、Ｎ，Ｎ－ジブチルペンタンアミド、Ｎ－エチル－Ｎ－メチルホルムアミド、Ｎ－エチル－Ｎ－メチルアセトアミド、Ｎ－エチル－Ｎ－メチルプロパンアミド、Ｎ－エチル－Ｎ－メチルブタンアミド、Ｎ－エチル－Ｎ－メチルイソブチルアミド、Ｎ－エチル－Ｎ－メチルペンタンアミド、Ｎ－メチル－Ｎ－プロピルホルムアミド、Ｎ－メチル－Ｎ－プロピルアセトアミド、Ｎ－メチル－Ｎ－プロピルプロパンアミド、Ｎ－メチル－Ｎ－プロピルブタンアミド、Ｎ－メチル－Ｎ－プロピルイソブチルアミド、Ｎ－メチル－Ｎ－プロピルペンタンアミド、Ｎ－エチル－Ｎ－プロピルホルムアミド、Ｎ－エチル－Ｎ－プロピルアセトアミド、Ｎ－エチル－Ｎ－プロピルプロパンアミド、Ｎ－メチル－Ｎ－（１－メチルエチル）ホルムアミド、Ｎ－ヒドロキシプロピル－Ｎ－メチルアセトアミド、Ｎ－エチル－Ｎ－プロピルブタンアミド、Ｎ－エチル－Ｎ－プロピルイソブチルアミド、Ｎ－エチル－Ｎ－プロピルペンタンアミド、３－メチル－２－オキサゾリジノン、３－エチル－２－オキサゾリジノン、Ｎ－ビニルメチルオキサゾリジノン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－メトキシプロパンアミド、３－ブトキシプロパンアミド、Ｎ，Ｎ－ジブチル－３－メトキシプロパンアミド、Ｎ，Ｎ－ジブチル－３－ブトキシプロパンアミド、Ｎ，Ｎ－ジメチル－３－ブトキシプロパンアミド等のアミド類；アセトン、ジアセトンアルコール、テキサノール等のケトン又はケトアルコール類；テトラヒドロフラン、ジオキサン（１，４－ジオキサン等を含む。）等のエーテル類；ポリエチレングリコール、ポリプロピレングリコール等のオキシエチレン又はオキシプロピレン共重合体；エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、イソブチレングリコール、トリエチレングリコール、トリプロピレングリコール、テトラエチレングリコール、１，３－プロパンジオール、２－メチル－１，２－プロパンジオール、２－メチル－１，２－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，２－ペンタンジオール、１，３－ペンタンジオール、１，２－ヘキサンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、３－メチル－１，３－ブタンジオール、３－メチル－１，５－ペンタンジオール、２－メチル－２，４－ペンタンジオール等のジオール類；グリセリン、トリメチロールエタン、トリメチロールプロパン、１，２，６－ヘキサントリオール等のトリオール類：メソエリスリトール、ペンタエリスリトール等の４価アルコール類；エチレングリコールモノメチル（又はエチル、イソプロピル、ｎ－ブチル、イソブチル、ｎ－ヘキシル、２－エチルヘキシル）エーテル、ジエチレングリコールモノメチル（又はエチル、イソプロピル、ｎ－ブチル、イソブチル、ｎ－ヘキシル、２－エチルヘキシル）エーテル、トリエチレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテル、プロピレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテル、ジプロピレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテル、トリプロピレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテル、テトラエチレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテル等のモノアルキルエーテル類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、トリエチレングリコールエチルメチルエーテル、テトラエチレングリコールジメチルエーテル、テトラエチレングリコールジエチルエーテル、テトラエチレングリコールエチルメチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールエチルメチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールエチルメチルエーテル、トリプロピレングリコールジメチルエーテル、トリプロピレングリコールジエチルエーテル、トリプロピレングリコールエチルメチルエーテル等の多価アルコールのジアルキルエーテル類；エチレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテルアセテート、ジエチレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテルアセテート、トリエチレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテルアセテート、プロピレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテルアセテート、ジプロピレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテルアセテート、トリプロピレングリコールモノメチル（又はエチル、プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ｎ－ヘキシル、２－エチルヘキシル）エーテルアセテート、エチレングリコールジアセテート、ジエチレングリコールジアセテート、プロピレングリコールジアセテート、ジプロピレングリコールジアセテート等のアセテート類；γ－ブチロラクトン、α－メチレン－γ－ブチロラクトン、ε－カプロラクトン、γ－バレロラクトン、γ－ヘキサノラクトン、γ－ヘプタノラクトン、δ－バレロラクトン、δ－ヘキサノラクトン、δ－ヘプタラクトン、δ－オクタラクトン、δ－ノナラクトン、δ－デカラクトン、δ－ウンデカラクトン、γ,γ－ジメチル－γ－ブチロラクトン、α－メチル－γ－ブチロラクトン、γ－クロトラクトン、α－メチレン－γ－ブチロラクトン、β－メチル－γ－ブチロラクトン、６-メチルバレロラクトン等のラクトン類、２，３-ブチレンカーボネート、エチレンカーボネート、プロピレンカーボネート等の炭酸エステル類、酢酸メチル、酢酸エチル、酢酸－ｎ－プロピル、酢酸イソプロピル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸ヘキシル、酢酸オクチル等の酢酸エステル類、乳酸メチル、乳酸エチル、乳酸ブチル、乳酸プロピル、乳酸エチルヘキシル、乳酸アミル、乳酸イソアミル等の乳酸エステル類、シュウ酸ジメチル、シュウ酸ジエチル、マロン酸ジメチル、マロン酸ジエチル、マロン酸ジプロピル、コハク酸ジメチル、コハク酸ジエチル、グルタル酸ジメチル、グルタル酸ジエチルなどの二塩基酸エステル類、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ－メチルエタノールアミン、Ｎ－エチルエタノールアミン、Ｎ－ブチルエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、Ｎ－ブチルジエタノールアミン等のアルカノールアミン類、ｎ－ヘキサン、イソヘキサン、ｎ－ノナン、イソノナン、ドデカン、イソドデカン等の飽和炭水素類、１－ヘキセン、１－ヘプテン、１－オクテン等の不飽和炭化水素類、シクロヘキサン、シクロヘプタン、シクロオクタン、シクロデカン、デカリン等の環状飽和炭化水素類、シクロヘキセン、シクロヘプテン、シクロオクテン、１，１，３，５，７－シクロオクタテトラエン、シクロドデセン等の環状不飽和炭化水素類、ベンゼン、トルエン、キシレン等の芳香族炭化水素類；Ｎ－メチル－２－ピロリドン、２－ピロリドン、β－ラクタム、δ－ラクタム、ε－カプロラクタム、Ｎ－メチル－イプシロン－カプロラクタム、２－ヒドロキシルエチルピロリドン、Ｎ－２－ヒドロキシエチル－２－ピロリドン、３－メチル－２－ピロリジノン、１，３－ジメチル－２－イミダゾリジノン等の含窒素複素環化合物；スルホラン等の環状化合物、Ｎ－メチルモルホリン、Ｎ－エチルモルホリン、Ｎ－ホルミルモルホリン、Ｎ－ヒドロキシエチルモルホリン、２－ヒドロキシルエチルモルフォリン、４－アセチルモルホリンなどのモルホリン類、テルペン系溶剤などが挙げられる。これらの単独、又はそれらを２種以上併用して用いることができる。この中でも、水性インクが所望の静的表面張力になるように水溶性溶媒を選択することが好ましく、例えばアルカンジオール類の水溶性溶媒を少なくとも１種含むことが好ましい。 Examples of 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. Alcohols; formamide, acetamide, propanamide, butanamide, isobutyramide, pentanamide, N-methylformamide, N-methylacetamide, N-methylpropanamide, N-methylbutanamide, N-methylisobutyramide, N- Methylpentanamide, N-ethylformamide, N-ethylacetamide, N-ethylpropanamide, N-ethylbutanamide, N-ethylisobutyramide, N-ethylpentanamide, N-propylformamide, N-propylacetamide, N- Propylpropanamide, N-propylbutanamide, N-propylisobutyramide, N-propylpentanamide, N-isopropylformamide, N-isopropylacetamide, N-isopropylpropanamide, N-isopropylbutanamide, N-isopropylisobutyramide, N-isopropylpentanamide, N-butylformamide, N-butylacetamide, N-butylpropanamide, N-butylbutanamide, N-butylisobutylamide, N-butylpentanamide, N,N-dimethylformamide, N,N -dimethylacetamide, N,N-dimethylpropanamide, N,N-dimethylbutanamide, N,N-dimethylisobutyramide, N,N-dimethylpentanamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-diethylpropanamide, N,N-diethylbutanamide, N,N-diethylisobutyramide, N,N-diethylpentanamide, N,N-dipropylformamide, N,N-dipropylacetamide, N, N-dipropylpropanamide, N,N-dipropylbutanamide, N,N-dipropylisobutyramide, N,N-dipropylpentanamide, N,N-diisopropylformamide, N,N-diisopropylacetamide, N, N-diisopropylpropanamide, N,N-diisopropylbutanamide, N,N-diisopropylisobutyramide, N,N-diisopropylpentanamide, N,N-dibutylformamide, N,N-dibutylacetamide, N,N-dibutylpropane Amide, N,N-dibutylbutanamide, N,N-dibutylisobutyramide, N,N-dibutylpentanamide, N-ethyl-N-methylformamide, N-ethyl-N-methylacetamide, N-ethyl-N- Methylpropanamide, N-ethyl-N-methylbutanamide, N-ethyl-N-methylisobutyramide, N-ethyl-N-methylpentanamide, N-methyl-N-propylformamide, N-methyl-N-propyl Acetamide, N-methyl-N-propylpropanamide, N-methyl-N-propylbutanamide, N-methyl-N-propylisobutyramide, N-methyl-N-propylpentanamide, N-ethyl-N-propylformamide , N-ethyl-N-propylacetamide, N-ethyl-N-propylpropanamide, N-methyl-N-(1-methylethyl)formamide, N-hydroxypropyl-N-methylacetamide, N-ethyl-N- Propyl butanamide, N-ethyl-N-propylisobutyramide, N-ethyl-N-propylpentanamide, 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, N-vinylmethyloxazolidinone, 3-methoxy- N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxypropanamide, 3-butoxypropanamide, N,N-dibutyl-3-methoxypropanamide, N,N-dibutyl- Amides such as 3-butoxypropanamide and N,N-dimethyl-3-butoxypropanamide; ketones or keto alcohols such as acetone, diacetone alcohol, and texanol; tetrahydrofuran, dioxane (including 1,4-dioxane, 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-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol; glycerin, trimethylol Triols such as ethane, trimethylolpropane, and 1,2,6-hexanetriol; Tetrahydric alcohols such as mesoerythritol and pentaerythritol; Ethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl) ether, diethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl) ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t- butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, propylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, dipropylene glycol Monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, tripropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t -butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, tetraethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, etc. 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 glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, diethylene glycol monomethyl ( or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t- Butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, propylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, Propylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, tripropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, Acetates such as isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether acetate, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate; γ-butyrolactone, α-methylene - γ-butyrolactone, ε-caprolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, δ-valerolactone, δ-hexanolactone, δ-heptalactone, δ-octalactone, δ-nonalactone , δ-decalactone, δ-undecalactone, γ,γ-dimethyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-crotolactone, α-methylene-γ-butyrolactone, β-methyl-γ-butyrolactone, Lactones such as 6-methylvalerolactone, carbonate esters such as 2,3-butylene carbonate, ethylene carbonate, propylene carbonate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Acetate esters such as isobutyl, hexyl acetate, octyl acetate, methyl lactate, ethyl lactate, butyl lactate, propyl lactate, ethylhexyl lactate, amyl lactate, isoamyl lactate, dimethyl oxalate, diethyl oxalate, dimethyl malonate , dibasic acid esters such as diethyl malonate, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N- Alkanolamines such as ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N-butyldiethanolamine, and saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, and isododecane. 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, cyclounsaturated hydrocarbons such as cyclododecene, aromatic hydrocarbons such as benzene, toluene, xylene; N-methyl-2-pyrrolidone, 2-pyrrolidone, β-lactam , δ-lactam, ε-caprolactam, N-methyl-epsilon-caprolactam, 2-hydroxylethylpyrrolidone, N-2-hydroxyethyl-2-pyrrolidone, 3-methyl-2-pyrrolidinone, 1,3-dimethyl-2- Nitrogen-containing heterocyclic compounds such as imidazolidinone; cyclic compounds such as sulfolane, N-methylmorpholine, N-ethylmorpholine, N-formylmorpholine, N-hydroxyethylmorpholine, 2-hydroxylethylmorpholine, 4-acetylmorpholine, etc. Examples include morpholines and terpene solvents. These can be used alone or in combination of two or more. Among these, it is preferable to select a water-soluble solvent so that the aqueous ink has a desired static surface tension, and preferably contains at least one water-soluble solvent such as an alkanediol, for example.
　水溶性溶媒の含有量としては、各成分を分散又は溶解可能なものであれば特に限定されるものではないが、水溶性溶媒の含有量の下限は、水性インク全量中５質量％以上の範囲内であることが好ましく、１０質量％以上の範囲内であることがより好ましく、１２質量％以上の範囲内であることがさらに好ましい。水溶性溶媒の含有量の上限は、水性インク全量中５０質量％以下の範囲内であることが好ましく、４５質量％以下の範囲内であることがより好ましく、４０質量％以下の範囲内であることがさらに好ましい。水溶性溶媒の含有量の範囲は、水性インク全量中５質量％以上５０質量％以下の範囲内であることが好ましく、１０質量％以上４５質量％以下の範囲内であることがより好ましく、１２質量％以上４０質量％以下の範囲内であることがさらに好ましい。 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 10% by mass or more and 45% by mass or less, based on the total amount of the water-based ink. It is more preferably within the range of 40% by mass or more.
　［色材］
　本実施の形態に係る水性インク組成物には色材を含有してもよい。本実施の形態に係るインク組成物は、色材を含有することは必須の構成ではないが、色材を含有することで、所望の画像パターンを形成するような着色インクにすることや、その下地層となるようなホワイトインクやメタリックインク等にすることが可能となる。色材としては、染料であっても顔料であってもよい。 [Color material]
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.
　本実施の形態に係る水性インク組成物において、使用することのできる顔料は特に限定されず、従来の水性インク組成物に使用されている有機顔料又は無機顔料等が挙げられる。これらは１種単独で用いても、２種以上を組み合わせて用いてもよい。なお、本実施の形態に係る水性インク組成物は、色材を含有しなくともよい。本実施の形態に係る水性インク組成物において顔料を用いる場合には、分散剤や分散助剤（顔料誘導体）を使用することで、顔料の分散安定性を向上させることができる。また、樹脂の中に顔料または染料を含ませて使用してもよい。 In the aqueous ink composition according to this embodiment, 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. When a pigment is used in the aqueous ink composition according to the present embodiment, 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.
　顔料としては、従来水性インク組成物に使用されている無機顔料、又は有機顔料等が挙げられる。これらは１種単独で用いても、２種以上を組み合わせて用いてもよい。具体的な有機顔料としては、例えば、不溶性アゾ顔料、溶性アゾ顔料、染料からの誘導体、フタロシアニン系有機顔料、キナクリドン系有機顔料、ペリレン系有機顔料、ペリノン系有機顔料、アゾメチン系有機顔料、アントラキノン系有機顔料（アントロン系有機顔料）、キサンテン系有機顔料、ジケトピロロピロール系有機顔料、ジオキサジン系有機顔料、ニッケルアゾ系顔料、イソインドリノン系有機顔料、ピランスロン系有機顔料、チオインジゴ系有機顔料、縮合アゾ系有機顔料、ベンズイミダゾロン系有機顔料、キノフタロン系有機顔料、イソインドリン系有機顔料、キナクリドン系固溶体顔料、ペリレン系固溶体顔料等の有機固溶体顔料、その他の顔料として、レーキ顔料やカーボンブラック等が挙げられる。 Examples of the pigment 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.
　有機顔料をカラーインデックス（Ｃ．Ｉ．）ナンバーで例示すると、Ｃ．Ｉ．ピグメントイエロー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．ピグメントレッド５、７、９、１２、４８、４８：２、４８：３、４９、５２、５３、５７、５７：１、９７、１１２、１２２、１２３、１４６、１４９、１５０、１６８、１７６、１７７、１８０、１８４、１８５、１９２、２０２、２０６、２０８、２０９、２１３、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２３８、２４０、２５４、２５５、２６９、２９１、Ｃ．Ｉ．ピグメントオレンジ１６、３６、４３、５１、５５、５９、６１、６４、７１、７３、Ｃ．Ｉ．ピグメントバイオレット１９、２３、２９、３０、３７、４０、５０、Ｃ．Ｉ．ピグメントブルー１５、１５：１、１５：３、１５：４、１５：６、１６、２２、６０、６４、Ｃ．Ｉ．ピグメントグリーン７、３６、５８、５９、６２、６３、Ｃ．Ｉ．ピグメントブラウン２３、２５、２６、Ｃ．Ｉ．ピグメントブラック７等が挙げられる。 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. Pigment Red 5, 7, 9, 12, 48, 48:2, 48:3, 49, 52, 53, 57, 57:1, 97, 112, 122, 123, 146, 149, 150, 168, 176, 177, 180, 184, 185, 192, 202, 206, 208, 209, 213, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 269, 291, C. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73, C. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C. I. Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 16, 22, 60, 64, C. I. Pigment Green 7, 36, 58, 59, 62, 63, C. I. Pigment Brown 23, 25, 26, C. I. Pigment Black 7 and the like.
　本実施の形態に係る水性インクにおいて、用いることのできる染料の具体例としては、アゾ系染料、ベンゾキノン系染料、ナフトキノン系染料、アントラキノン系染料、シアニン系染料、スクアリリウム系染料、クロコニウム系染料、メロシアニン系染料、スチルベン系染料、ジアリールメタン系染料、トリアリールメタン系染料、フルオラン系染料、スピロピラン系染料、フタロシアニン系染料、インジゴイド等のインジゴ系染料、フルギド系染料、ニッケル錯体系染料、及びアズレン系染料が挙げられる。 In the aqueous ink according to this embodiment, specific examples of 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.
　また、無機顔料の具体例としては、酸化チタン、硫酸バリウム、炭酸カルシウム、酸化亜鉛、炭酸バリウム、シリカ、タルク、クレー、合成マイカ、アルミナ、亜鉛華、硫酸鉛、黄色鉛、亜鉛黄、べんがら（赤色酸化鉄（ＩＩＩ））、カドミウム赤、群青、紺青、酸化クロム緑、コバルト緑、アンバー、チタンブラック、合成鉄黒、無機固溶体顔料等を挙げることができる。 In addition, specific examples of 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.
　顔料の平均分散粒径は、所望の発色が可能なものであれば特に限定されるものではない。顔料の種類によっても異なるが、顔料の分散安定性が良好で、充分な着色力を得る点から、顔料の平均分散粒径の下限は、１０ｎｍ以上の範囲内であることが好ましく、２０ｎｍ以上の範囲内であることがより好ましく、３０ｎｍ以上の範囲内であることがさらに好ましい。顔料の平均分散粒径の上限は、５００ｎｍ以下の範囲内であることが好ましく、４００ｎｍ以下の範囲内であることがより好ましく、３５０ｎｍ以下の範囲内であることがさらに好ましい。平均分散粒径が５００ｎｍ以下であれば、本実施の形態に係る水性インク組成物をインクジェット吐出した場合であっても、インクジェットヘッドのノズル目詰まりを起こしにくく、再現性の高い均質な画像を得ることができる。平均分散粒径が１０ｎｍ以上であれば、得られる記録物の耐光性を良好なものとすることができる。顔料の平均分散粒径の範囲は、１０ｎｍ以上５００ｎｍ以下の範囲内であることが好ましく、２０ｎｍ以上４００ｎｍ以下の範囲内であることがより好ましく、３０ｎｍ以上３５０ｎｍ以下の範囲内であることがさらに好ましい。なお、本実施形態において、顔料の平均分散粒径は、濃厚系粒径アナライザー（大塚電子（株）製、型式：ＦＰＡＲ－１０００）を用いて２５℃の条件下で測定した平均粒子径（Ｄ５０）である。 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. If 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. When 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. . In this embodiment, 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). ).
　本実施の形態に係るインク組成物は、顔料として光輝性顔料を含有してもよい。光輝性顔料としては、アルミニウム、銀、金、ニッケル、クロム、錫、亜鉛、インジウム、チタン、銅等の単体金属；金属化合物；合金およびそれら混合物の少なくとも１種である金属含有光輝性顔料や、雲母、魚鱗箔、酸塩化ビスマス、二酸化ケイ素、金属酸化物、金属化合物、およびそれらの積層等の真珠光沢や干渉光沢を有するパール顔料を挙げることができる。 The ink composition according to this embodiment may contain a glitter pigment as a pigment. Examples of 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; Examples include 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.
　本実施の形態に係る水性インク組成物に光輝性顔料を含有する場合、光輝性顔料は平板状（微細板状、鱗片状等とも表される）であることが好ましい。これにより、被体により好適な金属調の光沢を付与することができる。 When 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.
　本実施の形態に係る水性インク組成物に色材（染料、顔料、光輝性顔料を含む）を含有する場合、色材の含有量は、とくに限定されるものではないが、水性インク組成物全量中０．０５質量％以上であることが好ましく、０．０８質量％以上であることがより好ましく、０．１質量％以上であることがさらに好ましい。本実施の形態に係る水性インク組成物に色材を含有する場合、色材の含有量は、水性インク組成物全量中２０．０質量％以下であることが好ましく、１７．０質量％以下であることがより好ましく、１５．０質量％以下であることがさらに好ましい。色材の含有量は、水性インク組成物全量中０．０５質量％以上２０．０質量％以下であることが好ましく、０．０８質量％以上１７．０質量％以下であることがより好ましく、０．１質量％以上１５．０質量％以下であることがさらに好ましい。色材の含有量が０．０５質量％以上、又は２０質量％以下の範囲内であることにより、色材の分散安定性と着色力のバランスに優れたものとすることができる。 When the aqueous ink composition according to the present embodiment contains a coloring material (including dyes, pigments, and glitter pigments), 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. When the aqueous ink composition according to the present embodiment contains a coloring material, 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. More preferably, the content is 0.1% by mass or more and 15.0% by mass or less. When the content of the coloring material is within the range of 0.05% by mass or more or 20% by mass or less, the dispersion stability of the coloring material and the coloring power can be excellently balanced.
　［顔料分散剤］
　本実施の形態に係る水性インク組成物には顔料とともに顔料分散剤が含有されていてもよい。ここで顔料分散剤とは、顔料表面の一部に付着することでインク内での顔料の分散性を向上させる機能を有する樹脂又は界面活性剤のことを意味する。 [Pigment dispersant]
The aqueous ink composition according to this embodiment may contain a pigment dispersant together with a pigment. Here, 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.
　本実施の形態に係る水性インク組成物において、使用することのできる顔料分散剤は特に限定されない。例えば、カチオン系、アニオン系、ノニオン系、両性、シリコーン（シリコン）系、フッ素系等の界面活性剤を使用できる。界面活性剤の中でも、次に例示するような高分子界面活性剤（高分子分散剤）が好ましい。 The pigment dispersant that can be used in the aqueous ink composition according to this embodiment is not particularly limited. For example, cationic, anionic, nonionic, amphoteric, silicone, fluorine, and other surfactants can be used. Among the surfactants, polymer surfactants (polymer dispersants) such as those exemplified below are preferred.
　本実施の形態に係る水性インク組成物において用いることのできる顔料分散剤としては、水溶性高分子分散剤を好ましく用いることができる。水溶性高分子分散剤としては、例えば、ポリエステル系、ポリアクリル系、ポリウレタン系、ポリアミン系、ポリカプトラクトン系の主鎖を有し、側鎖に、アミノ基、カルボキシル基、スルホ基、ヒドロキシ基等の極性基を有する分散剤等が挙げられる。例えば、ポリアクリル酸エステル等の不飽和カルボン酸エステルの（共）重合体類；スチレン、α－メチルスチレン等の芳香族ビニル化合物とアクリル酸エステル等の不飽和カルボン酸エステルの共重合体類；ポリアクリル酸等の不飽和カルボン酸の（共）重合体の（部分）アミン塩、（部分）アンモニウム塩や（部分）アルキルアミン塩類；水酸基含有ポリアクリル酸エステル等の水酸基含有不飽和カルボン酸エステルの（共）重合体やそれらの変性物；ポリウレタン類；不飽和ポリアミド類；ポリシロキサン類；長鎖ポリアミノアミドリン酸塩類；ポリエチレンイミン誘導体（ポリ（低級アルキレンイミン）と遊離カルボキシル基含有ポリエステルとの反応により得られるアミドやそれらの塩基）；ポリアリルアミン誘導体（ポリアリルアミンと、遊離のカルボキシル基を有するポリエステル、ポリアミド又はエステルとアミドの共縮合物（ポリエステルアミド）の３種の化合物の中から選ばれる１種以上の化合物とを反応させて得られる反応生成物）等が挙げられる。中でも、（メタ）アクリル樹脂を含有する水溶性高分子分散剤が、インクの分散安定性と、印刷物の画像鮮明性の観点から好ましい。 As the pigment dispersant that can be used in the aqueous ink composition according to the present embodiment, a water-soluble polymer dispersant can be preferably used. Examples of water-soluble polymer dispersants include, for example, polyester-based, polyacrylic-based, polyurethane-based, polyamine-based, polycaptolactone-based main chains, and side chains containing amino groups, carboxyl groups, sulfo groups, and hydroxy groups. Examples include dispersants having polar groups such as. For example, (co)polymers of unsaturated carboxylic esters such as polyacrylic esters; copolymers of aromatic vinyl compounds such as styrene and α-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 alkylene imine) 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 carboxyl groups, polyamides, or co-condensates of esters and amides (polyesteramides)) (reaction products obtained by reacting one or more kinds of compounds), etc. Among these, water-soluble polymer dispersants containing (meth)acrylic resins are preferred from the viewpoint of ink dispersion stability and image clarity of printed matter.
　水溶性高分子分散剤の具体例としては、Ｃｒａｙ　Ｖａｌｌｅｙ製ＳＭＡ１４４０、ＳＭＡ２６２５、ＳＭＡ１７３５２、ＳＭＡ３８４０、ＳＭＡ１０００、ＳＭＡ２０００、ＳＭＡ３０００、ＢＡＳＦジャパン社製ＪＯＮＣＲＹＬ６７、ＪＯＮＣＲＹＬ６７８、ＪＯＮＣＲＹＬ５８６、ＪＯＮＣＲＹＬ６１１、ＪＯＮＣＲＹＬ６８０、ＪＯＮＣＲＹＬ６８２、ＪＯＮＣＲＹＬ６９０、ＪＯＮＣＲＹＬ８１９、ＪＯＮＣＲＹＬ－ＪＤＸ５０５０、ＥＦＫＡ４５５０、ＥＦＫＡ４５６０、ＥＦＫＡ４５８５、ＥＦＫＡ５２２０、ＥＦＫＡ６２３０、Ｄｉｓｐｅｘ　Ｕｌｔｒａ　ＰＸ４５７５、ルーブリゾール社製ＳＯＬＳＰＥＲＳＥ２００００、ＳＯＬＳＰＥＲＳＥ２７０００、ＳＯＬＳＰＥＲＳＥ４００００、ＳＯＬＳＰＥＲＳＥ４１０００、ＳＯＬＳＰＥＲＳＥ４１０９０、ＳＯＬＳＰＥＲＳＥ４３０００、ＳＯＬＳＰＥＲＳＥ４４０００、ＳＯＬＳＰＥＲＳＥ４５０００、ＳＯＬＳＰＥＲＳＥ４６０００、ＳＯＬＳＰＥＲＳＥ４７０００、ＳＯＬＳＰＥＲＳＥ５３０９５、ＳＯＬＳＰＥＲＳＥ５４０００、ＳＯＬＳＰＥＲＳＥ６４０００、ＳＯＬＳＰＥＲＳＥ６５０００、ＳＯＬＳＰＥＲＳＥ６６０００、ＳＯＬＳＰＥＲＳＥ　Ｊ４００、ＳＯＬＳＰＥＲＳＥ　Ｗ１００、ＳＯＬＳＰＥＲＳＥ　Ｗ２００、ＳＯＬＳＰＥＲＳＥ　Ｗ３２０、ＳＯＬＳＰＥＲＳＥ　ＷＶ４００、ビックケミー社製ＡＮＴＩ－ＴＥＲＲＡ－２５０、ＢＹＫＪＥＴ－９１５０、ＢＹＫＪＥＴ－９１５１、ＢＹＫＪＥＴ－９１５２、ＢＹＫＪＥＴ－９１７０、ＤＩＳＰＥＲＢＹＫ－１０２、ＤＩＳＰＥＲＢＹＫ－１６８、ＤＩＳＰＥＲＢＹＫ－１８０、ＤＩＳＰＥＲＢＹＫ－１８４、ＤＩＳＰＥＲＢＹＫ－１８５、ＤＩＳＰＥＲＢＹＫ－１８７、ＤＩＳＰＥＲＢＹＫ－１９０、ＤＩＳＰＥＲＢＹＫ－１９１、ＤＩＳＰＥＲＢＹＫ－１９３、ＤＩＳＰＥＲＢＹＫ－１９４Ｎ、ＤＩＳＰＥＲＢＹＫ－１９８、ＤＩＳＰＥＲＢＹＫ－１９９、ＤＩＳＰＥＲＢＹＫ－２０１０、ＤＩＳＰＥＲＢＹＫ－２０１２、ＤＩＳＰＥＲＢＹＫ－２０１３、ＤＩＳＰＥＲＢＹＫ－２０１４、ＤＩＳＰＥＲＢＹＫ－２０１５、ＤＩＳＰＥＲＢＹＫ－２０１８、ＤＩＳＰＥＲＢＹＫ－２０１９、ＤＩＳＰＥＲＢＹＫ－２０２３、ＤＩＳＰＥＲＢＹＫ－２０２６、ＤＩＳＰＥＲＢＹＫ－２０５５、ＤＩＳＰＥＲＢＹＫ－２０６０、ＤＩＳＰＥＲＢＹＫ－２０６１、ＤＩＳＰＥＲＢＹＫ－２０８１、ＤＩＳＰＥＲＢＹＫ－２０９６、ＤＩＳＰＥＲＢＹＫ－２１５７、ＤＩＳＰＥＲＢＹＫ－２１５８、ＤＩＳＰＥＲＢＹＫ－２１５９、ＤＩＳＰＥＲＢＹＫ－２１９０、ＤＩＳＰＥＲＢＹＫ－２２００、ＤＩＳＰＥＲＢＹＫ－２２９０、ＤＩＳＰＥＲＢＹＫ－２２９１、エボニック社製ＴＥＧＯ　ＤＩＳＰＥＲＳ６５０、ＴＥＧＯ　ＤＩＳＰＥＲＳ６５１、ＴＥＧＯ　ＤＩＳＰＥＲＳ６５２、ＴＥＧＯ　ＤＩＳＰＥＲＳ６５５、ＴＥＧＯ　ＤＩＳＰＥＲＳ６６０Ｃ、ＴＥＧＯ　ＤＩＳＰＥＲＳ６７０、ＴＥＧＯ　ＤＩＳＰＥＲＳ７１５Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７４０Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７４１Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７５０Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７５２Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７５５Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７５７Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７６０Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７６１Ｗ、ＴＥＧＯ　ＤＩＳＰＥＲＳ７６５Ｗ、ＺＥＴＡＳＰＥＲＳＥ１７０、ＺＥＴＡＳＰＥＲＳＥ１７９、ＺＥＴＡＳＰＥＲＳＥ１８２、ＺＥＴＡＳＰＥＲＳＥ３１００、ＺＥＴＡＳＰＥＲＳＥ３４００、ＺＥＴＡＳＰＥＲＳＥ３７００、ＺＥＴＡＳＰＥＲＳＥ３８００、サンノプコ社製ＳＮディスパーサント２０１０、ＳＮディスパーサント２０６０、ＳＮディスパーサント４２１５、ＳＮディスパーサント５０２７、ＳＮディスパーサント５０２９、ＳＮディスパーサント５０３４、ＳＮディスパーサント５４６８、ノプコール５２００、ノプコサントＫ、ノプコサントＲ、ノプコスパース４４－Ｃ、ノプコスパース６１００、ノプコスパース６１５０等が挙げられる。これらの顔料分散剤は、本実施の形態に係る水性インク組成物において好適に用いることができる。 Specific examples of 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, SOLSPERSE54000, SOLSPERSE64000, SOLSPERSE65000, SOLSPERSE66000 , SOLSPERSE J400, SOLSPERSE W100, SOLSPERSE W200, SOLSPERSE W320, SOLSPERSE WV400, BYKJET ANTI-TERRA-250, BYKJET-9150, BYKJ ET-9151, BYKJET-9152, BYKJET-9170, DISPERBYK-102, DISPERBYK-168, DISPERBYK -180, DISPERBYK-184, DISPERBYK-185, DISPERBYK-187, DISPERBYK-190, DISPERBYK-191, DISPERBYK-193, DISPERBYK-194N, DISPERBYK-198, DISPE RBYK-199, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2013 , DISPERBYK-2014, DISPERBYK-2015, DISPERBYK-2018, DISPERBYK-2019, DISPERBYK-2023, DISPERBYK-2026, DISPERBYK-2055, DISPERBYK-2060, DI SPERBYK-2061, DISPERBYK-2081, DISPERBYK-2096, DISPERBYK-2157, DISPERBYK -2158, DISPERBYK-2159, DISPERBYK-2190, DISPERBYK-2200, DISPERBYK-2290, DISPERBYK-2291, Evonik TEGO DISPERS650, TEGO DISPERS651, T EGO DISPERS652, TEGO DISPERS655, TEGO DISPERS660C, TEGO DISPERS670, TEGO DISPERS715W, TEGO DISPERS740W, TEGO DISPERS741W, TEGO DISPERS750W, TEGO DISPERS752W, TEGO DISPERS755W, TEGO DISPERS757W, TEGO DISPERS760W, TEGO DI SPERS761W, TEGO DISPERS765W, ZETASPERSE170, ZETASPERSE179, ZETASPERSE182, ZETASPERSE3100, ZETASPERSE3400, ZETASPERSE37 00, ZETASPERSE3800, San Nopco SN Dispersant 2010, SN Dispersant 2060 , SN Dispersant 4215, SN Dispersant 5027, SN Dispersant 5029, SN Dispersant 5034, SN Dispersant 5468, Nopcol 5200, Nopcosperth K, Nopcosperth R, Nopcosperse 44-C, Nopcosperse 6100, Nopcosperse 6150, and the like. These pigment dispersants can be suitably used in the aqueous ink composition according to this embodiment.
　［カチオン性又はアニオン性の化合物］
　本実施の形態に係る水性インク組成物にはカチオン性又はアニオン性の化合物を含有してもよい。本実施の形態に係る水性インク組成物は、カチオン性又はアニオン性の化合物を含有することは必須の構成ではないが、カチオン性又はアニオン性の化合物を含有することで、本実施の形態に係る水性インク組成物を受理溶液（前処理液）にすることができる。一般的に着色インクに含まれる色材がアニオン性であり、基材に着色インクを塗布するのに先立ち、カチオン性の化合物を含む受理溶液（前処理液）を基材に塗布することで、カチオン性の化合物により色材を凝集させることが可能となって、着色インクのにじみを抑制することができる。また、着色インクに含まれる色材がカチオン性である場合には、基材に着色インクを塗布するのに先立ち、アニオン性の化合物を含む受理溶液（前処理液）を基材に塗布することで、アニオン性の化合物により色材を凝集させることが可能となって、着色インクのにじみを抑制することができる。 [Cationic or anionic compound]
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 or anionic compound, by containing a cationic or anionic compound, the aqueous ink composition according to this embodiment can be used. The aqueous ink composition can be made into 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. In addition, if the coloring material contained in the colored ink is cationic, 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.
　カチオン性の化合物としては、カチオン性の樹脂や多価金属塩（多価金属のイオン）を挙げることができる。 Examples of cationic compounds include cationic resins and polyvalent metal salts (multivalent metal ions).
　カチオン性の樹脂は、公知の方法により合成することも、市販品を使用することもできる。以下に市販品を例示すると、ＡＰＣ－８１０，８１５；Ｄ－６０１０，６０２０、６０３０、６０４０、６０５０、６０６０、６０８０、６３１０、ＤＥＣ－５０，５３、５６，６５；ＦＬ－１４、４２，４４ＬＦ、６１、２０９９，２２５０，２２７３、２３５０、２５５０、２５６５、２５９９、２６５０、２８５０、２９４９、３０５０、３１５０、４３４０、４４２０、４４４０、４４５０、４５２０、４５３０、４５３５、４５４０、４６２０、４８２０；ＦＱＰ－１２６４；ＲＳＬ－１８－２２，４０７１Ｈ，４４００，８３９１、８３９１Ｈ、ＨＤ７０Ｃ、ＨＦ７０Ｄ；ＷＳ－７２（ＳＮＦ社製）、アラフィックス１００、２５１Ｓ、２５５、２５５ＬＯＸ（荒川化学社製）、ＤＫ－６８１０、６８５３、６８８５；ＷＳ－４０１０、４０１１、４０２０、４０２４、４０２７、４０３０（星光ＰＭＣ社製）、センカＦ－３００；パピオゲンＰ－１０５、Ｐ－１１３、Ｐ－２７１、Ｐ－３１６；ピッチノールＱＧ５Ａ；ミリオゲンＰ－２０；ユニセンスＦＰＡ１００Ｌ、ＦＰＡ１０１Ｌ、ＦＰＡ１０２Ｌ、ＦＰＡ１０００Ｌ、ＦＰＡ１００１Ｌ、ＦＰＡ１００ＬＵ、ＦＰＡ１０２ＬＵ、ＦＰＡ１０００ＬＵ；ユニセンスＦＣＡ１０００Ｌ、ＦＣＡ１００１Ｌ、ＦＣＡ１００２Ｌ、ＦＣＡ１００３Ｌ、ＦＣＡ５０００Ｌ；ユニセンスＫＣＡ１００Ｌ、ＫＣＡ１００ＬＵ、ＫＣＡ１０００ＬＵ、ＫＣＡ１００１ＬＵ；ユニセンスＫＨＥ１００Ｌ、ＫＨＥ１０１Ｌ、ＫＨＥ１０２Ｌ、Ｅ１０４Ｌ、ＫＨＥ１０５Ｌ、ＫＨＥ１０７Ｌ、ＫＨＥ１０００Ｌ、ＫＨＥ１００１Ｌ；ユニセンスＫＨＰ１０Ｐ、ＫＨＰ１１Ｌ、ＫＨＰ１０ＬＵ、ＫＨＰ１１ＬＵ、ＫＨＰ１２ＬＵ、ＫＨＰ２０ＬＵ：ユニセンスＫＨＦ１０Ｌ、ＫＨＦ１１Ｌ；ユニセンスＦＰＶ１０００Ｌ、ＦＰＶ１０００ＬＵ；ユニセンスＦＣＶ１０００Ｌ；ユニセンスＺＣＡ１０００Ｌ、ＺＣＡ１００１Ｌ、ＺＣＡ１００２Ｌ、ＺＣＡ５０００Ｌ；ユニセンスＫＰＶ１００ＬＵ、ＫＰＶ１０００ＬＵ（センカ社製）、パラロック４１０Ｋ１０１、４１０Ｋ１１１、４２０Ｋ３０８、４２０Ｋ３００、４６０Ｋ３１３、４６０Ｋ３１８、４７０Ｋ３０８、４８０Ｋ３００、４９０Ｋ３００、４９０Ｋ３０９、５００Ｋ３０Ｅ、５００Ｋ４０Ｅ、５９Ｄ、９２０ＡＰ５００、９７５ＡＰ５００、ＰＤ７００、ＰＤ７１４Ｌ、ＰＤ７１４Ｓ、Ｐ６００、（浅田化学社製）、スミレーズレジン６５０（３０）、６７５Ａ、６６１５、ＳＬＸ－１（田岡化学工業社製）、ＥＰ－１１３７；ＭＺ－４７７、４８０；ＮＳ－３１０Ｘ、６２５ＸＣ（高松油脂社製）、ＰＡＡ－Ｄ１１－ＨＣＬ、Ｄ１９－ＨＣＬ，Ｄ４１－ＨＣＬ、Ｄ１９Ａ；ＰＡＡ－ＨＣＬ－０３、０５、３Ｌ、１０Ｌ；ＰＡＡ－１１１２ＣＬ、２１ＣＬ、ＡＣ５０５０Ａ、Ｎ５０５０ＣＬ、ＳＡ；ＰＡＳ－Ａ－１、５；ＰＡＳ－Ｈ－１Ｌ、５Ｌ、１０Ｌ；ＰＡＳ－Ｊ－８１、８１Ｌ；ＰＡＳ－Ｍ－１、１Ａ、１Ｌ；ＰＡＳ－２１、２１ＣＬ，２２ＳＡ－４０、２４、９２、９２Ａ、８８０、２２０１ＣＬ、２４０１（ニットーボーメディカル社製）、ＰＰ－１７(明成化学社製)；カチオマスターＰＤ－１、７、３０、Ａ、ＰＤＴ－２、ＰＥ－１０、ＰＥ－３０、ＤＴ－ＥＨ、ＥＰＡ－ＳＫ０１、ＴＭＨＭＤＡ－Ｅ（四日市合成社製）、ジェットフィックス３６Ｎ、３８Ａ、５０５２（里田化工社製）、モビニール３５００、６９１０、６９４０、６９５０、６９５１、７８２０（ジャパンコーティングレジン社製）、ＣＴＷ－１１３Ｓ、ＷＥＭ－５０５Ｃ、ＷＢＲ－２１２２Ｃ（大成ファインケミカル社製）、ＡＰ－１３５０、ＡＥ－８０３、ＡＥ－８２１、ＡＭ－３５００（レゾナック社製）、ハイドランＣＰ－７０５０、ＣＰ－７５２０（ＤＩＣ社製）などとなる。 The cationic resin can be synthesized by a known method, or a commercially available product can be used. Examples of 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; Unisense FPA100L, FPA101L, FPA102L, FPA1000L, FPA1001L, FPA100LU, FPA102LU, FPA1000LU; Unisense FCA1000L, FCA1001L, FCA1002L, FCA1003L, FCA5000L; Sense KCA100L, KCA100LU, KCA1000LU, KCA1001LU; Unisense KHE100L, KHE101L, KHE102L, E104L, KHE105L, KHE107L, KHE1000L, KHE1001L; Unisense KHP10P, KHP11L, KHP10LU, KHP11LU, KHP12LU, KHP20LU: Unisense KHF10L, KHF11L; Unisense FPV1000L, FPV1000LU; Unisense FCV1000L; Sense ZCA1000L, ZCA1001L, ZCA1002L, ZCA5000L; Unisense KPV100LU, KPV1000LU (manufactured by Senka) , Paralock 410K101, 410K111, 420K308, 420K300, 460K313, 460K318, 470K308, 480K300, 490K300, 490K309, 500K30E, 500K40E, 59D, 920AP500, 975AP500, PD 700, PD714L, PD714S, P600, (manufactured by Asada Chemical Co., Ltd.), violet resin 650 (30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Industry Co., Ltd.), EP-1137; MZ-477, 480; NS-310X, 625XC (manufactured by Takamatsu Yushi Co., Ltd.), PAA-D11-HCL, D19- HCL, D41-HCL, D19A; PAA-HCL-03, 05, 3L, 10L; PAA-1112CL, 21CL, AC5050A, N5050CL, SA; PAS-A-1, 5; PAS-H-1L, 5L, 10L; PAS-J-81, 81L; PAS-M-1, 1A, 1L; PAS-21, 21CL, 22SA-40, 24, 92, 92A, 880, 2201CL, 2401 (manufactured by Nitto Bo Medical), PP-17 ( Catiomaster PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Gosei), Jetfix 36N, 38A, 5052 (manufactured by Satoda Kako Co., Ltd.), Movinyl 3500, 6910, 6940, 6950, 6951, 7820 (manufactured by Japan Coating Resin Co., Ltd.), CTW-113S, WEM-505C, WBR-2122C (manufactured by Taisei Fine Chemical Co., Ltd.), These include AP-1350, AE-803, AE-821, AM-3500 (manufactured by Resonac), Hydran CP-7050, and CP-7520 (manufactured by DIC).
　なお、カチオン性の樹脂は、水性インク組成物中に溶解した状態で存在していても、高分子微粒子分散体として分散された状態で存在していてもよい。 Note that the cationic resin may exist in the aqueous ink composition in a dissolved state or in a dispersed state as a polymer fine particle dispersion.
　金属塩としては、価数が少なくとも２価以上の多価金属のイオンと、陰イオンと、を含む多価金属塩を挙げることができる。多価金属イオンとしては、例えばカルシウムイオン、マグネシウムイオン、アルミニウムイオン、チタンイオン、鉄（ＩＩ）イオン、鉄（ＩＩＩ）イオン、コバルトイオン、ニッケルイオン、銅イオン、亜鉛イオン、バリウムイオン、ストロンチウムイオン等が挙げられる。なかでも、インク組成物中の色材との相互作用が大きく、にじみやムラを抑制する効果が高くなることから、カルシウムイオン、マグネシウムイオン、ニッケルイオン、亜鉛イオン、アルミニウムイオンより選択される１種以上を含有することが好ましい。 Examples of the metal salt include polyvalent metal salts containing an ion of a polyvalent metal with a valence of at least two or more and an anion. Examples of 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. Among them, 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.
　陰イオンは、無機物の陰イオンであってもよく、有機物の陰イオンであってもよい。有機物の陰イオンの具体例としては、酢酸、安息香酸、サリチル酸、２、４－ジヒドロキシ安息香酸、２、５－ジヒドロキシ安息香酸、ジメチロールプロピオン酸、パントテン酸、コハク酸、マレイン酸、グルタル酸、スベリン酸、トリメリット酸、メチルマロン酸の陰イオンを挙げることができる。無機物の陰イオンの具体例としては、塩化物イオン、臭化物イオン、硝酸イオン、硫酸イオン等を挙げることができる。 The anion may be an inorganic anion or an organic anion. Specific examples of 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.
　カチオン性又はアニオン性の化合物の含有量としては、特に限定されるものではないが、カチオン性又はアニオン性の化合物の含有量の下限は、水性インク組成物全量中０．１質量％以上の範囲内であることが好ましく、０．８質量％以上の範囲内であることがより好ましく、１．０質量％以上の範囲内であることがさらに好ましい。カチオン性又はアニオン性の化合物の含有量が水性インク組成物全量中０．５質量％以上の範囲内であることで、色材をより効果的に定着することが可能となり、着色インクのにじみをより効果的に抑制することができる。カチオン性又はアニオン性の化合物の含有量の上限は、水性インク組成物全量中１５質量％以下の範囲内であることが好ましく、８質量％以下の範囲内であることがより好ましく、７質量％以下の範囲内であることがさらに好ましい。カチオン性又はアニオン性の化合物の含有量が水性インク組成物全量中１５質量％以下の範囲内であることで、水性インク組成物の保存安定性及び吐出安定性が向上する。カチオン性又はアニオン性の化合物の含有量の範囲は、水性インク組成物全量中０．１質量％以上１５質量％以下の範囲内であることが好ましく、０．８質量％以上８質量％以下の範囲内であることがより好ましく、１．０質量％以上７質量％以下の範囲内であることがさらに好ましい。 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 0.1% 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. When 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 15% 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. When the content of the cationic or anionic compound is within the range of 15% 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 0.1% by mass or more and 15% by mass or less, and 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, and even more preferably within the range of 1.0% by mass or more and 7% by mass or less.
　［レベリング剤］
　本実施の形態に係る水性インクは、上述した共重合体に含まれる乳化剤や顔料分散剤とは異なる界面活性剤としてレベリング剤を含有してもよい。レベリング剤を含有することで、水性インク組成物の表面張力を適切な範囲に制御することができる。レベリング剤としては、特に限定されるものではないが、表面張力の調整性が優れる点から、アニオン系界面活性剤、非イオン性界面活性剤、シリコーン（シリコン）系界面活性剤、フッ素系界面活性剤、アセチレングリコール系界面活性剤等が好ましく用いられる。 [Leveling agent]
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. By containing the leveling agent, 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.
　具体例としては、エマール、ラテムル、ペレックス、ネオペレックス、デモール（いずれも、アニオン系界面活性剤；花王株式会社製）、サンノール、リポラン、ライポン、リパール（いずれも、アニオン系界面活性剤；ライオン株式会社製）、ノイゲン、エパン、ソルゲン（いずれも非イオン性界面活性剤；第一工業製薬株式会社製）エマルゲン、アミート、エマゾール（いずれも非イオン性界面活性剤；花王株式会社製）、ナロアクティー、エマルミン、サンノニック（いずれも非イオン性界面活性剤；三洋化成工業株式会社製）、サーフィノール１０４、８２、４２０、４４０、４６５、４８５、ＴＧ、２５０２、ＳＥ－Ｆ、１０７Ｌ、ダイノール３６０、ダイノール６０４、ダイノール６０７（いずれも、アセチレングリコール系界面活性剤；エボニック社製）、ダイノール９６０（アセチレングリコール系とシリコン系界面活性剤の配合物；エボニック社製）、サーフィノールＡＤ０１（アルカングリコール系界面活性剤；エボニック社製）、オルフィンＥ１００４、Ｅ１０１０、ＰＤ００４、ＥＸＰ４３００（いずれも、アセチレングリコール系界面活性剤；日信化学工業株式会社製）、メガファック（フッ素系界面活性剤；ＤＩＣ株式会社製）、サーフロン（フッ素系界面活性剤；ＡＧＣセイミケミカル社製）、ＢＹＫ３０２、３０６、３０７、３３１、３３３、３４５、３４６、３４７、３４８、３４９、３４２０、３４５０、３４５１、３４５５、３４５６（いずれもシリコーン（シリコン）系界面活性剤；ビックケミー社製）、ＫＰ－１１０、１１２、３２３、３４１、６００４（いずれもシリコーン（シリコン）系界面活性剤；信越化学株式会社製）、シルフェイスＳＡＧ００２、シルフェイスＳＡＧ００５、シルフェイスＳＡＧ００８、シルフェイスＳＡＧ０１４、シルフェイスＳＡＧ５０３Ａ、シルフェイスＳＪＭ－００２、シルフェイスＳＪＭ－００３（いずれもシリコーン（シリコン）系界面活性剤；日信化学工業（株）製）、ＴＥＧＯ　ＦＬＯＷ　４２５、ＴＥＧＯ　Ｇｌｉｄｅ　１００、１１０、１３０、４１０、４３２、４４０、４５０、４８２、４９０、４９２、４９４、４９６、ＺＧ４００、ＴＥＧＯ　Ｔｗｉｎ　４０００、ＴＥＧＯ　Ｔｗｉｎ　４１００、ＴＥＧＯ　Ｔｗｉｎ　４２００、ＴＥＧＯ　Ｗｅｔ　２４０、ＫＬ２４５、２５０、２６０、２６５、２７０、２８０、（いずれもシリコーン（シリコン）系界面活性剤；エボニック社製）、ＴＥＧＯ　Ｗｅｔ　５００、５０５、５１０、５２０（いずれもノニオン系界面活性剤；エボニック社製）などが挙げられる。 Specific examples include 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; manufactured by Evonik), Surfynol AD01 (alkane glycol surfactants) (manufactured by Evonik), Olfin E1004, E1010, PD004, EXP4300 (all acetylene glycol surfactants; manufactured by Nissin Chemical Industry Co., Ltd.), Megafac (fluorinated surfactants; manufactured by DIC Corporation), Surflon (fluorosurfactant; manufactured by AGC Seimi Chemical Co., Ltd.), BYK302, 306, 307, 331, 333, 345, 346, 347, 348, 349, 3420, 3450, 3451, 3455, 3456 (all silicone ) type surfactant; manufactured by Bikkemie Co., Ltd.), KP-110, 112, 323, 341, 6004 (all silicone type surfactants; manufactured by Shin-Etsu Chemical Co., Ltd.), Silface SAG002, Silface SAG005, Silface Face SAG008, Silface SAG014, Silface SAG503A, Silface SJM-002, Silface SJM-003 (all silicone surfactants; manufactured by Nissin Chemical Industry Co., Ltd.), TEGO FLOW 425, TEGO Glide 100, 110, 130, 410, 432, 440, 450, 482, 490, 492, 494, 496, ZG400, TEGO Twin 4000, TEGO Twin 4100, TEGO Twin 4200, TEGO Wet 240, KL245, 250, 260, 265, Examples include TEGO Wet 500, 505, 510, and 520 (all nonionic surfactants; manufactured by Evonik).
　レベリング剤の含有量は、特に限定されないが、レベリング剤の含有量の下限は、水性インク組成物全量中０．３０質量％以上の範囲内であることが好ましく、０．４０質量％以上の範囲内であることがより好ましく、０．５０質量％以上の範囲内であることがさらに好ましい。レベリング剤の含有量の上限は、水性インク組成物全量中５．０質量％以下の範囲内であることが好ましく、４．０質量％以下の範囲内であることがより好ましく、３．０質量％以下の範囲内であることがさらに好ましい。レベリング剤の含有量の範囲は、水性インク組成物全量中０．３０質量％以上５．０質量％以下の範囲内であることが好ましく、０．４０質量％以上４．０質量％以下の範囲内であることがより好ましく、０．５０質量％以上３．０質量％以下の範囲内であることがさらに好ましい。 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.
　［その他の成分］
　水性インク組成物は、必要に応じて、さらに、従来公知の添加剤を含んでもよい。添加剤としては、例えば、ワックス、粘度調整剤、ｐＨ調整剤、酸化防止剤、防腐剤、防黴剤、抗菌剤、抗ウイルス剤、紫外線吸収剤、光安定剤等が挙げられる。 [Other ingredients]
The aqueous ink composition may further contain conventionally known additives, if necessary. Examples of additives include waxes, viscosity modifiers, pH adjusters, antioxidants, preservatives, antifungal agents, antibacterial agents, antiviral agents, ultraviolet absorbers, light stabilizers, and the like.
　＜水性インク組成物の調製方法＞
　水性インク組成物の調製方法は、特に限定されない例えば、水溶性溶媒に自己分散型の顔料、樹脂、界面活性剤及び必要に応じてその他の成分を添加して調製する方法、水溶性溶媒に、顔料と分散剤を加えて分散した後、樹脂、界面活性剤及び必要に応じてその他の成分を添加して調製する方法、水溶性溶媒に顔料と樹脂と界面活性剤と必要に応じてその他の成分を添加した後、顔料を分散して調製する方法等が挙げられる。 <Method for preparing aqueous ink composition>
The method for preparing the aqueous ink composition is not particularly limited. For example, 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.
　本実施の形態に係る水性インク組成物を、基材の表面に塗布する方法は、特に制限はされず、例えば、インクジェット方式、グラビア方式、フレキソ方式、スプレー方式、スクリーン方式、コーター方式等を挙げることができる。この中でも、インクジェット方式が好ましい。インクジェット方式であれば、電子上の所望の画像の基材の任意の場所へ吐出して所望の画像を形成することが可能である。 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. Among these, 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.
　水性インク組成物の表面張力は、特に限定されないが、本実施の形態に係る非水系インク組成物の２５℃での表面張力の上限は、４０．０ｍＮ／ｍ以下が好ましく、３５．０ｍＮ／ｍ以下がより好ましく、３２．０ｍＮ／ｍ以下がさらに好ましい。本実施の形態に係る非水系インク組成物の２５℃での表面張力の下限は、１７．０ｍＮ／ｍ以上が好ましく、１８．０ｍＮ／ｍ以上がより好ましく、１９．０ｍＮ／ｍ以上がさらに好ましい。本実施の形態に係る非水系インク組成物の２５℃での表面張力の範囲は、１７．０ｍＮ／ｍ以上４０．０ｍＮ／ｍ以下が好ましく、１８．０ｍＮ／ｍ以上３５．０ｍＮ／ｍ以下がより好ましく、１９．０ｍＮ／ｍ以上３２．０ｍＮ／ｍ以下がさらに好ましい。 Although 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.
　≪２．インクセット≫
　上記の水性インク組成物は、着色インクであっても、メタリックインク等であっても、カチオン性の化合物を含む受理溶液であっても、色材を含有しないクリアインクであっても、オーバーコートインクであってもよい。本実施の形態に係るインクセットは、これらのインク組成物を組み合わせたインクセットとしてもよい。 ≪2. Ink set≫
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.
　本実施の形態に係るインクセットは、インクセットに含まれる少なくとも１つの水性インク組成物が上記の少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む水性インク組成物であればよい。例えば、水性インク組成物Ａと水性インク組成物Ｂとを含むインクセットにおいて、水性インク組成物Ａが上記の少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む水性インク組成物であり、水性インク組成物Ｂが上記の少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む水性インク組成物とは異なる水性インク組成物であってもよい。また、水性インク組成物Ａと水性インク組成物Ｂいずれもが上記の少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む水性インク組成物であってもよい。３種類以上の水性インク組成物を含むインクセットにおいても同様である。 In the ink set according to the present embodiment, at least one aqueous ink composition included in the ink set contains a copolymer containing at least two types of monomers as constituent units, and an acrylic resin having a Tg within a predetermined range. Any aqueous ink composition containing the following may be used. For example, in an ink set including a water-based ink composition A and a water-based ink composition B, the water-based ink composition A contains a copolymer containing the above-mentioned at least two types of monomers as constituent units, and has a Tg in a predetermined range. An aqueous ink composition containing an acrylic resin, wherein the aqueous ink composition B contains a copolymer containing the above-mentioned at least two types of monomers as constituent units, and the aqueous ink composition contains an acrylic resin having a Tg within a predetermined range. The aqueous ink composition may be different from the one described above. Further, both the water-based ink composition A and the water-based ink composition B contain a copolymer containing the above-mentioned at least two types of monomers as constituent units, and are water-based ink compositions containing an acrylic resin having a Tg within a predetermined range. There may be. The same applies to ink sets containing three or more types of aqueous ink compositions.
　本実施の形態に係るインクセットとしては、例えば、色材を含有する着色インク組成物とカチオン性の化合物を含む受理溶液（前処理液）とを含むインクセットや、色材を含有する着色インク組成物とカチオン性の化合物を含む受理溶液（前処理液）とオーバーコートインクを含むインクセットや、色材を含有する着色インク組成物とオーバーコートインクを含むインクセットを挙げることができる。 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.
　また、色材を含有する着色インク組成物同士を組み合わせたインクセットであってもよく、例えば、イエロー、マゼンタ、シアン、ブラック、及びこれらの中間色（例えば、オレンジインク、グリーンインク、ブルーインク、バイオレットインク、レッドインク）や淡色（例えば、ライトマゼンタインク、ライトシアンインク、ライトブラックインク）の着色インク組成物のような複数のインク組成物を組み合わせたインクセットであってもよい。また、白色色材を含有する白色インク組成物と、イエローインク組成物、マゼンタインク組成物、シアンインク組成物、ブラックインク組成物と、を含むインクセットや、白色色材を含有する白色インク組成物と、イエローインク組成物、マゼンタインク組成物、シアンインク組成物、ブラックインク組成物と、イエロー、マゼンタ、シアン、ブラックの中間色インク組成物や淡色インク組成物を含むインクセットであってもよい。さらに、光輝性顔料を含むメタリックインクと、イエローインク組成物、マゼンタインク組成物、シアンインク組成物、ブラックインク組成物と、を含むインクセットや、光輝性顔料を含むメタリックインクと、イエローインク組成物、マゼンタインク組成物、シアンインク組成物、ブラックインク組成物と、イエロー、マゼンタ、シアン、ブラックの中間色インク組成物や淡色インク組成物を含むインクセットであってもよい。 It 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, blue ink, violet). 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). Further, 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 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. . Further, 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.
　≪３．記録方法≫
　本実施の形態に係る記録方法は、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物を基材上に塗布する記録方法である。 ≪3. Recording method≫
The recording method according to the present embodiment includes applying the above water-based ink composition containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin having a Tg within a predetermined range onto a substrate. This is a recording method.
　少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物であれば保存安定性が高い状態で基材上に水性インク組成物を塗布することが可能である。 If the above water-based ink composition contains a copolymer containing at least two types of monomers as constituent units and contains an acrylic resin with a Tg within a predetermined range, the water-based ink composition can be coated on a substrate in a state with high storage stability. It is possible to apply objects.
　上記の水性インク組成物を、基材の表面に塗布する方法は、特に制限はされず、例えば、インクジェット方式、グラビア方式、フレキソ方式、スプレー方式、スクリーン方式、コーター方式等を挙げることができる。この中でも、インクジェット方式が好ましい。インクジェット方式であれば、基材上の任意の場所へ吐出することが可能である。 The method for applying the above aqueous ink composition onto the surface of the substrate 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, and the like. Among these, the inkjet method is preferred. With the inkjet method, it is possible to eject to any location on the base material.
　また、本実施の形態に係る記録方法は、基材の表面に塗布された水性インク組成物に対して乾燥する乾燥工程を備えていてもよい。これにより、印刷時の加熱温度を調節するとともに、記録物の生産性を向上させることができる。 Furthermore, 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.
　基材の表面に塗布された水性インク組成物を乾燥させる方法としては、例えば、インクジェット記録装置に備えられるプレヒーター、プラテンヒーター、アフターヒーター等の加温機構により乾燥させる方法や、記録物の表面に対して熱風や常温等の風を送風する送風機構であっても、赤外線などにより記録物の表面を加熱する輻射線照射機構であってもよい。また、これらの加温機構を複数組み合わせるものであってもよい。 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.
　特に、特定のモノマーを構成単位として含む共重合体を含有する上記の水性インク組成物は、比較的低温で乾燥させた場合であっても塗膜の十分に製膜されて、得られる記録物の耐溶剤性が高いものである。このため、低温で乾燥させることで、エネルギー負荷や装置への負荷を低減させながら生産性の高い状態で記録物を生産することが可能となる。 In particular, 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.
　具体的には、本実施の形態に係る記録方法では、記録物の表面が１１０℃以下となるように乾燥させることが好ましく、９０℃以下となるように乾燥させることがより好ましく、７０℃以下となるように乾燥させることがさらに好ましい。また、本実施の形態に係る記録方法では、記録物の表面が３０℃以上となるように乾燥させることが好ましく、３５℃以上となるように乾燥させることがより好ましく４０℃以上となるように乾燥させることがさらに好ましい。本実施の形態に係る記録方法では、記録物の表面が３０℃以上１１０℃以下となるように乾燥させることが好ましく、３５℃以上９０℃以下となるように乾燥させることがより好ましく、４０℃以上７０℃以下となるように乾燥させることがさらに好ましい。 Specifically, in the recording method according to the present embodiment, it is preferable to dry the surface of the recorded material to a temperature of 110°C or lower, more preferably to dry the surface to a temperature of 90°C or lower, and dry the surface to a temperature of 70°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. In the recording method according to this embodiment, it is preferable to dry the surface of the recorded material to a temperature of 30°C or higher and 110°C or lower, more preferably 35°C or higher and 90°C or lower, and 40°C or lower. It is more preferable to dry at a temperature of 70° C. or lower.
　また、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物をインクジェット吐出する場合、そのインクジェットの吐出方式は、ピエゾ方式、サーマル方式、静電方式等のいずれの方式であってもよい。 Further, when the above water-based ink composition containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin having a Tg within a predetermined range is inkjet discharged, the inkjet discharge method is a piezo method. , thermal method, electrostatic method, etc. may be used.
　≪４．記録物の製造方法≫
　上述した記録方法は、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物をインクジェット法により基材上に塗布する記録物の製造方法と定義することもできる。 ≪4. Method of manufacturing recorded materials≫
The above-mentioned recording method is a recording method in which the above-mentioned water-based ink composition containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin having a Tg within a predetermined range is applied onto a substrate by an inkjet method. It can also be defined as a method of manufacturing a product.
　≪５．記録物≫
　上記の実施形態の記録物の製造方法により製造された記録物を構成する各層について説明する。具体的に、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物、又は上記のインクセットに含まれる水性インク組成物が基材上に塗布された記録物である。以下、記録物を構成する媒体（記録媒体）や水性インク組成物の層について説明する。 ≪5. Records≫
Each layer constituting the recorded matter manufactured by the method for manufacturing a recorded matter of the above embodiment will be described. Specifically, the above aqueous ink composition containing a copolymer containing at least two types of monomers as constituent units and an acrylic resin having a Tg within a predetermined range, or the aqueous ink composition included in the above ink set. is the recorded material coated on the base material. Hereinafter, the medium (recording medium) and the layer of the aqueous ink composition that constitute the recorded matter will be explained.
　本実施の形態に係る記録物に含まれる基材（記録媒体）としては、特に限定はされず、樹脂基材、金属板、ガラスなどの非吸収性基材であっても、紙や布帛などの吸収性基材であっても、受容層を備える基材のような表面塗工が施された基材であってもよく、種々の基材を使用することができる。 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. Various types of base materials can be used, such as absorbent base materials such as the above, or surface-coated base materials such as base materials provided with a receptive layer.
　非吸収性基材としては、ポリエステル系樹脂、ポリプロピレン系合成紙、ポリプロピレン系樹脂、ポリエチレン系樹脂、アクリル樹脂、スチレン樹脂、ポリカーボネート樹脂、ＡＢＳ樹脂、塩化ビニル樹脂、ポリイミド樹脂等の樹脂基材や、金属、金属箔コート紙、ガラス、合成ゴム、天然ゴム等を挙げることができる。 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.
　吸収性基材としては、更紙、中質紙、上質紙、合成紙、綿、化繊織物、絹、麻、布帛、不織布、皮革等を挙げることができる。 Examples of the absorbent substrate include cardboard, medium-quality paper, high-quality paper, synthetic paper, cotton, synthetic fabric, silk, hemp, fabric, nonwoven fabric, and leather.
　表面塗工が施された基材としてはコート紙、アート紙、キャスト紙、軽量コート紙、微塗工紙等を挙げることができる。 Examples of the surface-coated base material include coated paper, art paper, cast paper, lightweight coated paper, lightly coated paper, and the like.
　［水性インク組成物の層］
　水性インク組成物の層とは、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物に含まれる溶媒（水や水溶性有機溶剤）が揮発することにより形成される層である。例えば、水性インク組成物に色材を含有した場合には、所望の画像を形成する加飾層やその下地層となる。 [Layer of water-based ink composition]
The layer of the aqueous ink composition is a layer containing a copolymer containing at least two types of monomers as constituent units, and a solvent (such as water or a water-soluble This layer is formed by the volatilization of organic solvents. For example, when the aqueous ink composition contains a coloring material, it becomes a decorative layer or a base layer for forming a desired image.
　また、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物をカチオン性の化合物を含む受理溶液とする場合には、基材上に少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物（受理溶液）を塗布し、その上に少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物（着色インク）を塗布してもよいし、基材上に少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物（受理溶液）を塗布し、その上に少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物（着色インク）とは異なるインク組成物（着色インク）を塗布してもよい。 Further, when the above water-based ink composition containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin having a Tg within a predetermined range is used as a receiving solution containing a cationic compound, The above water-based ink composition (receiving solution) containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin with a Tg within a predetermined range is applied onto a base material, and at least two The above water-based ink composition (colored ink) containing a copolymer containing various types of monomers as constituent units and an acrylic resin having a Tg within a predetermined range may be coated on the base material, or at least two types of the above water-based ink composition may be coated on the base material. The above water-based ink composition (receiving solution) containing a copolymer containing a monomer as a constituent unit and containing an acrylic resin with a Tg within a predetermined range is coated thereon, and at least two types of monomers as a constituent unit are applied thereon. An ink composition (colored ink) different from the above-mentioned aqueous ink composition (colored ink) containing a copolymer containing a copolymer and an acrylic resin having a Tg within a predetermined range may be applied.
　また、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物をオーバーコートインクとする場合には、記録物の表面に形成されるオーバーコート層となる。なお、この場合、記録物が備える記録層を形成するインク組成物は、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物であってもよいし、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物とは異なるインク組成物であってもよい。 In addition, when the above water-based ink composition containing a copolymer containing at least two types of monomers as constituent units and containing an acrylic resin having a Tg within a predetermined range is used as an overcoat ink, This becomes an overcoat layer to be formed. In this case, the ink composition forming the recording layer of the recorded matter contains the above water-based ink containing a copolymer containing at least two types of monomers as constituent units, and containing an acrylic resin having a Tg within a predetermined range. The ink composition may be an ink composition different from the above water-based ink composition, which contains a copolymer containing at least two types of monomers as constituent units, and contains an acrylic resin having a Tg within a predetermined range. It's okay.
　≪６．装置≫
　本実施の形態に係る装置は少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、所定範囲のＴｇのアクリル系樹脂を含む上記の水性インク組成物、又は上記のインクセットに含まれるインク組成物が充填された収容容器が搭載された装置である。 ≪6. Equipment≫
The apparatus according to the present embodiment contains a copolymer containing at least two types of monomers as constituent units, and is included in the above water-based ink composition or the above ink set containing an acrylic resin having a Tg within a predetermined range. This device is equipped with a container filled with an ink composition.
　本実施の形態に係る装置は、上記の水性インク組成物、又は上記のインクセットに含まれる水性インク組成物が充填された収容容器が搭載されたインクジェット記録装置であることが好ましい。 The apparatus according to the present embodiment is preferably an inkjet recording apparatus equipped with a container filled with the aqueous ink composition described above or the aqueous ink composition included in the ink set described above.
　なお、本実施の形態に係る装置に搭載される収容容器とは、とくに限定されず、例えば、インクボトル、パウチ、バッグインボックス、ドラム等の容器を挙げることができる。また、これらの容器をさらにカートリッジ等に収容したものであってもよい。収容容器の材質としては、とくに限定されず、従来公知の樹脂製であってもよいし、その一部の金属材料を含む材質（例えば、アルミ蒸着層を備えたアルミパウチ）であってもよい。 Note that the storage container installed in the apparatus according to the present embodiment 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 is not particularly limited, and may be made of conventionally known resin, or may be made of a material containing some metal material (for example, an aluminum pouch with an aluminum vapor deposition layer). .
　またこの装置には、水性インク組成物の塗布後に水性インク組成物を乾燥する乾燥機構を備えることが好ましい。これにより印刷時の記録物の表面温度を調整して、それぞれの水性インク組成物に含まれる揮発成分を効果的に除去することが可能となる。 Further, this apparatus preferably includes a drying mechanism that dries the aqueous ink composition after coating the aqueous 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 aqueous ink composition.
　乾燥機構は、被記録媒体を乾燥できるものであれば特に限定されないが、プレヒーター、プラテンヒーター、アフターヒーター等のヒーター、輻射線照射、送風機構(熱風や常温の風等)、の何れかが好ましい。また、これらの加温機構を複数組み合わせるものであってもよい。 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.
　また、本実施の形態に係る装置がインクジェット記録装置である場合、それぞれの吐出部における吐出方式は、ピエゾ方式、サーマル方式、静電方式等のいずれの方式であってもよい。 Furthermore, when the apparatus according to this embodiment is an inkjet recording apparatus, the ejection method in each ejection section may be any method such as a piezo method, a thermal method, or an electrostatic method.
　以下、実施例により、本発明を更に詳細に説明するが、本発明はこれらの記載に何ら制限を受けるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these descriptions in any way.
１．高分子微粒子分散体の合成
　［実施例１］ 
　シクロヘキシルメタクリレート７８．８部、ｎブチルメタクリレート１９．７部、メタクリル酸１．５０部からなる混合物を、水（脱イオン水）４１．０部に「エマルゲンＡ－９０（花王社製；ノニオン型界面活性剤、固形分１００％）」２．０部と「エマール２０ＣＭ（花王社製；アニオン型界面活性剤、固形分２５％）」６．２部を溶解した水溶液中に添加し、撹拌することで乳化モノマー組成物を作製した。 1. Synthesis of polymer fine particle dispersion [Example 1]
A mixture of 78.8 parts of cyclohexyl methacrylate, 19.7 parts of n-butyl methacrylate, and 1.50 parts of methacrylic acid was added to 41.0 parts of water (deionized water) with "Emulgen A-90 (manufactured by Kao Corporation; nonionic interface)". Activator, solid content 100%)'' and 6.2 parts of Emar 20CM (manufactured by Kao Corporation; anionic surfactant, solid content 25%) were added to an aqueous solution and stirred. An emulsified monomer composition was prepared.
　次いで、温度計、撹拌機、還流冷却管、窒素導入管および滴下ロートを備えたガラス製
反応容器に水（脱イオン水）１８５．０部、「エマール２０ＣＭ（花王社製；アニオン型界面活性剤、固形分２５％）」４．１部を仕込み、撹拌して溶解させ、７３℃まで昇温した。そこに上記乳化モノマーの５質量％を投入・撹拌し、反応容器に３％過硫酸カリウムを１．４部添加し、初期重合反応を行った。その後、８０℃に昇温し、温度を保ちつつ３％過硫酸カリウム６．７部と残りの上記乳化モノマー組成物を４時間かけて滴下し重合反応を進行させた。滴下終了後１０％アンモニア水溶液を用いてｐＨ８に調整したのち１時間反応を熟成させた。その後室温へと冷却することで、該高分子微粒子分散体を得た。 Next, in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction tube, and a dropping funnel, 185.0 parts of water (deionized water) was added, and "EMAL 20CM (manufactured by Kao Corporation; an anionic surfactant) was added. , solid content 25%) was charged, stirred to dissolve, and heated to 73°C. 5% by mass of the emulsified monomer was added thereto and stirred, and 1.4 parts of 3% potassium persulfate was added to the reaction vessel to perform an initial polymerization reaction. Thereafter, 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. After the dropwise addition was completed, the pH was adjusted to 8 using a 10% ammonia aqueous solution, and the reaction was aged for 1 hour. Thereafter, the dispersion of fine polymer particles was obtained by cooling to room temperature.
　［実施例２］
　シクロヘキシルメタクリレート７４．１部、ｎブチルメタクリレート１８．５部、メタクリル酸２－(ジメチルアミノ)エチル安息香酸塩１３．１部からなる混合物を、水（脱イオン水）４０．０部に「エマルゲンＡ－９０（花王社製；ノニオン型界面活性剤、固形分１００％）」２．０部と「サニゾールＢ－５０（花王社製；カチオン型界面活性剤、固形分５０％）」６．２部を溶解した水溶液中に添加し、撹拌することで乳化モノマー組成物を作製した。 [Example 2]
A mixture consisting of 74.1 parts of cyclohexyl methacrylate, 18.5 parts of n-butyl 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; nonionic surfactant, solid content 100%)" 2.0 parts and "Sanisol B-50 (manufactured by Kao Corporation; cationic surfactant, solid content 50%)" 6.2 parts An emulsified monomer composition was prepared by adding the monomer to an aqueous solution and stirring the mixture.
　次いで、温度計、撹拌機、還流冷却管、窒素導入管および滴下ロートを備えたガラス製反応容器に水（脱イオン水）１９０．０部、「サニゾールＢ－５０（花王社製；カチオン型界面活性剤、固形分５０％）」４．１部を仕込み、撹拌して溶解させ、７３℃まで昇温した。そこに上記乳化モノマーの５質量％を投入・撹拌し、反応容器に２，２－アゾビス（２－ジアミノプロパン）二塩酸塩の１５％水溶液を０．５部添加し、初期重合反応を行った。その後、８０℃に昇温し、温度を保ちつつ、２，２－アゾビス（２－ジアミノプロパン）二塩酸塩の１４％水溶液１．２部と残りの上記乳化モノマー組成物を４時間かけて滴下し重合反応を進行させた。滴下終了後１時間反応を熟成させた。その後室温へと冷却することで、該高分子微粒子分散体を得た。 Next, 190.0 parts of water (deionized water) was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a dropping funnel, and 190.0 parts of water (deionized water) was added to Sanisol B-50 (manufactured by Kao Corporation; cationic interface). 4.1 parts of activator (solid content: 50%) were added, stirred to dissolve, and heated to 73°C. 5% by mass of the emulsified monomer was added thereto and stirred, and 0.5 part of a 15% aqueous solution of 2,2-azobis(2-diaminopropane) dihydrochloride was added to the reaction vessel to perform an initial polymerization reaction. . Thereafter, the temperature was raised to 80°C, and while maintaining the temperature, 1.2 parts of a 14% aqueous solution of 2,2-azobis(2-diaminopropane) dihydrochloride and the remaining emulsifying monomer composition were added dropwise over 4 hours. The polymerization reaction was allowed to proceed. After completion of the dropwise addition, the reaction was allowed to mature for 1 hour. Thereafter, the dispersion of fine polymer particles was obtained by cooling to room temperature.
　［実施例３～５、７～１０、１３、１５～１７、１９～２３］ 
　実施例１において、モノマー種、配合量を下記表のように変更した以外は実施例１と同様にして該高分子微粒子分散体を得た。 [Examples 3-5, 7-10, 13, 15-17, 19-23]
The fine polymer 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.
　［実施例６、１８］ 
　実施例２において、モノマー種、配合量を下記表のように変更した以外は実施例１と同様にして該高分子微粒子分散体を得た。 [Example 6, 18]
In Example 2, the polymer fine particle dispersion was obtained in the same manner as in Example 1, except that the monomer species and blending amounts were changed as shown in the table below.
　［実施例１1］
　シクロヘキシルメタクリレート６９．０部、ｎ-ブチルメタクリレート２９．６部、メタクリル酸１．５０部からなる混合物を、水（脱イオン水）４１．０部に「ラテムルＰＤ－４２０（花王社製；反応型界面活性剤、固形分１００％）」5．０部を溶解した水溶液中に添加し、撹拌することで乳化モノマー組成物を作製した。 [Example 11]
A mixture of 69.0 parts of cyclohexyl methacrylate, 29.6 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.
　次いで、温度計、撹拌機、還流冷却管、窒素導入管および滴下ロートを備えたガラス製
反応容器に水（脱イオン水）１８５．０部、「ラテムルＰＤ－４２０（花王社製；反応型界面活性剤、固形分１００％）」5．０部を仕込み、撹拌して溶解させ、７３℃まで昇温した。そこに上記乳化モノマーの５質量％を投入・撹拌し、反応容器に３％過硫酸カリウムを１．４部添加し、初期重合反応を行った。その後、８０℃に昇温し、温度を保ちつつ３％過硫酸カリウム６．７部と残りの上記乳化モノマー組成物を４時間かけて滴下し重合反応を進行させた。滴下終了後１０％アンモニア水溶液を用いてｐＨ８に調整したのち１時間反応を熟成させた。その後室温へと冷却することで、該高分子微粒子分散体を得た。 Next, 185.0 parts of water (deionized water) was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a dropping funnel, and 185.0 parts of water (deionized water) was added to a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction tube, and a dropping funnel. Activator, solid content 100%)'' was charged, stirred to dissolve, and heated to 73°C. 5% by mass of the emulsified monomer was added thereto and stirred, and 1.4 parts of 3% potassium persulfate was added to the reaction vessel to perform an initial polymerization reaction. Thereafter, 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. After the dropwise addition was completed, the pH was adjusted to 8 using a 10% ammonia aqueous solution, and the reaction was aged for 1 hour. Thereafter, the dispersion of fine polymer particles was obtained by cooling to room temperature.
　［実施例１２］
　冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、ジエチレングリコールモノブチルエーテルを１００．０質量部仕込み、窒素雰囲気下で７０℃に昇温した後、そこへヨウ素０．４質量部、２，２‘－アゾビス（イソブチロニトリル）１．６質量部、シクロヘキシルメタクリレート６９.０質量部、及びジフェニルメタン０．１質量部を混合した溶液を２時間かけて連続的に滴下した。その後、７０℃を保持し、３．５時間の熟成を行い、Ａ鎖を得た。得られたＡ鎖の溶液を６０℃まで降温させた後、２，２‘－アゾビス（イソブチロニトリル）１．９質量部、ｎ－ブチルメタクリレート２９．６質量部、メタクリル酸１．５質量部を添加した。その後、７０℃に昇温し、４時間重合してＢ鎖を形成し、ブロックコポリマーを得た。水（脱イオン水）１３３．３質量部加えて希釈した。得られたブロックコポリマーの溶液を室温条件下、滴下終了後１０％アンモニア水溶液を用いてｐＨ８に調整したのち１時間反応を熟成させ、該高分子微粒子分散体を得た。 [Example 12]
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. A solution containing 0.4 parts by mass of iodine, 1.6 parts by mass of 2,2'-azobis(isobutyronitrile), 69.0 parts by mass of cyclohexyl methacrylate, and 0.1 parts by mass of diphenylmethane was continuously mixed over 2 hours. dripped onto the target. Thereafter, the temperature was maintained at 70° C. and aging was performed for 3.5 hours to obtain A chain. After cooling the obtained A chain solution to 60°C, 1.9 parts by mass of 2,2'-azobis(isobutyronitrile), 29.6 parts by mass of n-butyl methacrylate, and 1.5 parts by mass of methacrylic acid were added. part was added. Thereafter, the temperature was raised to 70°C and polymerization was performed for 4 hours to form a B chain and obtain a block copolymer. 133.3 parts by mass of water (deionized water) was added for dilution. After the dropwise addition of the resulting block copolymer solution was completed at room temperature, the pH was adjusted to 8 using a 10% ammonia aqueous solution, and the reaction was aged for 1 hour to obtain the polymer fine particle dispersion.
　［実施例１４］
　シクロヘキシルメタクリレート６９．０部、メタクリル酸１．５０部、2-(アクリロイルアミノ)-2-メチル-4-ペンタノン1部からなる混合物を、水（脱イオン水）４１．０部に「エマルゲンＡ－９０（花王社製；ノニオン型界面活性剤、固形分１００％）」２．０部と「エマール２０ＣＭ（花王社製；アニオン型界面活性剤、固形分２５％）」６．２部を溶解した水溶液中に添加し、撹拌することで乳化モノマー組成物を作製した。 [Example 14]
A mixture of 69.0 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.
　次いで、温度計、撹拌機、還流冷却管、窒素導入管および滴下ロートを備えたガラス製
反応容器に水（脱イオン水）１８５．０部、「エマール２０ＣＭ（花王社製；アニオン型界面活性剤、固形分２５％）」４．１部を仕込み、撹拌して溶解させ、７３℃まで昇温した。そこに上記乳化モノマーの５重量％を投入・撹拌し、反応容器に３％過硫酸カリウムを１．４部添加し、初期重合反応を行った。その後、８０℃に昇温し、温度を保ちつつ３％過硫酸カリウム６．７部と残りの上記乳化モノマー組成物を４時間かけて滴下し重合反応を進行させた。滴下終了後１０％アンモニア水溶液を用いてｐＨ８に調整したのち１時間反応を熟成させた。その後室温へと冷却させ、アジピン酸ジヒドラジド1部を加え攪拌することで、該高分子微粒子分散体を得た。 Next, in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction tube, and a dropping funnel, 185.0 parts of water (deionized water) was added, and "EMAL 20CM (manufactured by Kao Corporation; an anionic surfactant) was added. , solid content 25%) was charged, stirred to dissolve, and heated to 73°C. 5% by weight of the above emulsified monomer was added thereto and stirred, and 1.4 parts of 3% potassium persulfate was added to the reaction vessel to perform an initial polymerization reaction. Thereafter, 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. After the dropwise addition was completed, 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 the polymer fine particle dispersion.
　［比較例１～４］
　実施例１において、モノマー種、配合量を下記表のように変更した以外は実施例１と同様にして該高分子微粒子分散体を得た。 [Comparative Examples 1 to 4]
The fine polymer 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.
　［比較例５］
　実施例２において、モノマー種、配合量を下記表のように変更した以外は実施例１と同様にして該高分子微粒子分散体を得た。 [Comparative example 5]
In Example 2, the polymer fine particle dispersion was obtained in the same manner as in Example 1, except that the monomer species and blending amounts were changed as shown in the table below.
　２．顔料分散体の調製
　水（脱イオン水）８１．８５ｇに、顔料分散樹脂（（メタ）アクリル系樹脂　重量平均分子量２００００、酸価１４３ｍｇＫＯＨ／ｇ）２．５ｇと、Ｎ，Ｎ－ジメチルアミノエタノール０．６ｇを溶解させ、Ｃ．Ｉ．ピグメントブルー１５：３を１５ｇと消泡剤（エアープロダクツ社製「サーフィノール１０４ＰＧ」）を０．０５ｇ加え、ジルコニアビーズを用いてペイントシェーカーにて分散し、顔料分散体を得た。 2. Preparation of pigment dispersion 81.85 g of water (deionized water), 2.5 g of pigment dispersion resin ((meth)acrylic resin, weight average molecular weight 20000, acid value 143 mgKOH/g) and 0 N,N-dimethylaminoethanol Dissolve .6g of C. I. 15 g of Pigment Blue 15:3 and 0.05 g of an antifoaming agent ("Surfynol 104PG" manufactured by Air Products) were added and dispersed in a paint shaker using zirconia beads to obtain a pigment dispersion.
　３．水性インク組成物の調製
　（着色インクの調製方法）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１、３～５、７～１７、１９～２３、比較例１～４　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２５質量％とポリシロキサン化合物０．５質量％と水（脱イオン水）２９．５質量％と、を含む水性インク組成物を製造した。 3. Preparation of water-based ink composition (method for preparing colored ink)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 1, 3 to 5, 7 to 17, 19 to 23, Comparative Examples 1 to 4 solid content concentration 30%), and 1,2- An aqueous ink composition containing 25% by weight of propanediol, 0.5% by weight of a polysiloxane compound, and 29.5% by weight of water (deionized water) was produced.
　（受理溶液の調製方法）
　高分子微粒子分散体（実施例２、６、１８　比較例５　固形分濃度３０％）２５質量％と、１，２－ヘキサンジオール９質量％、１，２－プロパンジオール２５質量％とポリシロキサン化合物０．５質量％と水（脱イオン水）４０．５質量％と、を含む水性インク組成物を製造した。 (Preparation method of receiving solution)
25% by mass of polymer fine particle dispersion (Examples 2, 6, 18 Comparative Example 5 Solid content concentration 30%), 9% by mass of 1,2-hexanediol, 25% by mass of 1,2-propanediol, and a polysiloxane compound An aqueous ink composition containing 0.5% by weight and 40.5% by weight of water (deionized water) was prepared.
　（実施例２４、２６の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例２４、２６　固形分濃度３０％）２５質量％と、１，２－ヘキサンジオール２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 24 and 26)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 24, 26 solid content concentration 30%), 25% by mass of 1,2-hexanediol, and 0.5% by mass of polysiloxane compound. , a residual amount of water (deionized water), and an aqueous ink composition (colored ink) was produced.
　（実施例２５、２７の水性インク組成物の調製）
　高分子微粒子分散体（実施例２５、２７　固形分濃度３０％）２５質量％と、１，２－ヘキサンジオール２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 25 and 27)
25% by mass of polymer fine particle dispersion (Examples 25, 27 solid content concentration 30%), 25% by mass of 1,2-hexanediol, 0.5% by mass of polysiloxane compound, and water (deionized water) remaining. An aqueous ink composition (receiving solution) was prepared comprising:
　（実施例２８、２９の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例２８、２９　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、１，２－ヘキサンジオール９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 28 and 29)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 28 and 29 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 1,2-hexanediol. 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.
　（実施例３０、３２の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例３０、３２　固形分濃度３０％）２５質量％と、Ｎ－Ｎ－ジエチルホルムアミド２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 30 and 32)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 30, 32 solid content concentration 30%), 25% by mass of NN-diethylformamide, and 0.5% by mass of polysiloxane compound. , a residual amount of water (deionized water), and an aqueous ink composition (colored ink) was produced.
　（実施例３１、３３の水性インク組成物の調製）
　高分子微粒子分散体（実施例３１、３３　固形分濃度３０％）２５質量％と、Ｎ－Ｎ－ジエチルホルムアミド２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 31 and 33)
25% by mass of polymer fine particle dispersion (Examples 31, 33 solid content concentration 30%), 25% by mass of N-N-diethylformamide, 0.5% by mass of polysiloxane compound, and water (deionized water) remaining. An aqueous ink composition (receiving solution) was prepared comprising:
　（実施例３４、３６の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例３４、３６　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、Ｎ－Ｎ－ジエチルホルムアミド９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 34 and 36)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 34, 36 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.
　（実施例３５、３７の水性インク組成物の調製）
　高分子微粒子分散体（実施例３５、３７　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、Ｎ－Ｎ－ジエチルホルムアミド９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 35 and 37)
25% by mass of polymer fine particle dispersion (Examples 35, 37 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of NN-diethylformamide, and 0.5% by mass of polysiloxane compound. An aqueous ink composition (receiving solution) was produced, which contained % by mass and a residual amount of water (deionized water).
　（実施例３８、４０の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例３８、４０　固形分濃度３０％）２５質量％と、３－メトキシ－１－ブタノール２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 38 and 40)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 38 and 40 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 the remaining amount of water (deionized water) and the remaining amount of water (deionized water) was produced.
　（実施例３９、４１の水性インク組成物の調製）
　高分子微粒子分散体（実施例３９、４１　固形分濃度３０％）２５質量％と、３－メトキシ－１－ブタノール２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 39 and 41)
Aqueous ink composition containing 25% by mass of polymer fine particle dispersion (Examples 39, 41 solid content concentration 30%), 25% by mass of 3-methoxy-1-butanol, and remaining amount of water (deionized water) (receiving solution) was produced.
　（実施例４２、４４の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例４２、４４　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、３－メトキシ－１－ブタノール９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 42 and 44)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 42, 44 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 3-methoxy-1-butanol. %, 0.5% by mass of a polysiloxane compound, and a remaining amount of water (deionized water).
　（実施例４３、４５の水性インク組成物の調製）
　高分子微粒子分散体（実施例４３、４５　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、３－メトキシ－１－ブタノール９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 43 and 45)
25% by mass of polymer fine particle dispersion (Examples 43, 45 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methoxy-1-butanol, water (deionized water ) remaining amount, and an aqueous ink composition (receiving solution) was produced.
　（実施例４６、４８の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例４６、４８　固形分濃度３０％）２５質量％と、２－ピロリドン２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 46 and 48)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 46, 48 solid content concentration 30%), 25% by mass of 2-pyrrolidone, 0.5% by mass of polysiloxane compound, and water ( An aqueous ink composition (colored ink) containing the remaining amount of deionized water was produced.
　（実施例４７、４９の水性インク組成物の調製）
　高分子微粒子分散体（実施例４７、４９　固形分濃度３０％）２５質量％と、２－ピロリドン２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 47 and 49)
Aqueous ink composition (receiving solution) containing 25% by mass of polymer fine particle dispersion (Examples 47, 49 solid content concentration 30%), 25% by mass of 2-pyrrolidone, and remaining amount of water (deionized water). was manufactured.
　（実施例５０、５２の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例５０、５２　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、２－ピロリドン９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 50 and 52)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 50, 52 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-pyrrolidone, 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.
　（実施例５１、５３の水性インク組成物の調製）
　高分子微粒子分散体（実施例５１、５３　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、２－ピロリドン９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 51 and 53)
25% by mass of polymer fine particle dispersion (Examples 51, 53 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-pyrrolidone, and the remaining amount of water (deionized water). An aqueous ink composition (receiving solution) was produced.
　（実施例５４、５６の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例５４、５６　固形分濃度３０％）２５質量％と、３－メチル－１,３－ブタンジオール２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 54 and 56)
20% by mass of a pigment dispersion, 25% by mass of a polymer fine particle dispersion (Examples 54 and 56 solid content concentration 30%), 25% by mass of 3-methyl-1,3-butanediol, and 0.0% by mass of a polysiloxane compound. An aqueous ink composition (colored ink) containing 5% by mass and a remaining amount of water (deionized water) was produced.
　（実施例５５、５７の水性インク組成物の調製）
　高分子微粒子分散体（実施例５５、５７　固形分濃度３０％）２５質量％と、３－メチル－１,３－ブタンジオール２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 55 and 57)
An aqueous solution containing 25% by mass of polymer fine particle dispersion (Examples 55, 57 solid content concentration 30%), 25% by mass of 3-methyl-1,3-butanediol, and the remaining amount of water (deionized water). An ink composition (receiving solution) was produced.
　（実施例５８、６０の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例５８、６０　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、３－メチル－１,３－ブタンジオール９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 58 and 60)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 58 and 60 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-methyl-1,3-butane. An aqueous ink composition (colored ink) containing 9% by mass of diol, 0.5% by mass of polysiloxane compound, and the remaining amount of water (deionized water) was produced.
　（実施例５９、６１の水性インク組成物の調製）
　高分子微粒子分散体（実施例５９、６１　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、３－メチル－１,３－ブタンジオール９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 59 and 61)
25% by mass of polymer fine particle dispersion (Examples 59, 61 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methyl-1,3-butanediol, water ( An aqueous ink composition (receiving solution) containing the remaining amount of deionized water was prepared.
　（実施例６２、６４の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例６２、６４　固形分濃度３０％）２５質量％と、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 62 and 64)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 62 and 64 solid content concentration 30%), 25% by mass of 3-methoxy-N,N-dimethylpropanamide, and 0% by mass of polysiloxane compound. An aqueous ink composition (colored ink) containing .5% by mass and a residual amount of water (deionized water) was produced.
　（実施例６３、６５の水性インク組成物の調製）
　高分子微粒子分散体（実施例６３、６５　固形分濃度３０％）２５質量％と、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 63 and 65)
Contains 25% by mass of polymer fine particle dispersion (Examples 63, 65 solid content concentration 30%), 25% by mass of 3-methoxy-N,N-dimethylpropanamide, and remaining amount of water (deionized water). An aqueous ink composition (receiving solution) was produced.
　（実施例６６、６８の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例６６、６８　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 66 and 68)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 66 and 68 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-methoxy-N,N-dimethyl An aqueous ink composition (colored ink) containing 9% by mass of propanamide, 0.5% by mass of a polysiloxane compound, and a residual amount of water (deionized water) was produced.
　（実施例６７、６９の水性インク組成物の調製）
　高分子微粒子分散体（実施例６７、６９　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 67 and 69)
25% by mass of polymer fine particle dispersion (Examples 67, 69 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-methoxy-N,N-dimethylpropanamide, and water. (Deionized water) An aqueous ink composition (receiving solution) containing the remaining amount was produced.
　（実施例７０、７２の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例７０、７２　固形分濃度３０％）２５質量％と、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 70 and 72)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 70 and 72 solid content concentration 30%), 25% by mass of 3-butoxy-N,N-dimethylpropanamide, and 0% by mass of polysiloxane compound. An aqueous ink composition (colored ink) containing .5% by mass and a residual amount of water (deionized water) was produced.
　（実施例７１、７３の水性インク組成物の調製）
　高分子微粒子分散体（実施例７１、７３　固形分濃度３０％）２５質量％と、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 71 and 73)
Contains 25% by mass of polymer fine particle dispersion (Examples 71, 73 solid content concentration 30%), 25% by mass of 3-butoxy-N,N-dimethylpropanamide, and the remaining amount of water (deionized water). An aqueous ink composition (receiving solution) was produced.
　（実施例７４、７６の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例７４、７６　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 74 and 76)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 74 and 76 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 3-butoxy-N,N-dimethyl An aqueous ink composition (colored ink) containing 9% by mass of propanamide, 0.5% by mass of a polysiloxane compound, and a residual amount of water (deionized water) was produced.
　（実施例７５、７７の水性インク組成物の調製）
　高分子微粒子分散体（実施例７５、７７　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 75 and 77)
25% by mass of polymer fine particle dispersion (Examples 75, 77 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 3-butoxy-N,N-dimethylpropanamide, and water. (Deionized water) An aqueous ink composition (receiving solution) containing the remaining amount was produced.
　（実施例７８、８０の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例７８、８０　固形分濃度３０％）２５質量％と、テキサノール２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 78 and 80)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 78 and 80 solid content concentration 30%), 25% by mass of Texanol, 0.5% by mass of polysiloxane compound, and water (deionized). An aqueous ink composition (colored ink) containing the remaining amount of water) was produced.
　（実施例７９、８１の水性インク組成物の調製）
　高分子微粒子分散体（実施例７９、８１　固形分濃度３０％）２５質量％と、テキサノール２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 79 and 81)
Produced an aqueous ink composition (receiving solution) containing 25% by mass of polymer fine particle dispersion (Examples 79, 81 solid content concentration 30%), 25% by mass of Texanol, and the remaining amount of water (deionized water). did.
　（実施例８２、８４の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例８２、８４　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、テキサノール９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 82 and 84)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 82, 84 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of Texanol, polysiloxane compound An aqueous ink composition (colored ink) containing 0.5% by mass and a residual amount of water (deionized water) was produced.
　（実施例８３、８５の水性インク組成物の調製）
　高分子微粒子分散体（実施例８３、８５　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、テキサノール９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 83 and 85)
25% by mass of polymer fine particle dispersion (Examples 83, 85 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of Texanol, and the remaining amount of water (deionized water). An aqueous ink composition (receiving solution) was prepared.
　（実施例８６、８８の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例８６、８８　固形分濃度３０％）２５質量％と、γ－バレロラクトン２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 86 and 88)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 86 and 88 solid content concentration 30%), 25% by mass of γ-valerolactone, 0.5% by mass of polysiloxane compound, and water. (deionized water) An aqueous ink composition (colored ink) containing the remaining amount.
　（実施例８７、８９の水性インク組成物の調製）
　高分子微粒子分散体（実施例８７、８９　固形分濃度３０％）２５質量％と、γ－バレロラクトン２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 87 and 89)
An aqueous ink composition (receiving solution) containing 25% by mass of a polymer fine particle dispersion (Examples 87, 89 solid content concentration 30%), 25% by mass of γ-valerolactone, and the remaining amount of water (deionized water). ) was manufactured.
　（実施例９０、９２の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例９０、９２　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、γ－バレロラクトン９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 90 and 92)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 90, 92 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of γ-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.
　（実施例９１、９３の水性インク組成物の調製）
　高分子微粒子分散体（実施例９１、９３　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、γ－バレロラクトン９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 91 and 93)
25% by mass of polymer fine particle dispersion (Examples 91, 93 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of γ-valerolactone, and remaining amount of water (deionized water) An aqueous ink composition (receiving solution) containing the following was produced.
　（実施例９４、９６の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例９４、９６　固形分濃度３０％）２５質量％と、Ｎ－メチル－イプシロン－カプロラクタム２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 94 and 96)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 94, 96 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 the remaining amount of water (deionized water) and the remaining amount of water (deionized water) was produced.
　（実施例９５、９７の水性インク組成物の調製）
　高分子微粒子分散体（実施例９５、９７　固形分濃度３０％）２５質量％と、Ｎ－メチル－イプシロン－カプロラクタム２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 95 and 97)
Aqueous ink composition containing 25% by mass of polymer fine particle dispersion (Examples 95, 97 solid content concentration 30%), 25% by mass of N-methyl-epsilon-caprolactam, and remaining amount of water (deionized water). (receiving solution) was produced.
　（実施例９８、１００の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例９８、１００　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、Ｎ－メチル－イプシロン－カプロラクタム９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 98 and 100)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 98 and 100 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of N-methyl-epsilon-caprolactam. %, a polysiloxane compound of 0.5% by mass, and a residual amount of water (deionized water).
　（実施例９９、１０１の水性インク組成物の調製）
　高分子微粒子分散体（実施例９９、１０１　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、Ｎ－メチル－イプシロン－カプロラクタム９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 99 and 101)
25% by mass of polymer fine particle dispersion (Examples 99, 101 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of N-methyl-epsilon-caprolactam, water (deionized water ) remaining amount, and an aqueous ink composition (receiving solution) was produced.
　（実施例１０２、１０４の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１０２、１０４　固形分濃度３０％）２５質量％と、２－ヒドロキシルエチルモルフォリン２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 102 and 104)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 102, 104 solid content concentration 30%), 25% by mass of 2-hydroxylethylmorpholine, and 0.5% by mass of polysiloxane compound. , a residual amount of water (deionized water), and an aqueous ink composition (colored ink) was produced.
　（実施例１０３、１０５の水性インク組成物の調製）
　高分子微粒子分散体（実施例１０３、１０５　固形分濃度３０％）２５質量％と、２－ヒドロキシルエチルモルフォリン２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 103 and 105)
Aqueous ink composition ( A receiving solution) was prepared.
　（実施例１０６、１０８の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１０６、１０８　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、２－ヒドロキシルエチルモルフォリン９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 106 and 108)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 106 and 108 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 2-hydroxylethylmorpholine. 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.
　（実施例１０７、１０９の水性インク組成物の調製）
　高分子微粒子分散体（実施例１０７、１０９　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、２－ヒドロキシルエチルモルフォリン９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 107 and 109)
25% by mass of polymer fine particle dispersion (Examples 107, 109 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-hydroxylethylmorpholine, and water (deionized water) An aqueous ink composition (receiving solution) containing the remaining amount was produced.
　（実施例１１０、１１２の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１１０、１１２　固形分濃度３０％）２５質量％と、２－ヒドロキシルエチルピロリドン２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 110 and 112)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 110, 112 solid content concentration 30%), 25% by mass of 2-hydroxylethylpyrrolidone, and 0.5% by mass of polysiloxane compound, An aqueous ink composition (colored ink) containing a residual amount of water (deionized water) was produced.
　（実施例１１１、１１３の水性インク組成物の調製）
　高分子微粒子分散体（実施例１１１、１１３　固形分濃度３０％）２５質量％と、２－ヒドロキシルエチルピロリドン２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 111 and 113)
An aqueous ink composition (accepted) containing 25% by mass of polymer fine particle dispersion (Examples 111, 113 solid content concentration 30%), 25% by mass of 2-hydroxylethylpyrrolidone, and the remaining amount of water (deionized water). solution) was produced.
　（実施例１１４、１１６の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１１４、１１６　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、２－ヒドロキシルエチルピロリドン９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 114 and 116)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 114, 116 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of 2-hydroxylethylpyrrolidone. , 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.
　（実施例１１５、１１７の水性インク組成物の調製）
　高分子微粒子分散体（実施例１１５、１１７　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、２－ヒドロキシルエチルピロリドン９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 115 and 117)
25% by mass of polymer fine particle dispersion (Examples 115, 117 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of 2-hydroxylethylpyrrolidone, and the remainder of water (deionized water). An aqueous ink composition (receiving solution) was prepared comprising:
　（実施例１１８、１２０の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１１８、１２０　固形分濃度３０％）２５質量％と、トリプロピレングリコールモノメチルエーテル２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 118 and 120)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 118 and 120 solid content concentration 30%), 25% by mass of tripropylene glycol monomethyl ether, and 0.5% by mass of polysiloxane compound. An aqueous ink composition (colored ink) containing a residual amount of water (deionized water) was produced.
　（実施例１１９、１２１の水性インク組成物の調製）
　高分子微粒子分散体（実施例１１９、１２１　固形分濃度３０％）２５質量％と、トリプロピレングリコールモノメチルエーテル２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 119 and 121)
An aqueous ink composition (accepted) containing 25% by mass of polymer fine particle dispersion (Examples 119, 121 solid content concentration 30%), 25% by mass of tripropylene glycol monomethyl ether, and the remaining amount of water (deionized water). solution) was produced.
　（実施例１２２、１２４の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１２２、１２４　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、トリプロピレングリコールモノメチルエーテル９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 122 and 124)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 122, 124 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of tripropylene glycol monomethyl ether. , 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.
　（実施例１２３、１２５の水性インク組成物の調製）
　高分子微粒子分散体（実施例１２３、１２５　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、トリプロピレングリコールモノメチルエーテル９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 123 and 125)
25% by mass of polymer fine particle dispersion (Examples 123, 125 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of tripropylene glycol monomethyl ether, and the remainder of water (deionized water). An aqueous ink composition (receiving solution) was prepared comprising:
　（実施例１２６、１２８の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１２６、１２８　固形分濃度３０％）２５質量％と、ジプロピレングリコールモノメチルエーテル２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 126 and 128)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 126 and 128 solid content concentration 30%), 25% by mass of dipropylene glycol monomethyl ether, and 0.5% by mass of polysiloxane compound, An aqueous ink composition (colored ink) containing a residual amount of water (deionized water) was produced.
　（実施例１２７、１２９の水性インク組成物の調製）
　高分子微粒子分散体（実施例１２７、１２９　固形分濃度３０％）２５質量％と、ジプロピレングリコールモノメチルエーテル２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 127 and 129)
An aqueous ink composition (accepted) containing 25% by mass of polymer fine particle dispersion (Examples 127, 129 solid content concentration 30%), 25% by mass of dipropylene glycol monomethyl ether, and the remaining amount of water (deionized water). solution) was produced.
　（実施例１３０、１３２の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１３０、１３２　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、ジプロピレングリコールモノメチルエーテル９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 130 and 132)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 130, 132 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of dipropylene glycol monomethyl ether. , 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.
　（実施例１３１、１３３の水性インク組成物の調製）
　高分子微粒子分散体（実施例１３１、１３３　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、ジプロピレングリコールモノメチルエーテル９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 131 and 133)
25% by mass of polymer fine particle dispersion (Examples 131, 133 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of dipropylene glycol monomethyl ether, and the remainder of water (deionized water). An aqueous ink composition (receiving solution) was prepared comprising:
　（実施例１３４、１３６の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１３４、１３６　固形分濃度３０％）２５質量％と、トリエチレングリコールモノメチルエーテル２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 134 and 136)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 134, 136 solid content concentration 30%), 25% by mass of triethylene glycol monomethyl ether, 0.5% by mass of polysiloxane compound, An aqueous ink composition (colored ink) containing a residual amount of water (deionized water) was produced.
　（実施例１３５、１３７の水性インク組成物の調製）
　高分子微粒子分散体（実施例１３５、１３７　固形分濃度３０％）２５質量％と、トリエチレングリコールモノメチルエーテル２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 135 and 137)
An aqueous ink composition (accepted) containing 25% by mass of a polymer fine particle dispersion (Examples 135, 137 solid content concentration 30%), 25% by mass of triethylene glycol monomethyl ether, and the remaining amount of water (deionized water). solution) was produced.
　（実施例１３８、１４０の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１３８、１４０　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、トリエチレングリコールモノメチルエーテル９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 138 and 140)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 138 and 140 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of triethylene glycol monomethyl ether. , 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.
　（実施例１３９、１４１の水性インク組成物の調製）
　高分子微粒子分散体（実施例１３９、１４１　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、トリエチレングリコールモノメチルエーテル９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 139 and 141)
25% by mass of polymer fine particle dispersion (Examples 139, 141 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of triethylene glycol monomethyl ether, and water (deionized water) remaining. An aqueous ink composition (receiving solution) was prepared comprising:
　（実施例１４２、１４４の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１４２、１４４　固形分濃度３０％）２５質量％と、トリエチレングリコールモノブチルエーテル２５質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 142 and 144)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 142, 144 solid content concentration 30%), 25% by mass of triethylene glycol monobutyl ether, 0.5% by mass of polysiloxane compound, An aqueous ink composition (colored ink) containing a residual amount of water (deionized water) was produced.
　（実施例１４３、１４５の水性インク組成物の調製）
　高分子微粒子分散体（実施例１４３、１４５　固形分濃度３０％）２５質量％と、トリエチレングリコールモノブチルエーテル２５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。 (Preparation of aqueous ink compositions of Examples 143 and 145)
An aqueous ink composition (accepted) containing 25% by mass of a polymer fine particle dispersion (Examples 143, 145 solid content concentration 30%), 25% by mass of triethylene glycol monobutyl ether, and the remaining amount of water (deionized water). solution) was produced.
　（実施例１４６、１４８の水性インク組成物の調製）
　顔料分散体２０質量％と、高分子微粒子分散体（実施例１４６、１４８　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、トリエチレングリコールモノブチルエーテル９質量％と、ポリシロキサン化合物０．５質量％と、水（脱イオン水）残量と、を含む水性インク組成物（着色インク）を製造した。 (Preparation of aqueous ink compositions of Examples 146 and 148)
20% by mass of pigment dispersion, 25% by mass of polymer fine particle dispersion (Examples 146, 148 solid content concentration 30%), 20% by mass of 1,2-propanediol, and 9% by mass of triethylene glycol monobutyl ether. , 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.
　（実施例１４７、１４９の水性インク組成物の調製）
　高分子微粒子分散体（実施例１４７、１４９　固形分濃度３０％）２５質量％と、１，２－プロパンジオール２０質量％と、トリエチレングリコールモノブチルエーテル９質量％と、水（脱イオン水）残量と、を含む水性インク組成物（受理溶液）を製造した。
  (Preparation of aqueous ink compositions of Examples 147 and 149)
25% by mass of polymer fine particle dispersion (Examples 147, 149 solid content concentration 30%), 20% by mass of 1,2-propanediol, 9% by mass of triethylene glycol monobutyl ether, and the remainder of water (deionized water). An aqueous ink composition (receiving solution) was prepared comprising:
　（実施例１５０～１５４の水性インク組成物の調製）
　上記の実施例１～３、６の水性インク組成物において、高分子微粒子分散体の含有割合を１３質量％に変更し、合計含有量が１００質量％となるように水（脱イオン水）の含有割合を変更して水性インク組成物を製造した。 (Preparation of aqueous ink compositions of Examples 150 to 154)
In the aqueous ink compositions of Examples 1 to 3 and 6 above, the content of the polymer fine particle dispersion was changed to 13% by mass, and water (deionized water) was added so that the total content was 100% by mass. Aqueous ink compositions were manufactured by changing the content ratio.
　４．水性インク組成物の評価
　（耐溶剤性）
　実施例及び比較例の水性インク組成物について耐溶剤性を評価した。具体的には、実施例及び比較例の水性インク組成物を被印刷基材（糊付きポリ塩化ビニルフィルム、表面改質処理基材：コロナ処理ＯＰＰ）にインクジェット記録装置により印字濃度１００％のベタ画像の印刷物を製造し、下記表に記載の温度（６０℃、８０℃、１００℃）で８分乾燥後、印刷直後のインク組成物の塗布面の塗膜に対して学振型摩擦堅牢度試験機ＩＩ型にて、加重１ｋｇ（糊付きポリ塩化ビニルフィルム）及び加重２００g（コロナ処理ＯＰＰ）、当布：質量濃度５０％のエタノール水溶液に浸した金巾３号の条件で塗膜の外観を観察し、下記評価基準（塗膜外観指標）により塗膜の外観を評価した（表中、耐溶剤性と表記）。 4. Evaluation of water-based ink composition (solvent resistance)
The solvent resistance of the aqueous ink compositions of Examples and Comparative Examples was evaluated. Specifically, the aqueous ink compositions of Examples and Comparative Examples were applied to a printing substrate (adhesive polyvinyl chloride film, surface-modified substrate: corona-treated OPP) using an inkjet recording device to print a solid image with a printing density of 100%. After producing a printed image of the image and drying it for 8 minutes at the temperatures listed in the table below (60°C, 80°C, 100°C), the Gakushin type abrasion fastness test was applied to the coating film on the coated surface of the ink composition immediately after printing. The appearance of the coating film was examined using a Type II tester under the conditions of a weight of 1 kg (adhesive polyvinyl chloride film) and a weight of 200 g (corona-treated OPP), and a No. 3 cloth immersed in an ethanol aqueous solution with a mass concentration of 50%. The appearance of the coating film was evaluated using the following evaluation criteria (coating film appearance index) (indicated as solvent resistance in the table).
　評価基準
　　　Ａ：１００回後に外観変化無し
　　　Ｂ：７５回後に外観変化無し・１００回後にやや外観変化有り
　　　Ｃ：５０回後に外観変化無し・７５回後にやや外観変化有り
　　　Ｄ：２５回後に外観変化無し・５０回後にやや外観変化有り
　　　Ｅ：２５回後に外観変化有り（実用範囲外） Evaluation criteria A: No change in appearance after 100 times B: No change in appearance after 75 times / Slight change in appearance after 100 times C: No change in appearance after 50 times / Slight change in appearance after 75 times D: No change in appearance after 25 times・There is a slight change in appearance after 50 times E: There is a change in appearance after 25 times (outside the practical range)
　（保存安定性）
　実施例及び比較例の水性インク組成物について保存安定性を評価した。具体的には、インク組成物を６０℃オーブン内で１週間加温し、液温２５℃で測定した加温前後の粘度を測定し、以下の評価基準に基づき評価を行った。評価結果を下記表に記載した（表中、「保存安定性」と表記）。 (Storage stability)
The storage stability of the aqueous ink compositions of Examples and Comparative Examples was evaluated. Specifically, the 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).
　評価基準
　Ａ：粘度変化率５％以下
　Ｂ：粘度変化率５％超７．５％未満
　Ｃ：粘度変化率７．５％以上１０％未満
　Ｄ：粘度変化率１０％以上（実用範囲外） Evaluation criteria A: Viscosity change rate 5% or less B: Viscosity change rate more than 5% but less than 7.5% C: Viscosity change rate 7.5% or more and less than 10% D: Viscosity change rate 10% or more (outside practical range)
　（間欠吐出性）
　実施例及び比較例のインク組成物について間欠吐出性(吐出安定性)を評価した。具体的には、インク組成物をインクカートリッジ（収容容器）に充填し、そのインクカートリッジ（収容容器）を、ピエゾ式インクジェットヘッド搭載のシリアル方式のインクジェット記録装置に搭載して、そのインクジェット記録装置により、ノズルチェックパターンを印刷し、ヘッドキャップをしない状態で１０分間静置後に同様の印刷を行った。静置前後でノズル欠け有無を確認し、静置前のパターンに対するノズル欠けが１０％未満になるまで同印刷を繰り返し、その回数により吐出性を以下の評価基準に基づき評価を行った。評価結果を下記表に記載した（表中、「間欠吐出性」と表記）。 (Intermittent discharge)
The ink compositions of Examples and Comparative Examples were evaluated for intermittent ejection performance (ejection stability). Specifically, an ink composition is filled into an ink cartridge (accommodation container), the ink cartridge (accommodation container) is mounted on a serial type inkjet recording device equipped with a piezo type inkjet head, and the inkjet recording device is used to print the inkjet recording device. , a nozzle check pattern was printed, the head was left standing for 10 minutes without a head cap, and then similar printing was performed. 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).
　評価基準
　Ａ：静置後の印刷１回目でノズル欠け１０％以下
　Ｂ：静置後の印刷２回目でノズル欠け１０％以下
　Ｃ：静置後の印刷３回目でノズル欠け１０％以下
　Ｄ：静置後の印刷４回目でノズル欠け１０％以下
　Ｅ：静置後の印刷４回目でノズル欠け１１％以上（実用範囲外） 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)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　表中、「ＭＡＡ」とは、メタクリル酸である。
　表中、「ＤＭＭＡ」とはメタクリル酸２－（ジメチルアミノ）エチルである。
　表中、「ＣＨＭＡ」とは、シクロヘキシルメタクリレートである。
　表中、「ＰｈＭＡ」とは、フェニルメタクリレートである。
　表中、「ＭＭＡ」とは、メチルメタクリレートである。
　表中、「ＩＢＸＭＡ」とは、イソボルニルメタクリレート
　表中、「ＮＭＡ」とは、ナフタレニルメタクリレート
　表中、「ＢＭＡ」とは、ブチルメタクリレートである。
　表中、「ＣＨＡ」とは、シクロヘキシルアクリレートである。
　表中、「ＭＡ」とは、メチルアクリレート
　表中、「２－ＥＨＡ」とは、２－エチルヘキシルアクリレート
　表中、「Ｓｔ」とは、スチレンである。
　表中、「塩ビ」とは、糊付きポリ塩化ビニルフィルムである。
　表中、「コロナ処理ＯＰＰ」とは、表面に対してコロナ処理が施されたポリプロピレン系樹脂基材（ポリオレフィン系樹脂基材）である。 In the table, "MAA" is methacrylic acid.
In the table, "DMMA" is 2-(dimethylamino)ethyl methacrylate.
In the table, "CHMA" is cyclohexyl methacrylate.
In the table, "PhMA" is phenyl methacrylate.
In the table, "MMA" is methyl methacrylate.
In the table, "IBXMA" is isobornyl methacrylate. In the table, "NMA" is naphthalenyl methacrylate. In the table, "BMA" is butyl methacrylate.
In the table, "CHA" is cyclohexyl acrylate.
In the table, "MA" means methyl acrylate. In the table, "2-EHA" means 2-ethylhexyl acrylate. In the table, "St" means styrene.
In the table, "PVC" refers to adhesive polyvinyl chloride film.
In the table, "corona-treated OPP" is a polypropylene resin base material (polyolefin resin base material) whose surface has been subjected to corona treatment.
　上記表から分かるように、ガラス転移温度（Ｔｇ）が０℃以上１２０℃以下のアクリル系樹脂を含有し、少なくとも２種類のモノマーを構成単位として含む共重合体を含有する水性インク組成物であれば、６０℃、８０℃、１００℃で乾燥させた場合であっても、得られる記録物の耐溶剤性が高いことが分かる。 As can be seen from the table above, any aqueous ink composition containing an acrylic resin with a glass transition temperature (Tg) of 0°C or more and 120°C or less and a copolymer containing at least two types of monomers as constituent units. For example, it can be seen that even when dried at 60°C, 80°C, or 100°C, the obtained recorded matter has high solvent resistance.
　このなかでも、水／１－オクタノールでの分配係数（ＬｏｇＰ）が１．０以上のアクリルモノマーＡを含有する実施例１～１４の水性インク組成物は、実施例１５、１６、１７の水性インク組成物と比較しても、耐溶剤性の高い塗膜を形成できた。 Among these, the aqueous ink compositions of Examples 1 to 14 containing acrylic monomer A having a water/1-octanol partition coefficient (LogP) of 1.0 or more are the aqueous ink compositions of Examples 15, 16, and 17. Even compared to the composition, a coating film with high solvent resistance could be formed.
　また、モノマーＢを加えホモポリマーのＴｇが６０℃以下のモノマーＣを含有する実施例１～１４であれば、実施例１８の水性インク組成物と比較しても、耐溶剤性の高い塗膜を形成できた。 In addition, in Examples 1 to 14 containing monomer C in which monomer B is added and the homopolymer Tg is 60°C or less, even compared to the aqueous ink composition of Example 18, the coating film has high solvent resistance. was able to form.
　また、水／１－オクタノールでの分配係数（ＬｏｇＰ）が１．９以上のアクリルモノマーＡを含有する実施例１～１４であれば、実施例１９の水性インク組成物と比較しても耐溶剤性の高い塗膜を形成できた。 In addition, in Examples 1 to 14 containing acrylic monomer A having a water/1-octanol partition coefficient (LogP) of 1.9 or more, the solvent resistance was higher than that of the aqueous ink composition of Example 19. A coating film with high properties was formed.
　また、水／１－オクタノールでの分配係数（ＬｏｇＰ）が４以下のアクリルモノマーＡを含有する実施例１～１４であれば、実施例２０の水性インク組成物と比較しても溶剤性の高い塗膜を形成できた。 In addition, Examples 1 to 14 containing acrylic monomer A with a water/1-octanol partition coefficient (LogP) of 4 or less have high solvent properties compared to the aqueous ink composition of Example 20. A coating film was formed.
　また、ガラス転移温度が４０℃以上である実施例１～１４であれば、実施例２１の水性インク組成物と比較しても耐溶剤性の高い塗膜を形成できた。 In addition, in Examples 1 to 14 in which the glass transition temperature was 40° C. or higher, coating films with high solvent resistance could be formed compared to the aqueous ink composition of Example 21.
　また、ガラス転移温度が８０℃以下である実施例１～１４であれば、実施例２２、２３の水性インク組成物と比較しても耐溶剤性の高い塗膜を形成できた。 Furthermore, in Examples 1 to 14, in which the glass transition temperature was 80° C. or lower, coating films with high solvent resistance could be formed compared to the aqueous ink compositions of Examples 22 and 23.
　また、有機溶剤の種類を変更した実施例２４～１５４の水性インク組成物であっても実施例１～２３の水性インク組成物同様に得られる記録物の耐溶剤性が高いことが分かる。 Furthermore, it can be seen that even with the aqueous ink compositions of Examples 24 to 154 in which the type of organic solvent was changed, the solvent resistance of the resulting recorded matter is high, similar to the aqueous ink compositions of Examples 1 to 23.
　一方、ガラス転移温度（Ｔｇ）が１２０℃超の共重合体を含有する比較例２の水性インク組成物やガラス転移温度（Ｔｇ）が０℃未満の共重合体を含有する比較例３の水性インク組成物は、得られる記録物の耐溶剤性が低く、本発明の効果を奏するものとなっていない。また、アクリルモノマーの単独重合体を含有する比較例１の水性インク組成物は、６０℃での耐溶剤性が低く、本発明の効果を奏するものとなっていない。 On the other hand, the aqueous ink composition of Comparative Example 2 containing a copolymer with a glass transition temperature (Tg) of more than 120°C and the aqueous ink composition of Comparative Example 3 containing a copolymer with a glass transition temperature (Tg) of less than 0°C. The ink composition provides a recorded matter with low solvent resistance, and does not exhibit the effects of the present invention. Further, the aqueous ink composition of Comparative Example 1 containing a homopolymer of acrylic monomer had low solvent resistance at 60° C., and did not exhibit the effects of the present invention.
　また、モノマーＢを含有しない比較例４やモノマーＡを含有しない比較例５は、保存安定性が低下するか、又は得られる記録物の耐溶剤性が低下しており、本発明の効果を奏するものとなっていない。 In addition, Comparative Example 4 that does not contain monomer B and Comparative Example 5 that does not contain monomer A have a decreased storage stability or a decreased solvent resistance of the obtained recorded material, and the effects of the present invention are not achieved. It has not become a thing.

Claims (11)

  1. 　水と、樹脂と、を含有する水性インク組成物であって、
    　前記樹脂の少なくとも一部は、高分子微粒子分散体として含有し、
    　前記樹脂は、アクリル系樹脂を含有し、
    　前記アクリル系樹脂は、少なくとも２種類のモノマーを構成単位として含む共重合体を含有し、
    　前記アクリル系樹脂のＴｇは、０℃以上１２０℃以下である
    　水性インク組成物。     An aqueous ink composition containing water and a resin,
    At least a portion of the resin is contained as a polymer fine particle dispersion,
    The resin contains an acrylic resin,
    The acrylic resin contains a copolymer containing at least two types of monomers as constituent units,
    The acrylic resin has a Tg of 0°C or more and 120°C or less.A water-based ink composition.
  2. 　前記アクリル系樹脂は、以下のモノマーＡ、モノマーＢを構成単位として含む共重合体を含有する
    　請求項１に記載の水性インク組成物。
    　モノマーＡ：水／１－オクタノールでの分配係数（ＬｏｇＰ）が１．０以上のアクリルモノマー
    　モノマーＢ：モノマーＡ以外であって、酸性基または塩基性基を有するモノマー     The aqueous ink composition according to claim 1, wherein the acrylic resin contains a copolymer containing the following monomers A and B as constituent units.
    Monomer A: an acrylic monomer with a water/1-octanol partition coefficient (LogP) of 1.0 or more Monomer B: a monomer other than monomer A that has an acidic group or a basic group
  3. 　前記モノマーＡのホモポリマーのＴｇが６０℃以上である
    　請求項２に記載の水性インク組成物。     The aqueous ink composition according to claim 2, wherein the homopolymer of monomer A has a Tg of 60°C or higher.
  4. 　前記アクリル系樹脂は、さらに以下のモノマーＣを構成単位として含む共重合体を含有する
    　請求項３に記載の水性インク組成物。
    　モノマーＣ：モノマーＡ、モノマーＢ以外であって、ホモポリマーのＴｇが６０℃未満のモノマー     The aqueous ink composition according to claim 3, wherein the acrylic resin further contains a copolymer containing the following monomer C as a constituent unit.
    Monomer C: A monomer other than Monomer A and Monomer B whose homopolymer Tg is less than 60°C
  5. 　前記モノマーＡの水／１－オクタノールでの分配係数（ＬｏｇＰ）が１．９以上４．８以下である
    　請求項２から４のいずれかに記載の水性インク組成物。     The aqueous ink composition according to any one of claims 2 to 4, wherein the monomer A has a water/1-octanol partition coefficient (LogP) of 1.9 or more and 4.8 or less.
  6. 　前記アクリル系樹脂のＴｇは、４０℃以上８０℃以下である
    　請求項１から５のいずれかに記載の水性インク組成物。     The aqueous ink composition according to any one of claims 1 to 5, wherein the acrylic resin has a Tg of 40°C or more and 80°C or less.
  7. 　請求項１から６のいずれかに記載の水性インク組成物を含む
    　インクセット。     An ink set comprising the aqueous ink composition according to any one of claims 1 to 6.
  8. 　請求項１から６のいずれかに記載の水性インク組成物をインクジェット吐出する
    　記録方法。     A recording method comprising inkjet-discharging the aqueous ink composition according to any one of claims 1 to 6.
  9. 　請求項１から６のいずれかに記載の水性インク組成物をインクジェット吐出して記録物を得る
    　記録物の製造方法。     A method for producing a recorded matter, comprising obtaining a recorded matter by inkjet discharging the aqueous ink composition according to any one of claims 1 to 6.
  10. 　基材の表面に請求項１から６のいずれかに記載の水性インク組成物が塗布された記録物。 A recorded matter in which the aqueous ink composition according to any one of claims 1 to 6 is coated on the surface of a base material.
  11. 　請求項１から６のいずれかに記載の水性インク組成物を搭載したインク貯蔵機構を備えた
    　インクジェット記録装置。     An inkjet recording device comprising an ink storage mechanism loaded with the aqueous ink composition according to claim 1.
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JP2004203996A (en) * 2002-12-25 2004-07-22 Kao Corp Water-based ink
JP2005272790A (en) * 2003-04-07 2005-10-06 Seiko Epson Corp Water-borne ink composition and method of manufacturing the same
JP2007077371A (en) * 2005-09-16 2007-03-29 Kao Corp Water-based ink for ink-jet recording
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