WO2023163063A1 - Ink composition, ink set, recorded product having ink composition applied on base material, recording method, manufacturing method for recorded product, and inkjet recording device equipped with accommodation container filled with ink composition - Google Patents

Ink composition, ink set, recorded product having ink composition applied on base material, recording method, manufacturing method for recorded product, and inkjet recording device equipped with accommodation container filled with ink composition Download PDF

Info

Publication number
WO2023163063A1
WO2023163063A1 PCT/JP2023/006538 JP2023006538W WO2023163063A1 WO 2023163063 A1 WO2023163063 A1 WO 2023163063A1 JP 2023006538 W JP2023006538 W JP 2023006538W WO 2023163063 A1 WO2023163063 A1 WO 2023163063A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink composition
ink
composition according
resin
resins
Prior art date
Application number
PCT/JP2023/006538
Other languages
French (fr)
Japanese (ja)
Inventor
保真 齋藤
祐二 牧本
充功 田村
Original Assignee
株式会社Dnpファインケミカル
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社Dnpファインケミカル filed Critical 株式会社Dnpファインケミカル
Publication of WO2023163063A1 publication Critical patent/WO2023163063A1/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41JTYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005Typewriters 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
    • B41J2/01Ink jet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks

Definitions

  • the present invention provides an ink composition, an ink set, a recorded matter obtained by applying the ink composition onto a substrate, a recording method, a method for producing a recorded matter, and an ink jet recording method equipped with a container filled with the ink composition. Regarding the device.
  • the inkjet recording method is a recording method in which droplets of an ink composition are directly ejected from very fine nozzles onto a base material such as paper and applied to obtain letters and images.
  • This recording method is easy to reduce size, increase speed, reduce noise, save power, and colorize. , and the range of application has expanded to include commercial printing applications.
  • Aqueous ink compositions in which various coloring materials are dissolved or dispersed in water or a mixture of water and a water-soluble organic solvent are widely used as ink compositions used in inkjet recording systems.
  • Such water-based ink compositions have less impact on the environment than non-aqueous ink compositions containing organic solvents used in the same inkjet recording system, and are non-flammable. Safe for people.
  • the aqueous ink composition requires a larger amount of heat for drying, so in terms of productivity, it was necessary to set the drying temperature higher than extending the drying time. As a result, the power consumption of the device increases, so the need for a 200V power supply limits the installation location and makes it difficult to comply with safety standards. giving.
  • Patent Document 1 describes a technique relating to an inkjet recording method including a step of ejecting an aqueous ink composition containing 2-pyrrolidone and water-insoluble thermoplastic resin particles containing a urethane resin.
  • Japanese Patent Laid-Open No. 2002-100001 describes that this inkjet recording method can obtain an image with little ink bleeding, high image quality, and excellent abrasion resistance.
  • An object of the present invention is to provide an ink composition with high drying properties and high productivity of the resulting recorded matter.
  • the present inventors found that the above problems can be solved with an ink composition containing an amide-based solvent having a predetermined boiling point or less. Arrived. Specifically, the present invention provides the following.
  • the amide solvent includes N-ethyl-N-methylformamide, N-methyl-N-propylformamide, N,N-diethylformamide, N-ethyl-N-propylformamide, N,N-dimethylacetamide, selected from the group consisting of N-ethyl-N-methylacetamide, N-methyl-N-propylacetamide, N,N-diethylacetamide, N,N-dimethylpropanamide, and N-ethyl-N-methylpropanamide
  • the ink composition according to (1) or (2).
  • the content of the leveling agent is in the range of 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the amide solvent contained in the ink composition ( The ink composition according to any one of 1) to (9).
  • the dispersible resin includes acrylic resin, polyurethane resin, polyester resin, vinyl chloride resin, vinyl acetate resin, polyether resin, vinyl chloride vinyl acetate copolymer resin, polyethylene resin, and acrylamide resin.
  • the ink composition according to any one of (11) to (13), containing one or more resins or copolymer resins selected from the group consisting of resins, epoxy resins, polycarbonate resins, silicone resins, and polystyrene resins. thing.
  • the ink composition according to any one of (11) to (15) is applied onto a substrate by an ink jet method, and then the substrate is coated at a temperature lower than the Tg of the resin contained in the ink composition.
  • (21) A method for producing recorded matter, comprising applying the ink composition according to any one of (1) to (16) or the ink composition contained in the ink set according to (17) onto a substrate by an inkjet method. .
  • the ink composition of the present invention has high drying properties, and the productivity of the resulting recorded matter is high.
  • the ink composition according to the present embodiment is an ink composition for inkjet and contains a water-soluble organic solvent.
  • the water-soluble organic solvent is characterized by containing an amide-based solvent having a boiling point of 230°C or less.
  • An ink composition containing such an amide-based solvent having a boiling point of 230° C. or less has high drying properties and high productivity of the resulting recorded matter.
  • an amide-based solvent with a boiling point of 230° C. or less acts as a film-forming aid when the ink composition contains a resin.
  • a temperature equal to or higher than a predetermined temperature (minimum film-forming temperature) during film formation of the ink composition, the resin contained in the ink composition can be fused to form a scratch-resistant coating film.
  • a predetermined temperature minimum film-forming temperature
  • This minimum film-forming temperature is generally near the Tg of the resin, but it is possible to lower the minimum film-forming temperature by using an amide-based solvent with a boiling point of 230° C. or less contained in the ink composition. Even at a low drying temperature such as a temperature below the Tg of , the resin can be fused on the substrate, and a coating film having sufficient scratch resistance can be formed.
  • the ink composition according to the present embodiment may be a colored ink containing a coloring material.
  • coloring material includes dyes and pigments, such as yellow, magenta, cyan, black, and dyes contained in colored inks that form images such as intermediate colors and light colors thereof, or The concept includes pigments, white dyes or white pigments contained in white ink, and bright pigments contained in metallic ink.
  • the colored inks may be yellow, magenta, cyan, black, and colored inks that form images such as intermediate colors and light colors thereof. Further, the colored ink may be white ink containing a white colorant, metallic ink containing a bright pigment, or the like.
  • the ink composition according to the present embodiment may be a receiving solution containing a cationic compound that is applied to the substrate prior to applying the colored ink to the substrate.
  • it may be a clear ink containing no coloring material, or an overcoat ink for forming an overcoat layer on the surface of a printed matter.
  • the ink composition according to this embodiment contains a water-soluble organic solvent.
  • the water-soluble organic solvent is 5 parts by mass or more, preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 70 parts by mass in 100 parts by mass of water at 25°C under 1 atmosphere. Parts or more, more preferably 90 parts by mass or more can be dissolved.
  • this water-soluble organic solvent contains an amide-based solvent with a boiling point of 230°C or less.
  • the amide-based solvent having a boiling point of 230° C. or less will be described below.
  • An amide-based solvent having a boiling point of 230° C. or lower is an organic solvent having a boiling point of 230° C. or lower and having a —C( ⁇ O)—N— group (amide bond).
  • Examples of amide-based solvents having a boiling point of 230° C. or lower include alkoxyalkylamide-based solvents having an alkoxyalkyl group (C n H 2n+1 —O—C m H 2m —) and alkyl groups having an alkyl group (C n H 2n+1 —).
  • Examples include amide-based solvents and cyclic amide-based solvents having a cyclic structure and a —C( ⁇ O)—N— group in the cyclic structure.
  • the amide-based solvent having a boiling point of 230°C or lower is preferably an alkylamide-based solvent, an alkoxyalkylamide-based solvent, or a cyclic amide-based solvent, and more preferably an alkylamide-based solvent.
  • an alkylamide-based solvent, an alkoxyalkylamide-based solvent, or a cyclic amide-based solvent By containing an alkylamide-based solvent, an alkoxyalkylamide-based solvent, or a cyclic amide-based solvent, the ink composition exhibits the effects of the present invention.
  • amide-based solvents with a high water/1-octanol partition coefficient are preferred.
  • the partition coefficient is an index of the hydrophobicity of an organic solvent, and a higher organic solvent with a higher partition coefficient (LogP) in water/1-octanol means that the organic solvent has relatively higher hydrophobicity. is.
  • An ink composition containing an amide-based solvent having a boiling point of 230°C or less has high drying properties and high productivity of the resulting recorded matter.
  • the drying property is high and the solvent penetration into the substrate is high, so bleeding is especially prevented on absorbent substrates and vinyl chloride resin substrates. is suppressed, making it possible to produce clear recorded matter.
  • the organic solvent contained in the ink composition remains in the coating film formed by the ink composition.
  • Containing an amide-based solvent with a high water/1-octanol partition coefficient (LogP) that is, an amide-based solvent with relatively high hydrophobicity
  • the ink composition can form a coating film having high water friction resistance.
  • the amide solvent having a boiling point of 230° C. or less preferably has a water/1-octanol partition coefficient (LogP) of ⁇ 0.6 or more, more preferably ⁇ 0.4 or more. It is preferably ⁇ 0.3 or more, and more preferably ⁇ 0.3 or more.
  • the amide-based solvent having a boiling point of 230° C. or less preferably has a water/1-octanol distribution coefficient (LogP) of 1.5 or less, more preferably 1.0 or less, and 0.5 or less. It is even more preferable to have By containing an amide-based solvent having a water/1-octanol partition coefficient (LogP) of 1.5 or less, the compatibility with other organic solvents is increased, and the storage stability of the ink composition is improved. Become.
  • the boiling point of the amide-based solvent having a boiling point of 230°C or lower is preferably 220°C or lower, more preferably 210°C or lower. As a result, an ink composition having higher drying properties can be obtained.
  • the boiling point of the amide-based solvent having a boiling point of 230° C. or lower is preferably 130° C. or higher, more preferably 140° C. or higher, and even more preferably 150° C. or higher. When the boiling point of the amide-based solvent is 130° C. or higher, it is possible to suppress deterioration in ejection stability due to increased drying properties on the nozzle surface.
  • alkylamide-based solvent an alkoxyalkylamide-based solvent, and a cyclic amide-based solvent will be described below as suitable examples of amide-based solvents having a boiling point of 230°C or lower.
  • alkylamide-based solvent for example, an alkylamide-based solvent having an alkylamide-based structure represented by formula (1) can be preferably used.
  • R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 are functional groups which may be independent.
  • R 2 and R 3 are not particularly limited as long as they are functional groups.
  • R 2 and R 3 are preferably hydrogen, an alkyl group, an alkoxy group, a hydroxyalkyl group or a hydroxyl group. more preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • alkylamide-based solvents in which R 1 to R 3 in formula (1) are hydrogen or alkyl groups include formamide, acetamide, propanamide, butanamide, isobutylamide, pentanamide, and N-methylformamide.
  • R 2 and R 3 in formula (1) are alkoxy groups, hydroxyl groups, and hydroxyalkyl groups
  • R 2 and R 3 in formula (1) are alkoxy groups, hydroxyl groups, and hydroxyalkyl groups
  • examples of those in which R 2 and R 3 in formula (1) are alkoxy groups, hydroxyl groups, and hydroxyalkyl groups include N-ethyl-N-(2-methoxyethyl)formamide and N-methoxymethylformamide. , N-hydroxymethyl-N-methylacetamide, N-(2-hydroxyethyl)-N-methylacetamide, N-methoxymethyl-N-methylformamide, or those having a different carbon number or a branched carbon chain structure etc.
  • Alkylamide solvents selected from the group are particularly preferred.
  • alkoxyalkylamide-based solvent for example, among alkylamide-based solvents having an alkylamide-based structure represented by formula (2), those having a boiling point of 230° C. or lower can be preferably used.
  • R 12 is each independently an alkyl group having 1 to 4 carbon atoms
  • R 13 is an alkylene group having 1 to 4 carbon atoms
  • R 10 and R 11 are each independently It is a functional group that may be independent.
  • R 12 is preferably an alkyl group having 1 or more and 2 or less carbon atoms, more preferably an alkyl group having 1 or more and 2 or less carbon atoms.
  • R 13 is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms.
  • R 10 and R 11 are not particularly limited as long as they are functional groups.
  • R 10 and R 11 are preferably hydrogen, an alkyl group, an alkoxy group, a hydroxyalkyl group, or a hydroxyl group. is more preferred, hydrogen or an alkyl group having 1 to 4 carbon atoms is more preferred, and hydrogen or an alkyl group having 1 to 2 carbon atoms is even more preferred.
  • alkoxyalkylamide-based solvent 3-methoxy-N,N-dimethylpropanamide, 3-propoxy-N,N-dimethylpropanamide, or the difference in the number of carbon atoms in the alkoxy group or alkyl group or the branched structure of the carbon chain. of those having a boiling point of 230° C. or lower are preferred. Among these, 3-methoxy-N,N-dimethylpropanamide is particularly preferable from the viewpoint of exhibiting the effects of the present invention.
  • the cyclic amide-based solvent for example, among the cyclic amide-based solvents represented by formulas (3) to (5), those having a boiling point of 230° C. or less can be preferably used.
  • R 4 is an optionally branched alkylene group having 3 to 5 carbon atoms
  • R 5 is hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group. represent.
  • R 4 is preferably an alkylene group having 3 or more and 4 or less carbon atoms.
  • R5 is preferably hydrogen, an alkyl group having 1 to 2 carbon atoms, or an unsaturated hydrocarbon group.
  • R 14 is hydrogen, an optionally branched alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group, and R 15 represents an alkylene group having 1 to 4 carbon atoms.
  • R 16 and R 17 are each independently hydrogen, an optionally branched alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group, and R 18 is 1 to 4 carbon atoms. represents the following optionally branched alkylene group.
  • Cyclic amide solvents include N-vinylmethyloxazolidinone, 1,3-dimethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -lactam, 4-methoxy-1-methyl -2-pyrrolidinone, N-propyl-2-pyrrolidone, N-methyl-2-piperidinone, or those having a branched carbon chain structure or differences in the number of carbon atoms in their alkoxy or alkyl groups, those having a boiling point of 230°C or less is preferred.
  • N-methyl-2-pyrrolidone is particularly preferable from the viewpoint of exhibiting the effects of the present invention.
  • the content of the amide-based solvent having a boiling point of 230° C. or lower is not particularly limited, but is preferably in the range of 2% by mass or more, and preferably in the range of 5% by mass or more, based on the total amount of the ink composition. More preferably, it is 10% by mass or more. As a result, the ink composition has a higher drying property.
  • the content of the amide-based solvent having a boiling point of 230° C. or less is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less in the total amount of the ink composition. .
  • an ink composition having good compatibility with other components and good ink storage stability can be obtained.
  • the amide-based solvent having a boiling point of 230°C or lower preferably contains at least two or more amide-based solvents.
  • the amide-based solvent having a boiling point of 230°C or lower preferably contains at least two or more amide-based solvents.
  • at least two or more amide solvents it is preferable that at least one amide solvent is an amide solvent of 200° C. or lower.
  • the ink composition has a high drying property and the productivity of the obtained recorded matter is further increased.
  • the ink composition according to the present embodiment may contain a water-soluble organic solvent other than the amide-based solvent having a boiling point of 230° C. or less.
  • diol-based solvents are preferred, alkanediol-based solvents are more preferred, and 1,2-alkanediol-based solvents are even more preferred.
  • Diol-based solvents are highly miscible with other components contained in the ink composition, and have lower volatility than amide-based solvents with a boiling point of 230° C. or less. is possible, and the ejection stability can be improved.
  • organic solvents B selected from the group consisting of cyclic ester-based solvents and glycol ether-based solvents.
  • the organic solvent B has a boiling point of 230° C. or lower and a water/1-octanol partition coefficient (LogP) of ⁇ 0.4 or more and 1.5 or less.
  • the content of the other water-soluble organic solvent is not particularly limited. is more preferably 10% by mass or more, and even more preferably 15% by mass or more. It is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less, based on the total amount of the ink composition.
  • the ink composition according to this embodiment may contain water.
  • the water content is not particularly limited, but the lower limit of the water content is preferably in the range of 30% by mass or more, more preferably in the range of 45% by mass or more, based on the total amount of the ink composition. , 50% by mass or more.
  • the upper limit of the water content is preferably within the range of 85% by mass or less, more preferably within the range of 80% by mass or less, and within the range of 75% by mass or less in the total amount of the ink composition. is more preferred.
  • the solvent other than water in the ink composition when water is contained, the solvent other than water in the ink composition must be composed of a highly hydrophilic solvent from the standpoint of storage stability.
  • a water-soluble solvent is selected.
  • the drying property tends to deteriorate particularly in low-temperature drying, and the problem of the present invention that the drying property deteriorates occurs more remarkably. will do.
  • the ink composition according to the present embodiment contains an amide-based solvent having a predetermined boiling point or less, even if it is an aqueous ink composition containing water, it becomes possible to improve the drying property, and it is possible to obtain It is possible to increase the productivity of printed matter.
  • the ink composition according to this embodiment may contain a resin.
  • the ink composition according to the present embodiment does not necessarily contain a resin, but the resin can improve the abrasion resistance of the coating film.
  • the amide-based solvent having a boiling point of 230° C. or less contained in the ink composition according to the present embodiment acts as a film-forming aid, the drying temperature at a low temperature such as a temperature not higher than the Tg of the resin, for example,
  • the resin can be fused on the base material, and a coating film having sufficient abrasion resistance can be formed.
  • the ink composition according to the present embodiment is used as an overcoat ink, it is possible to impart suitable scratch resistance to a recorded matter by containing a resin.
  • a dispersible resin is preferable from the viewpoint of excellent fixability and excellent water resistance of the ink layer. Further, by forming a dispersible resin, the resin can be dispersed in the ink as fine resin particles by electrostatic repulsion or steric repulsion, and dispersion stability can be improved.
  • the dispersible resin is a resin that is dispersed in the ink composition in the form of particles, and means a resin that can be dispersed in the ink composition in the form of particles.
  • One or more resins selected from the group consisting of acrylamide-based resins, epoxy-based resins, polycarbonate-based resins, silicone-based resins, and polystyrene-based resins, or copolymer resins, or mixtures thereof can be used. .
  • These are preferable because they can improve not only water resistance but also solvent resistance.
  • at least one of the constituent monomers contains an acrylic resin or a copolymer with an acrylic resin having an acrylic skeleton. is preferred.
  • the Tg (glass transition temperature) of the resin contained in the ink composition according to the present embodiment is not particularly limited, it is preferably higher than the drying temperature of the ink composition. Specifically, the Tg of the resin is preferably 50° C. or higher, more preferably 55° C. or higher, and even more preferably 60° C. or higher. Originally, when the Tg of the resin contained in the ink composition becomes high, the resin cannot be fused onto the base material unless the drying temperature is increased, thereby imparting suitable scratch resistance to the recorded matter. becomes difficult. If the ink composition according to the present embodiment contains an amide-based solvent of 230° C. or less that acts as a film-forming aid, even if it contains a resin having a high Tg, the resin can be dried on the substrate at a low temperature. It is possible to fuse and impart suitable scratch resistance to the recorded matter.
  • dispersible resins include, for example, ACRYT WEM-031U, WEM-200U, WEM-321, WEM-3000, WEM-202U, WEM-3008 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic-urethane dispersible resin). , AKW107, RKW-500 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic dispersible resin), LUBRIJET N240 (manufactured by Lubrizol, acrylic dispersible resin), Superflex 150, 210, 470, 500M, E2000, E4800, R5002 (No.
  • the content of the resin (dispersible resin) contained in the ink composition is not particularly limited, but the lower limit of the resin content is 0.05 in the total amount of the ink. It is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and more preferably at least 1% by mass. Thereby, the scratch resistance of the coating film can be further improved.
  • the upper limit of the resin content is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total amount of the ink. This makes it possible to improve the ejection stability when the ink is ejected onto the surface of the substrate by an inkjet method.
  • the average particle size of the dispersible resin is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more, from the viewpoint of dispersion stability in the ink composition and inkjet dischargeability.
  • the average particle size of the dispersible resin is preferably 300 nm or less, more preferably 270 nm or less, and even more preferably 250 nm or less. This further improves the ejection stability of the ink composition. Further, when at least a portion of the resin contains a dispersible resin, the resin particles contained in the ink composition are more densely packed as the water-soluble organic solvent gradually volatilizes during film formation of the ink composition.
  • the ink composition according to the present embodiment contains an amide-based solvent having a boiling point of 230° C. or less that acts as a film-forming aid, the drying temperature at a low temperature such as a temperature not higher than the Tg of the resin, for example, Even so, the resin can be fused onto the base material, and the abrasion resistance and water abrasion resistance of the coating film can be further enhanced.
  • the average particle size of the dispersible resin 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 mass average molecular weight of the dispersible resin is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more. From the viewpoint of dispersion stability in the ink composition, the mass average molecular weight of the dispersible resin is preferably 2,000,000 or less, more preferably 1,500,000 or less, and more preferably 1,000,000 or less. In the present embodiment, the molecular weight of the resin indicates the mass 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 a calibration curve as a standard.
  • GPC gel permeation chromatography
  • the ink composition according to this embodiment may contain a leveling agent. Although it is not essential that the ink composition according to the present embodiment contains a leveling agent, the inclusion of the leveling agent allows the ink composition applied on the substrate to spread more wetly.
  • the ink composition according to the present embodiment contains an amide-based solvent having a boiling point of 230° C. or less, so that the dot diameter of the obtained recorded matter increases and the surface area of the interface between the ink composition and the outside air increases. is dried more effectively, and the effects of the present invention are particularly effective.
  • the type of leveling agent is not particularly limited.
  • examples include surfactants such as anionic surfactants, nonionic surfactants, silicone (silicon) surfactants, fluorine surfactants, acetylene glycol surfactants, and alkane glycol surfactants. be able to.
  • the ink composition according to the present embodiment preferably contains a silicone surfactant.
  • Emal Latemul
  • Pelex Neoperex
  • Demol all of which are anionic surfactants; manufactured by Kao Corporation
  • Sunol Liporan, Lipon, and Ripal (all of which are anionic surfactants; Lion Co., Ltd.
  • a leveling agent with an HLB value of 15 or less is preferable. If the leveling agent has an HLB value of 15 or less, the leveling agent tends to be oriented at the interface between the ink composition applied on the substrate and the outside air, and the ink composition spreads more easily. The ink composition dries more effectively as the dot diameter of the recorded matter becomes larger.
  • the content of the leveling agent is the content of the amide-based solvent having a boiling point of 230° C. or less contained in the ink composition according to the present embodiment. It is preferable to control according to Amide-based solvents having a boiling point of 230° C. or less are relatively hydrophobic water-soluble organic solvents among water-soluble organic solvents. It becomes easy to dissolve in the amide-based solvent, and it may become difficult for the leveling agent to be oriented at the interface with the outside air. Therefore, by appropriately controlling the content of the amide-based solvent having a boiling point of 230° C. or less, the ink composition spreads out and dries effectively.
  • the content of the leveling agent is preferably in the range of 0.1 parts by mass or more with respect to 100 parts by mass of the amide solvent contained in the ink composition. As a result, the ink composition is further wetted and spread, so that the ink composition dries more effectively.
  • the range of 0.3 parts by mass or more is more preferable, the range of 0.6 parts by mass or more is even more preferable, and the range of 1.0 parts by mass or more is even more preferable.
  • the content of the leveling agent is preferably in the range of 50 parts by mass or less with respect to 100 parts by mass of the amide solvent contained in the ink composition. This improves the compatibility of the leveling agent with the amide solvent.
  • the range of 49 parts by mass or less is more preferable, and the range of 48 parts by mass or less is even more preferable.
  • the ink composition according to this embodiment may contain a coloring material.
  • the ink composition according to the present embodiment does not necessarily contain a coloring material. It is possible to use white ink or metallic ink that will serve as a base layer.
  • the colorant may be either a dye or a pigment.
  • the pigment that can be used in the ink composition according to the present embodiment is not particularly limited, and examples thereof include organic pigments and inorganic pigments used in conventional ink compositions. These may be used individually by 1 type, or may be used in combination of 2 or more type. Note that the ink composition according to the present embodiment may not contain a coloring material.
  • the dispersion stability of the pigment can be improved by using a dispersant or a dispersing aid (pigment derivative).
  • organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine-based organic pigments, quinacridone-based organic pigments, perylene-based organic pigments, perinone-based organic pigments, azomethine-based organic pigments, and anthraquinone-based pigments.
  • Organic pigments (anthrone-based organic pigments), xanthene-based organic pigments, diketopyrrolopyrrole-based organic pigments, dioxazine-based organic pigments, nickel azo-based pigments, isoindolinone-based organic pigments, pyranthrone-based organic pigments, thioindigo-based organic pigments, condensed azo organic solid solution pigments such as organic pigments, 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. be done.
  • C.I. color index
  • azo dyes benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, Merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dye
  • inorganic pigments that can be used in the ink composition according to the present embodiment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, alumina, and zinc.
  • flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron (III)), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, titanium black, aluminum, titanium, indium, synthetic iron black, Inorganic solid solution pigments and the like can be mentioned.
  • the average dispersed particle size of these organic pigments or inorganic pigments is not particularly limited as long as the desired color development is possible. Although it varies depending on the type of pigment, the lower limit of the average dispersed particle diameter of the pigment is preferably in the range of 10 nm or more, preferably 20 nm or more, from the viewpoint of obtaining sufficient coloring power with good dispersion stability of the pigment. It is more preferably within the range, and even more preferably within the range of 30 nm or more.
  • the upper limit of the average dispersed particle size of the pigment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less.
  • the average dispersed particle size is 500 nm or less, nozzle clogging of an inkjet head is unlikely to occur, and a uniform image with high reproducibility can be obtained.
  • the average dispersed particle diameter is 10 nm or more, the light resistance of the resulting printed matter can be improved.
  • the average dispersed particle diameter of the pigment is the average particle diameter ( D50).
  • the ink composition according to the present embodiment may contain a luster pigment as a pigment.
  • Luminous pigments include metal-containing luster 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; Pearl pigments having pearl luster or interference luster such as mica, fish scale foil, bismuth oxychloride, silicon dioxide, metal oxides, metal compounds, and laminates thereof may be mentioned.
  • the glitter pigment preferably has a plate-like shape (also referred to as a fine plate-like shape, a scale-like shape, or the like). This makes it possible to impart a more suitable metallic luster to the subject.
  • the content of the coloring material is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, based on the total amount of the ink composition. is more preferable, and 0.1% by mass or more is even more preferable.
  • 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 ink composition. is more preferable, and 15.0% by mass or less is even more preferable.
  • the ink composition according to this embodiment may contain a pigment dispersant.
  • the ink composition according to the present embodiment does not necessarily contain a pigment dispersant, but by containing the pigment dispersant together with the pigment, the dispersibility of the pigment can be improved.
  • pigment dispersant means a resin or surfactant that adheres to a part of the pigment surface and has a function of improving the dispersibility of the pigment in the ink composition.
  • the pigment dispersant that can be used in the ink composition according to the present embodiment is not particularly limited.
  • cationic, anionic, nonionic, amphoteric, silicone (silicon), and fluorine surfactants can be used.
  • surfactants polymer surfactants (polymer dispersants) such as those exemplified below are preferable.
  • a water-soluble polymer dispersant can be preferably used as a pigment dispersant that can be used in the ink composition according to the present embodiment.
  • water-soluble polymer dispersants include polyester-, polyacrylic-, polyurethane-, polyamine-, and polycaptolactone-based main chains, and side chains containing amino, carboxy, sulfo, and hydroxy groups.
  • (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; copolymers of aromatic vinyl compounds such as styrene and ⁇ -methylstyrene and unsaturated carboxylic acid esters such as acrylic acid 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 acid esters Polyurethanes; Unsaturated polyamides; Polysiloxanes; Long-chain polyaminoamide phosphates; Polyethyleneimine derivatives (poly (lower alkylene imine) and free carboxyl group-containing polyester amides obtained by reaction and their bases); polyallylamine derivatives (polyallylamine and polyester having a free carboxyl group
  • water-soluble polymer dispersant examples include Cray Valley's SMA1440, SMA2625, SMA17352, SMA3840, SMA1000, SMA2000, SMA3000, BASF Japan's JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL690, JONCRYL819, JONCRYL -JDX5050, EFKA4550, EFKA4560, EFKA4585, EFKA5220, EFKA6230, Dispex Ultra PX4575, Lubrizol SOLSPERSE20000, SOLSPERSE27000, SOLSPERSE40000, SOLSPERSE410 00, SOLSPERSE41090, SOLSPERSE43000, SOLSPERSE44000, SOLSPERSE45000, SOLSPERSE46000, SOLSPERSE47000, SOLSPERSE53095, SOLSPERSE54000,
  • the ink according to this embodiment may contain a cationic compound.
  • the ink composition according to the present embodiment does not necessarily contain a cationic compound. can do.
  • the coloring ink containing the coloring material is anionic.
  • cationic compounds include polyvalent metal salts (polyvalent metal ions) and cationic resins.
  • Polyvalent metal salts mainly contain ions and anions of polyvalent metals.
  • the concept of "containing a polyvalent metal salt” includes not only those to which a polyvalent metal salt is added during preparation of the receiving solution, but also compounds capable of generating polyvalent metal ions and compounds capable of generating anions. and are added at the time of preparation of the receiving solution to contain the polyvalent metal ions and the anions constituting the polyvalent metal salt.
  • the anion may be an anion of an inorganic substance or an anion of an organic substance.
  • the anions preferably include organic anions.
  • inorganic anions include chloride ions, bromide ions, nitrate ions, and sulfate ions.
  • 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, methylmalonic acid.
  • a polyvalent metal ion is an ion of a metal with a valence of at least two. Bleeding of the ink composition can be suppressed by using polyvalent metal ions.
  • 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, and the like. is mentioned.
  • one selected from calcium ions, magnesium ions, nickel ions, zinc ions, and aluminum ions because it has a large interaction with the colorant in the ink composition and has a high effect of suppressing bleeding and unevenness. It is preferable to contain the above.
  • the cationic compound may contain a cationic resin having a cationic group instead of the polyvalent metal salt.
  • cationic resins include resins having cationic groups such as amino groups, ammonium groups, amide groups, and --NHCONH2 groups.
  • the cationic resin can be synthesized by a known method, or a commercially available product can be used.
  • Examples of commercially available products are as follows: APC-810, 815; D-6010, 6020, 6030, 6040, 6050, 6060, 6080, 6310; 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; Myriogen P- 20; Unisense FPA100L, FPA101L, FPA
  • the cationic resin may be a water-soluble cationic resin that dissolves in water or a water-soluble organic solvent, or a dispersible cationic resin that disperses in water or a water-soluble organic solvent.
  • the cationic resin is preferably a dispersible cationic resin.
  • the coating film resistance (scratch resistance) of the ink composition layer can be improved.
  • the cationic compound contains a polyvalent metal ion and a dispersible cationic resin, or the cationic compound contains a water-soluble cationic resin and a dispersible cationic resin. more preferably.
  • the ink composition layer can be coated while suppressing bleeding of the colored ink more effectively.
  • Film resistance shock resistance
  • the content of the cationic compound is not particularly limited. It is preferably in the range of 5% by mass or more, more preferably in the range of 0.8% by mass or more, and even more preferably in the range of 1.0% by mass or more. When the content of the cationic compound is within the range of 0.5% by mass or more based on the total amount of the ink composition, it becomes possible to fix the coloring material more effectively, and the bleeding of the colored ink is effectively suppressed. can do.
  • the upper limit of the content of the cationic compound is preferably within the range of 9% by mass or less, more preferably within the range of 8% by mass or less, and within the range of 7% by mass or less in the total amount of the ink composition. is more preferable. When the content of the cationic compound is within the range of 9% by mass or less based on the total amount of the ink composition, the storage stability of the ink composition is improved.
  • the ink composition may further contain conventionally known additives, if necessary.
  • additives include waxes, viscosity modifiers, pH modifiers, antioxidants, preservatives, antifungal agents, and the like.
  • a method for preparing the ink composition is not particularly limited. For example, a method of adding a self-dispersing pigment, a resin, a surfactant and, if necessary, other components to a water-soluble organic solvent for preparation, a method of adding a pigment and a dispersant to a water-soluble organic solvent, and then dispersing , A method of adding a resin, a surfactant and other ingredients if necessary. After adding the pigment, resin, surfactant and other ingredients if necessary to a water-soluble organic solvent, the pigment is dispersed. and the like.
  • the surface tension of the ink composition is not particularly limited, but the upper limit of the static surface tension at 25° C. is preferably 40.0 mN/m or less, more preferably 35.0 mN/m or less, and 32.0 mN/m or less. More preferred.
  • the lower limit of the static surface tension at 25°C is preferably 19.0 mN/m or more, more preferably 20.0 mN/m or more, and even more preferably 21.0 mN/m or more.
  • the static surface tension can be measured, for example, by the Wilhelmy method (DY-300 manufactured by Kyowa Interface Science) at a measurement temperature of 25°C.
  • the conductivity of the ink composition is not particularly limited, it is preferably 2500 ⁇ S/cm or less.
  • the conductivity of the ink composition is preferably 2500 ⁇ S/cm or less.
  • the conductivity of the ink composition is preferably 2450 ⁇ S/cm or less, more preferably 2400 ⁇ S/cm or less.
  • the electrical conductivity can be measured at 25° C. with EC Testr 11+ manufactured by Eutech Instruments, for example.
  • the above ink composition may be a colored ink, a metallic ink or the like, a receiving solution containing a cationic compound, or a clear ink containing no coloring material, and may be an overcoat ink.
  • the ink set according to the present embodiment may be an ink set in which these ink compositions are combined.
  • one ink composition contained in the ink set is a colored ink composition (C) containing a coloring material
  • the other ink composition contained in the ink set contains a cationic compound.
  • the ink set that is the receiving solution (P) and one ink composition contained in the ink set are the overcoat inks (O) that form an overcoat layer on the surface of the object, and the other ink compositions contained in the ink set.
  • the ink composition is an ink set that is a receiving solution (P) containing a cationic compound, and one ink composition included in the ink set is a colored ink composition (C) that contains a coloring material, and the ink Other ink compositions included in the set include an ink set that is an overcoat ink (O) that forms an overcoat layer on the surface of a substrate.
  • P receiving solution
  • C colored ink composition
  • O overcoat ink
  • the ink set may be a combination of colored ink compositions (C) containing a coloring material. ink, red ink) or light colored ink compositions (for example, light magenta ink, light cyan ink, light black ink).
  • an ink set containing a white ink composition containing a white colorant, 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 colorant and 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, and black.
  • an ink set containing a metallic ink containing a glitter pigment, a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition containing a metallic ink containing a glitter pigment and a yellow ink composition
  • a metallic ink containing a glitter pigment and a yellow ink composition A magenta ink composition, a cyan ink composition, a black ink composition, and intermediate color ink compositions or light color ink compositions of yellow, magenta, cyan, and black.
  • the conductivity is preferably 1000 ⁇ S/cm or less. Since the coloring ink composition (C) containing the coloring material contains the coloring material (pigment) in the coloring ink composition (C), when the conductivity is high, the coloring material (pigment) tends to aggregate and become less stable.
  • the colored ink composition (C) contains components such as a colorant dispersant (pigment dispersant) and a leveling agent (surfactant) that disperse the colorant (pigment) so that the conductivity is 1000 ⁇ S/cm or less. By doing so, it is possible to suppress the interaction between the components (especially between the coloring materials), and it is possible to further improve the stability.
  • the electrical conductivity of the colored ink composition (C) is more preferably 950 ⁇ S/cm or less, even more preferably 900 ⁇ S/cm or less.
  • the electrical conductivity of the overcoat ink (O) is preferably 1000 ⁇ S/cm or less.
  • the overcoat ink (O) that forms the overcoat layer on the surface of the object contains a resin for forming the overcoat layer. tend to decline.
  • the electrical conductivity of the overcoat ink (O) is 1000 ⁇ S/cm or less. interaction can be suppressed, and the stability can be further improved.
  • the conductivity of the overcoat ink (O) is more preferably 950 ⁇ S/cm or less, even more preferably 900 ⁇ S/cm or less.
  • the electrical conductivity of the receiving solution (P) is preferably 1000 ⁇ S/cm or more and 2500 ⁇ S/cm or less. Since the receiving solution (P) contains a cationic compound, the receiving solution (P ) while maintaining the storage stability of the receiving solution (P), it is possible to improve the reactivity with the colored ink (C) and the overcoat ink (O) that land on the receiving solution (P), suppressing bleeding and unevenness. It becomes possible to
  • the electrical conductivity of the receiving solution (P) is more preferably 1050 ⁇ S/cm or higher, more preferably 1100 ⁇ S/cm or higher.
  • the recording method according to the present embodiment is a recording method in which the ink composition described above is applied onto a substrate by an inkjet method.
  • this ink composition contains an amide-based solvent having a boiling point of 230° C. or less and is highly drying, it can be applied onto a substrate by an inkjet method according to the recording method according to the present embodiment. can be recorded at high speed.
  • the partition coefficient (LogP) of water/1-octanol of this amide solvent with a boiling point of 230° C. or less is ⁇ 0.6 or more, the solvent permeability to the substrate is high, especially the absorption Bleeding on a flexible base material or a vinyl chloride base material (vinyl chloride resin base material) is further suppressed, making it possible to produce clear recorded matter.
  • the maximum recording speed in the recording method according to the present embodiment is 7.5 m 2 /h or more in the case of the serial method, although it depends on the type of the base material, the type of the ink jet recording apparatus, and the like. It is preferably 10 m 2 /h or more, more preferably 15 m 2 /h or more. In the case of the single pass method, the speed is preferably 30 m/min or more, more preferably 40 m/min or more, and even more preferably 50 m/min or more.
  • the drying temperature in the recording method according to the present embodiment may be 80°C or lower, preferably 70°C or lower, and more preferably 60°C or lower.
  • the above-described recording method can also be defined as a method for producing a recorded matter in which the above-described ink composition is applied onto a substrate by an inkjet method.
  • the base material (recording medium) that can be used in the recording method according to the present embodiment is not particularly limited.
  • Various substrates can be used, such as an absorbent substrate such as a woven fabric, or a surface-coated substrate such as a substrate having a receiving layer. The same applies to the base material that can be used in the method of manufacturing a recorded matter according to an embodiment described later.
  • non-absorbent substrates include resin substrates such as polyester resins, polypropylene synthetic paper, polypropylene resins, polyethylene resins, acrylic resins, styrene resins, polycarbonate resins, ABS resins, vinyl chloride resins, polyimide resins, Metal, metal foil coated paper, glass, synthetic rubber, natural rubber and the like can be mentioned.
  • resin substrates such as polyester resins, polypropylene synthetic paper, polypropylene resins, polyethylene resins, acrylic resins, styrene resins, polycarbonate resins, ABS resins, vinyl chloride resins, polyimide resins, Metal, metal foil coated paper, glass, synthetic rubber, natural rubber and the like can be mentioned.
  • absorbent substrates include dry paper, medium-quality paper, high-quality paper, synthetic paper, cotton, synthetic fiber fabric, silk, hemp, fabric, non-woven fabric, leather, and the like.
  • Examples of surface-coated substrates include coated paper, art paper, cast paper, lightweight coated paper, and lightly coated paper.
  • the layer of the ink composition is a layer formed by volatilization of the solvent contained in the ink composition described above. For example, when a coloring material is contained in the ink, it becomes a decorative layer forming a desired image and its underlying layer.
  • the above-described ink composition when used as a receiving solution containing a cationic compound, the above-described ink composition (receiving solution) is applied onto a substrate, and the above-described ink composition (coloring ink) is applied thereon. ) may be applied, or the above-described ink composition (receiving solution) is applied on the substrate, and an ink composition (colored ink) different from the above-described ink composition (colored ink) is applied thereon. You may
  • the ink composition described above when used as an overcoat ink, it becomes an overcoat layer formed on the surface of a recorded matter.
  • the ink composition that forms the recording layer of the recorded matter may be the ink composition described above, or may be an ink composition different from the ink composition described above.
  • the inkjet recording apparatus is an inkjet recording apparatus equipped with a container filled with the ink composition described above or the ink composition contained in the ink set described above. Since the above-described ink composition has high drying properties, an inkjet recording apparatus equipped with a container filled with the above-described ink composition or the ink composition contained in the above-described ink set can be used to quickly print a printed matter. can be manufactured.
  • the storage container mounted on the inkjet recording apparatus is not particularly limited, and examples include containers such as ink bottles, pouches, bag-in-boxes, and drums. Also, 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 a conventionally known resin, or a material containing a part of metal material (for example, an aluminum pouch having an aluminum deposition layer). .
  • this apparatus include a drying mechanism for drying the ink composition after the ink composition is ejected. This makes it possible to effectively remove volatile components contained in each ink composition.
  • the drying mechanism for drying the ink after ejection of the ink composition is not particularly limited, and may be a heater or the like, or a mechanism for blowing hot air or normal temperature air.
  • the ink composition applied on the substrate at a temperature lower than the Tg of the resin contained in the ink composition. Since the above ink composition is highly drying, it can be sufficiently dried even at a temperature lower than the Tg of the resin contained in the ink composition.
  • the ejection method in each ejection part may be any method such as a piezo method, a thermal method, or an electrostatic method.
  • Drying properties of the ink compositions of Examples and Comparative Examples were evaluated. Specifically, after applying 5 g/m 2 of the ink composition onto a vinyl chloride resin substrate with a bar coater, the ink composition was placed in an oven at 60° C. and the time until drying was evaluated by touch. The surface was touched with a finger every 30 seconds, and the time until the ink composition stopped adhering was measured, and evaluation was performed based on the following evaluation criteria. The evaluation results are shown in the table below (indicated as "drying property" in the table). Evaluation Criteria A: Dried in 3 minutes. B: Dried in 3.5 to 4 minutes. C: Dried in 4.5 to 5 minutes. D: Dried in 5.5 to 6 minutes. E: Not dried in 6 minutes (out of practical range).
  • Storage stability was evaluated for the ink compositions of Examples and Comparative Examples. 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 (indicated as "storage stability" in the table). Evaluation Criteria A: Viscosity change rate of 5% or less B: Viscosity change rate of more than 5% and less than 10% C: Viscosity change rate of 10% or more and less than 20% D: Viscosity change rate of 20% or more (outside practical range)
  • Density unevenness Density unevenness was evaluated for recorded matter obtained with the ink compositions of Examples and Comparative Examples. Specifically, the ink composition is filled in an ink cartridge (container), and the ink cartridge (container) is mounted on a serial head type inkjet recording apparatus. A solid image with a droplet size of 6 pl and a printing density of 100% was printed on a vinyl chloride resin substrate, and the presence or absence of density unevenness was visually observed, and evaluation was made based on the following evaluation criteria. The evaluation results are shown in the table below (denoted as "density unevenness" in the table). Evaluation Criteria A: No density unevenness B: Density unevenness C: Image formation not possible due to poor ink wetting (outside practical range)
  • Liquid repellency Liquid repellency was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, the nozzle plate of a 600 dpi printer head in an inkjet recording apparatus is immersed in the ink composition, and the exposed area of the ink composition on the plate after being removed from the liquid surface is visually observed every 30 seconds. was evaluated based on the evaluation criteria of The evaluation results are shown in the table below (indicated as "liquid repellency" in the table). Evaluation criteria A: The exposed area of the plate after 30 seconds is 80% or more B: The exposed area of the plate after 1 minute is 80% or more C: The exposed area of the plate is less than 80% even after 1 minute (outside the practical range)
  • the intermittent discharge properties of the ink compositions of Examples and Comparative Examples were evaluated. Specifically, the ink composition is filled in an ink cartridge (container), the ink cartridge (container) is mounted in a serial head type inkjet recording apparatus, and a nozzle check pattern is printed by the inkjet recording apparatus. Then, after standing still for a certain period of time, the same printing was performed. The presence or absence of nozzle chipping was checked before and after standing, and evaluation was performed based on the following evaluation criteria. The evaluation results are shown in the table below (indicated as "intermittent discharge property" in the table). Evaluation Criteria A: 10% or less nozzle missing after standing for 15 minutes B: 10% or less nozzle missing after standing for 10 minutes C: 10% or less nozzle missing after standing for 5 minutes D: more than 10% nozzle missing after standing for 5 minutes (out of practical range)
  • the scratch resistance was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, a coating film was dried at 60° C. for 6 minutes in the same manner as in the above dryness evaluation, and the coating film on the coated surface of the ink composition was subjected to a Gakushin type rubbing fastness tester type II, The appearance of the coating film was observed under the conditions of a weight of 500 g and a cloth of Kanawa No. 3. The evaluation results are shown in the table below (indicated as "scratch resistance" in the table).
  • the ink compositions of Examples containing an amide-based solvent having a boiling point of 230°C or lower are excellent in drying properties.
  • Examples 1 to 11 in which the type of amide solvent having a boiling point of 230°C or lower was changed, Examples 1 to 4, 6, 7, and 9 containing an amide solvent having a boiling point of 220°C or lower , and 11, even when compared with the ink compositions of Examples 5, 8, and 10, the "drying property" evaluation was even better.
  • the ink compositions of Examples 12, 16, and 18 to 23 containing a leveling agent evaluated the "drying property" and "bleeding" of the obtained recorded matter. was good in Further, in the ink compositions of Examples 12, 16, 18, and 19 in which the HLB value of the leveling agent was changed, the ink compositions of Examples 12 and 16 containing a leveling agent having an HLB value of 15 or less were Even when compared with the ink compositions of Examples 18 and 19, the "drying property" and "bleeding" evaluations were even better.
  • the ink compositions of Examples 12, 25, and 26 containing a resin had better "scratch resistance" than the ink composition of Example 24 containing no resin.
  • the ink compositions of Examples 12 and 25 containing a resin having a Tg of 50° C. or more were even more favorable in the evaluation of "scratch resistance" than the ink composition of Example 26.
  • the ink compositions (receiving solutions) of Examples 27 and 28 containing cationic compounds had even better "storage stability" evaluations when compared to the ink composition of Example 28 (accepting solution).
  • the content of the amide solvent with a boiling point of 230°C or lower was 6% by mass or more.
  • the ink compositions of Examples 1, 12, 32, and 34, in which the content of the amide-based solvent having a boiling point of 230° C. or less was in the range of 35% by mass or less were compared with the ink composition of Example 35.
  • the "storage stability" rating was even better.
  • the "1,3-propanediol" of Examples 12, 16, and 29 containing N,N-diethylformamide as an amide-based solvent having a boiling point of 230°C or less and further containing 1,3-propanediol.
  • the 1,2-alkanediol solvent "propylene glycol” was changed, the "bleeding" evaluation for the PET film was even better.
  • Example 48 containing a dispersible cationic resin as a cationic compound was " The "scratch resistance” evaluation was even better.
  • the ink composition of the comparative example which does not contain an amide-based solvent having a boiling point of 230°C or less, does not exhibit the effects of the present invention.
  • an ink set containing an amide-based solvent with a boiling point of 230° C. or less has excellent drying properties.
  • Example 27 having a conductivity of 1000 ⁇ S/cm or more and 2500 ⁇ S/cm or less and the ink composition of Example 12 having a conductivity of 1000 ⁇ S/cm or less.
  • the ink set of Example 37 containing .
  • the ink sets of Examples 51 and 55 were compared with the ink sets of Examples 50 and 54. "Scratch resistance" is good.
  • the ink sets of Examples 51 and 55 contain the ink composition of Experimental Example 47 containing a silicone surfactant. From this, it was confirmed that an ink set containing an ink composition containing a silicone (silicon)-based surfactant can form a coating film with high scratch resistance.
  • Example 52, 53, 56, and 57 containing the ink composition (receiving solution) of Example 48 containing a dispersible cationic resin as a cationic compound were the inks of Example 27. Even when compared to the ink sets of Examples 50 and 54 containing the composition (receiving solution), the "scratch resistance" rating was even better.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Provided is an ink composition that has high drying characteristics and acheives high productivity for a recorded product to be obtained. The ink-jet ink composition contains a water-soluble organic solvent. The water-soluble organic solvent contains an amide-based solvent having a boiling point of 230ºC or lower.

Description

インク組成物、インクセット、インク組成物を基材上に塗布された記録物、記録方法、記録物の製造方法、及び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Ink composition, ink set, recorded matter coated with ink composition on substrate, recording method, method for producing recorded matter, and ink jet recording apparatus equipped with storage container filled with ink composition
 本発明は、インク組成物、インクセット、インク組成物を基材上に塗布された記録物、記録方法、記録物の製造方法、及び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に関する。 The present invention provides an ink composition, an ink set, a recorded matter obtained by applying the ink composition onto a substrate, a recording method, a method for producing a recorded matter, and an ink jet recording method equipped with a container filled with the ink composition. Regarding the device.
 インクジェット記録方式は、非常に微細なノズルからインク組成物の液滴を紙等の基材に直接吐出し、塗布して文字や画像を得る記録方式である。この記録方式は、小型化、高速化、低騒音化、省電力化、カラー化が容易であり、しかも基材に対して非接触印刷が可能であることから、家庭用途のみならず、オフィス用途、商業印刷用途にまで適用範囲が拡大している。 The inkjet recording method is a recording method in which droplets of an ink composition are directly ejected from very fine nozzles onto a base material such as paper and applied to obtain letters and images. This recording method is easy to reduce size, increase speed, reduce noise, save power, and colorize. , and the range of application has expanded to include commercial printing applications.
 インクジェット記録方式に使用される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、もしくは分散させた水性インク組成物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、同じインクジェット記録方式に使用される有機溶剤を含んだ非水性インク組成物と比較して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。 Aqueous ink compositions in which various coloring materials are dissolved or dispersed in water or a mixture of water and a water-soluble organic solvent are widely used as ink compositions used in inkjet recording systems. Such water-based ink compositions have less impact on the environment than non-aqueous ink compositions containing organic solvents used in the same inkjet recording system, and are non-flammable. Safe for people.
 一方、水性インク組成物は前記非水性インク組成物と比較すると乾燥により多くの熱量が必要となるため、生産性の面では乾燥時間を延ばすよりも、乾燥温度を高く設定する必要があった。これにより装置の消費電力が大きくなるため、200V電源が必要になってしまうことで設置場所が限定されてしまうことや、安全性規格への準拠が難しくなるなど、印刷装置側にも大きな影響を与えている。 On the other hand, compared to the non-aqueous ink composition, the aqueous ink composition requires a larger amount of heat for drying, so in terms of productivity, it was necessary to set the drying temperature higher than extending the drying time. As a result, the power consumption of the device increases, so the need for a 200V power supply limits the installation location and makes it difficult to comply with safety standards. giving.
 また、乾燥温度を高くすること無く汎用の水性インクを印刷した場合、乾燥が遅いことにより吐出された液滴同士が基材上で混じり、滲みとなって画質を低下させてしまう。そのため、生産性を考慮した高速印刷条件下においては低温での乾燥性と滲みのない画質を両立させることは困難であった。 In addition, when general-purpose water-based ink is printed without increasing the drying temperature, the jetted droplets mix on the substrate due to slow drying, resulting in bleeding and degraded image quality. Therefore, it has been difficult to achieve both low-temperature dryness and bleeding-free image quality under high-speed printing conditions in consideration of productivity.
 そこで、例えば、特許文献1には、2-ピロリドンとウレタン樹脂を含む水不溶性の熱可塑性樹脂粒子と、を含有する水性インク組成物を吐出する工程を含むインクジェット記録方法に関する技術が記載されている。特許文献1には、このインクジェット記録方法は、インクの滲みが少なく高画質であり、耐擦過性が優れた画像が得られることが記載されている。 Therefore, for example, Patent Document 1 describes a technique relating to an inkjet recording method including a step of ejecting an aqueous ink composition containing 2-pyrrolidone and water-insoluble thermoplastic resin particles containing a urethane resin. . Japanese Patent Laid-Open No. 2002-100001 describes that this inkjet recording method can obtain an image with little ink bleeding, high image quality, and excellent abrasion resistance.
特開2015-091658号公報JP 2015-091658 A
 本発明は、乾燥性が高く、得られる記録物の生産性が高い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 ink composition with high drying properties and high productivity of the resulting recorded matter.
 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、所定沸点以下のアミド系溶剤を含有する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 found that the above problems can be solved with an ink composition containing an amide-based solvent having a predetermined boiling point or less. Arrived. Specifically, the present invention provides the following.
 (1)インクジェット用のインク組成物であって、水溶性有機溶剤を含有し、前記水溶性有機溶剤は、沸点が230℃以下のアミド系溶剤を含有するインク組成物。 (1) An inkjet ink composition containing a water-soluble organic solvent, the water-soluble organic solvent containing an amide-based solvent having a boiling point of 230°C or less.
 (2)前記アミド系溶剤は、以下式(1)のアルキルアミド系構造を有する(1)に記載のインク組成物。
Figure JPOXMLDOC01-appb-C000002
(式(1)中、R1は水素、若しくは炭素数1~4のアルキル基であり、R,Rは官能基である。)
(2) The ink composition according to (1), wherein the amide-based solvent has an alkylamide-based structure represented by formula (1) below.
Figure JPOXMLDOC01-appb-C000002
(In formula (1), R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 are functional groups.)
 (3)前記アミド系溶剤は、N-エチル-N-メチルホルムアミド、N-メチル-N-プロピルホルムアミド、N,N-ジエチルホルムアミド、N-エチル-N-プロピルホルムアミド、N,N-ジメチルアセトアミド、N-エチル-N-メチルアセトアミド、N-メチル-N-プロピルアセトアミド、N,N-ジエチルアセトアミド、N,N-ジメチルプロパンアミド、及びN-エチル-N-メチルプロパンアミドからなる群より選択される(1)又は(2)に記載のインク組成物。 (3) the amide solvent includes N-ethyl-N-methylformamide, N-methyl-N-propylformamide, N,N-diethylformamide, N-ethyl-N-propylformamide, N,N-dimethylacetamide, selected from the group consisting of N-ethyl-N-methylacetamide, N-methyl-N-propylacetamide, N,N-diethylacetamide, N,N-dimethylpropanamide, and N-ethyl-N-methylpropanamide The ink composition according to (1) or (2).
 (4)さらに、アルカンジオール系溶剤を含む(1)から(3)のいずれかに記載のインク組成物。 (4) The ink composition according to any one of (1) to (3), further comprising an alkanediol solvent.
 (5)前記アルカンジオール系溶剤は沸点が230℃以下のアルカンジオール系溶剤を含有する(4)に記載のインク組成物。 (5) The ink composition according to (4), wherein the alkanediol-based solvent contains an alkanediol-based solvent having a boiling point of 230°C or lower.
 (6)前記アミド系溶剤は、少なくとも2種以上のアミド系溶剤を含有する(1)から(4)のいずれかに記載のインク組成物。 (6) The ink composition according to any one of (1) to (4), wherein the amide solvent contains at least two or more amide solvents.
 (7)前記アミド系溶剤は、少なくとも1種の沸点が200℃以下のアミド系溶剤を含有する(6)に記載のインク組成物。 (7) The ink composition according to (6), wherein the amide solvent contains at least one amide solvent having a boiling point of 200°C or less.
 (8)さらに、環状エステル系溶剤、及びグリコールエーテル系溶剤からなる群より選択される少なくとも1以上の有機溶剤Bを含む(1)から(7)のいずれかに記載のインク組成物。 (8) The ink composition according to any one of (1) to (7), further comprising at least one organic solvent B selected from the group consisting of cyclic ester solvents and glycol ether solvents.
 (9)前記有機溶剤Bは、沸点は230℃以下の有機溶剤Bを含有する(8)に記載のインク組成物。 (9) The ink composition according to (8), wherein the organic solvent B has a boiling point of 230°C or less.
 (10)さらにレベリング剤を含有し、前記レベリング剤の含有量は、前記インク組成物に含まれる前記アミド系溶剤100質量部に対して0.1質量部以上50質量部以下の範囲である(1)から(9)のいずれかに記載のインク組成物。 (10) Further containing a leveling agent, the content of the leveling agent is in the range of 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the amide solvent contained in the ink composition ( The ink composition according to any one of 1) to (9).
 (11)さらに樹脂を含有し、前記樹脂の少なくとも一部を分散性樹脂として含有する、(1)から(10)のいずれかに記載のインク組成物。 (11) The ink composition according to any one of (1) to (10), which further contains a resin, and contains at least part of the resin as a dispersible resin.
 (12)前記分散性樹脂のTgは、インク組成物の乾燥温度よりも高い(11)に記載のインク組成物。 (12) The ink composition according to (11), wherein the Tg of the dispersible resin is higher than the drying temperature of the ink composition.
 (13)前記分散性樹脂のTgは、50℃以上である(11)又は(12)に記載のインク組成物。 (13) The ink composition according to (11) or (12), wherein the Tg of the dispersible resin is 50°C or higher.
 (14)前記分散性樹脂は、アクリル系樹脂、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(11)から(13)のいずれかに記載のインク組成物。 (14) The dispersible resin includes acrylic resin, polyurethane resin, polyester resin, vinyl chloride resin, vinyl acetate resin, polyether resin, vinyl chloride vinyl acetate copolymer resin, polyethylene resin, and acrylamide resin. The ink composition according to any one of (11) to (13), containing one or more resins or copolymer resins selected from the group consisting of resins, epoxy resins, polycarbonate resins, silicone resins, and polystyrene resins. thing.
 (15)前記分散性樹脂は、少なくともアクリル系樹脂、又はアクリル系共重合樹脂を含む(14)に記載のインク組成物。 (15) The ink composition according to (14), wherein the dispersible resin contains at least an acrylic resin or an acrylic copolymer resin.
 (16)導電率が2500μS/cm以下である(1)から(15)のいずれかに記載のインク組成物。 (16) The ink composition according to any one of (1) to (15), which has a conductivity of 2500 μS/cm or less.
 (17)(1)から(16)のいずれかに記載のインク組成物を含むインクセット。 (17) An ink set containing the ink composition according to any one of (1) to (16).
 (18)(1)から(16)のいずれかに記載のインク組成物、又は(17)に記載のインクセットに含まれるインク組成物が基材上に塗布された記録物。 (18) A recorded matter in which the ink composition according to any one of (1) to (16) or the ink composition contained in the ink set according to (17) is applied onto a substrate.
 (19)(1)から(16)のいずれかに記載のインク組成物、又は(17)に記載のインクセットに含まれる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方法。 (19) A recording method in which the ink composition according to any one of (1) to (16) or the ink composition contained in the ink set according to (17) is applied onto a substrate by an inkjet method.
 (20)(11)から(15)のいずれかに記載のインク組成物をインクジェット法により基材上に塗布し、その後、該インク組成物に含まれる樹脂のTgよりも低い温度で基材上に塗布されたインク組成物を乾燥する記録方法。 (20) The ink composition according to any one of (11) to (15) is applied onto a substrate by an ink jet method, and then the substrate is coated at a temperature lower than the Tg of the resin contained in the ink composition. A recording method in which the ink composition applied to the surface is dried.
 (21)(1)から(16)のいずれかに記載のインク組成物、又は(17)に記載のインクセットに含まれる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。 (21) A method for producing recorded matter, comprising applying the ink composition according to any one of (1) to (16) or the ink composition contained in the ink set according to (17) onto a substrate by an inkjet method. .
 (22)(1)から(16)のいずれかに記載のインク組成物、又は(17)に記載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インクジェット記録装置。 (22) An inkjet recording apparatus equipped with a container filled with the ink composition according to any one of (1) to (16) or the ink composition contained in the ink set according to (17).
 本発明のインク組成物は、乾燥性が高く、得られる記録物の生産性が高い。 The ink composition of the present invention has high drying properties, and the productivity of the resulting recorded matter is high.
 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, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the purpose of the present invention. can do.
 <インク組成物>
 本実施の形態に係るインク組成物は、インクジェット用のインク組成物であって、水溶性有機溶剤を含有する。
<Ink composition>
The ink composition according to the present embodiment is an ink composition for inkjet and contains a water-soluble organic solvent.
 そして、水溶性有機溶剤は、沸点が230℃以下のアミド系溶剤を含有することを特徴とする。このような、沸点が230℃以下のアミド系溶剤を含有するインク組成物であれば、乾燥性が高く、得られる記録物の生産性が高い。 The water-soluble organic solvent is characterized by containing an amide-based solvent having a boiling point of 230°C or less. An ink composition containing such an amide-based solvent having a boiling point of 230° C. or less has high drying properties and high productivity of the resulting recorded matter.
 特に、樹脂を含むインク組成物である場合には、沸点が230℃以下のアミド系溶剤が造膜助剤として作用することが本発明の研究により明らかとなった。一般にインク組成物の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の含まれる樹脂が融着して耐擦過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分散性樹脂である場合には、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ので、最低造膜温度と乾燥温度との関係は、塗膜の耐擦過性により強く影響する。 In particular, the research of the present invention has revealed that an amide-based solvent with a boiling point of 230° C. or less acts as a film-forming aid when the ink composition contains a resin. In general, by applying a temperature equal to or higher than a predetermined temperature (minimum film-forming temperature) during film formation of the ink composition, the resin contained in the ink composition can be fused to form a scratch-resistant coating film. Become. In particular, when this resin is a particulate dispersible resin, the state of the coating film varies greatly depending on the degree of fusion between the resin particles. have a stronger effect on the scratch resistance of
 この最低造膜温度は、樹脂のTg付近となることが一般的ではあるが、インク組成物に含まれる沸点が230℃以下のアミド系溶剤により最低造膜温度を下げることが可能となり、例えば樹脂のTg以下の温度のような低温での乾燥温度であっても、樹脂を基材上で融着させることが可能となり、十分に耐擦過性の有する塗膜を形成することが可能となる。 This minimum film-forming temperature is generally near the Tg of the resin, but it is possible to lower the minimum film-forming temperature by using an amide-based solvent with a boiling point of 230° C. or less contained in the ink composition. Even at a low drying temperature such as a temperature below the Tg of , the resin can be fused on the substrate, and a coating film having sufficient scratch resistance can be formed.
 なお、本実施の形態に係るインク組成物は、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 ink composition according to the present embodiment may be a colored ink containing a coloring material. As used herein, the term “coloring material” includes dyes and pigments, such as yellow, magenta, cyan, black, and dyes contained in colored inks that form images such as intermediate colors and light colors thereof, or The concept includes pigments, white dyes or white pigments contained in white ink, and bright 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。 The colored inks may be yellow, magenta, cyan, black, and colored inks that form images such as intermediate colors and light colors thereof. Further, the colored ink may be white ink containing a white colorant, metallic ink containing a bright pigment, or the like.
 また、本実施の形態に係るインク組成物は、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、カチオン性の化合物を含む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、記録物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い。 In addition, the ink composition according to the present embodiment may be a receiving solution containing a cationic compound that is applied to the substrate prior to applying the colored ink to the substrate. Furthermore, it may be a clear ink containing no coloring material, or an overcoat ink for forming an overcoat layer on the surface of a printed matter.
 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。 Each component contained in the ink composition according to the present embodiment will be described below.
 [水溶性有機溶剤]
 本実施の形態に係るインク組成物は水溶性有機溶剤を含有する。本明細書において水溶性有機溶剤とは、25℃の水100質量部中に、1気圧下で5質量部以上、好ましくは20質量部以上、より好ましくは50質量部以上、更に好ましくは70質量部以上、更になお好ましくは90質量部以上溶解することができるものをいう。
[Water-soluble organic solvent]
The ink composition according to this embodiment contains a water-soluble organic solvent. In this specification, the water-soluble organic solvent is 5 parts by mass or more, preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 70 parts by mass in 100 parts by mass of water at 25°C under 1 atmosphere. Parts or more, more preferably 90 parts by mass or more can be dissolved.
 そして、この水溶性有機溶剤は、沸点が230℃以下のアミド系溶剤を含有する。以下、沸点が230℃以下のアミド系溶剤について説明する。 And this water-soluble organic solvent contains an amide-based solvent with a boiling point of 230°C or less. The amide-based solvent having a boiling point of 230° C. or less will be described below.
 (沸点が230℃以下のアミド系溶剤)
 沸点が230℃以下のアミド系溶剤とは、沸点が230℃以下であって、-C(=O)-N-基(アミド結合)を有する有機溶剤である。沸点が230℃以下のアミド系溶剤としては、アルコキシアルキル基(C2n+1-O-C2m-)を有するアルコキシアルキルアミド系溶剤や、アルキル基(C2n+1-)を有するアルキルアミド系溶剤や、環状構造を有し、その環状構造に-C(=O)-N-基を有する環状アミド系溶剤が挙げられる。
(Amide solvent with a boiling point of 230°C or less)
An amide-based solvent having a boiling point of 230° C. or lower is an organic solvent having a boiling point of 230° C. or lower and having a —C(═O)—N— group (amide bond). Examples of amide-based solvents having a boiling point of 230° C. or lower include alkoxyalkylamide-based solvents having an alkoxyalkyl group (C n H 2n+1 —O—C m H 2m —) and alkyl groups having an alkyl group (C n H 2n+1 —). Examples include amide-based solvents and cyclic amide-based solvents having a cyclic structure and a —C(═O)—N— group in the cyclic structure.
 沸点が230℃以下のアミド系溶剤としては、アルキルアミド系溶剤、アルコキシアルキルアミド系溶剤、又は環状アミド系溶剤であることが好ましく、アルキルアミド系溶剤であることがさらに好ましい。アルキルアミド系溶剤、アルコキシアルキルアミド系溶剤、又は環状アミド系溶剤を含有することで、本発明の効果を特に奏するインク組成物となる。 The amide-based solvent having a boiling point of 230°C or lower is preferably an alkylamide-based solvent, an alkoxyalkylamide-based solvent, or a cyclic amide-based solvent, and more preferably an alkylamide-based solvent. By containing an alkylamide-based solvent, an alkoxyalkylamide-based solvent, or a cyclic amide-based solvent, the ink composition exhibits the effects of the present invention.
 そのなかでも、水/1-オクタノールでの分配係数(LogP)が高いアミド系溶剤であることが好ましい。分配係数は、有機溶剤の疎水性の指標であり、水/1-オクタノールでの分配係数(LogP)が高い有機溶剤であるほど、疎水性が相対的に高い有機溶剤であることを意味するものである。 Among them, amide-based solvents with a high water/1-octanol partition coefficient (LogP) are preferred. The partition coefficient is an index of the hydrophobicity of an organic solvent, and a higher organic solvent with a higher partition coefficient (LogP) in water/1-octanol means that the organic solvent has relatively higher hydrophobicity. is.
 沸点が230℃以下のアミド系溶剤を含有するインク組成物であれば、乾燥性が高く、得られる記録物の生産性が高いものであり、さらにこの230℃以下のアミド系溶剤の水/1-オクタノールでの分配係数(LogP)が高いものを選択することで乾燥性が高く、かつ基材への溶剤浸透性が高くなるので、特に吸収性基材や塩化ビニル系樹脂基材での滲みが抑制され、鮮明な記録物を作製することが可能となる。 An ink composition containing an amide-based solvent having a boiling point of 230°C or less has high drying properties and high productivity of the resulting recorded matter. -By selecting a material with a high partition coefficient (LogP) in octanol, the drying property is high and the solvent penetration into the substrate is high, so bleeding is especially prevented on absorbent substrates and vinyl chloride resin substrates. is suppressed, making it possible to produce clear recorded matter.
 また、記録物の生産性を高くしようとして乾燥処理を短くし、あるいは低温で乾燥処理を施すと、インク組成物により形成される塗膜中にインク組成物に含まれる有機溶剤が残留して、塗膜耐水性が相対的に低下することとなるが、水/1-オクタノールでの分配係数(LogP)が高いアミド系溶剤(すなわち、疎水性が相対的に高いアミド系溶剤)を含有することにより、塗膜中に残留する有機溶剤による塗膜耐水性の低下を抑制することが可能となり、結果として耐水摩擦性の高い塗膜を形成することが可能なインク組成物となる。 In addition, if the drying process is shortened or the drying process is performed at a low temperature in order to increase the productivity of the recorded matter, the organic solvent contained in the ink composition remains in the coating film formed by the ink composition. Containing an amide-based solvent with a high water/1-octanol partition coefficient (LogP) (that is, an amide-based solvent with relatively high hydrophobicity), although the water resistance of the coating film is relatively reduced. As a result, it becomes possible to suppress the deterioration of the water resistance of the coating film due to the organic solvent remaining in the coating film, and as a result, the ink composition can form a coating film having high water friction resistance.
 具体的には、沸点が230℃以下のアミド系溶剤は、水/1-オクタノールでの分配係数(LogP)が-0.6以上であることが好ましく、-0.4以上であることがより好ましく、-0.3以上であることがさらに好ましい。 Specifically, the amide solvent having a boiling point of 230° C. or less preferably has a water/1-octanol partition coefficient (LogP) of −0.6 or more, more preferably −0.4 or more. It is preferably −0.3 or more, and more preferably −0.3 or more.
 沸点が230℃以下のアミド系溶剤は、水/1-オクタノールでの分配係数(LogP)が1.5以下であることが好ましく、1.0以下であることがより好ましく、0.5以下であることがさらに好ましい。水/1-オクタノールでの分配係数(LogP)が1.5以下であるアミド系溶剤を含有することで、他の有機溶剤との相溶性が高くなってインク組成物の保存安定性が良好となる。 The amide-based solvent having a boiling point of 230° C. or less preferably has a water/1-octanol distribution coefficient (LogP) of 1.5 or less, more preferably 1.0 or less, and 0.5 or less. It is even more preferable to have By containing an amide-based solvent having a water/1-octanol partition coefficient (LogP) of 1.5 or less, the compatibility with other organic solvents is increased, and the storage stability of the ink composition is improved. Become.
 沸点が230℃以下のアミド系溶剤の沸点は、220℃以下であることが好ましく、210℃以下であることがより好ましい。これにより、より乾燥性が高いインク組成物となる。沸点が230℃以下のアミド系溶剤の沸点は、130℃以上であることが好ましく、140℃以上であることがより好ましく、150℃以上であることがさらに好ましい。アミド系溶剤の沸点は、130℃以上であることにより、ノズル面での乾燥性が高くなることによる吐出安定性の低下を抑制することが可能となる。 The boiling point of the amide-based solvent having a boiling point of 230°C or lower is preferably 220°C or lower, more preferably 210°C or lower. As a result, an ink composition having higher drying properties can be obtained. The boiling point of the amide-based solvent having a boiling point of 230° C. or lower is preferably 130° C. or higher, more preferably 140° C. or higher, and even more preferably 150° C. or higher. When the boiling point of the amide-based solvent is 130° C. or higher, it is possible to suppress deterioration in ejection stability due to increased drying properties on the nozzle surface.
 以下、沸点が230℃以下のアミド系溶剤の好適な一例として、アルキルアミド系溶剤、アルコキシアルキルアミド系溶剤、及び環状アミド系溶剤について説明する。 An alkylamide-based solvent, an alkoxyalkylamide-based solvent, and a cyclic amide-based solvent will be described below as suitable examples of amide-based solvents having a boiling point of 230°C or lower.
((アルキルアミド系溶剤))
 アルキルアミド系溶剤とは、アルキル基(C2n+1-)と-C(=O)-N-基(アミド結合)を有する化合物であって、水素若しくはアルキル基と-C(=O)-N-基から構成された化合物からなる溶剤である。アルキルアミド系溶剤は、例えば式(1)のアルキルアミド系構造を有するアルキルアミド系溶剤を好ましく用いることができる。
((alkylamide solvent))
An alkylamide solvent is a compound having an alkyl group (C n H 2n+1 -) and a -C(=O)-N- group (amide bond), wherein hydrogen or an alkyl group and -C(=O)- It is a solvent consisting of a compound composed of N-groups. As the alkylamide-based solvent, for example, an alkylamide-based solvent having an alkylamide-based structure represented by formula (1) can be preferably used.
Figure JPOXMLDOC01-appb-C000003
(式(1)中、Rは水素、若しくは炭素数1~4のアルキル基であり、R、Rはそれぞれ独立してもよい官能基である。)
Figure JPOXMLDOC01-appb-C000003
(In Formula (1), R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 are functional groups which may be independent.)
 R,Rは官能基であれば特に限定されないが、例えば、R,Rは、水素、アルキル基、アルコキシ基、ヒドロキシアルキル基、水酸基であることが好ましく、水素、あるいはアルキル基であることがより好ましく、水素、あるいは炭素数1~4のアルキル基であることがさらに好ましい。 R 2 and R 3 are not particularly limited as long as they are functional groups. For example, R 2 and R 3 are preferably hydrogen, an alkyl group, an alkoxy group, a hydroxyalkyl group or a hydroxyl group. more preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
 アルキルアミド系溶剤としては、前記式(1)のR~Rが水素、あるいはアルキル基で構成される例として、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-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、あるいはこれらアルキル基の炭素数違いや炭素鎖が分岐構造を有するものなどが挙げられる。 Examples of alkylamide-based solvents in which R 1 to R 3 in formula (1) are hydrogen or alkyl groups include formamide, acetamide, propanamide, butanamide, isobutylamide, pentanamide, and N-methylformamide. , N-methylacetamide, N-methylpropanamide, N-methylbutanamide, N-methylisobutyramide, N-methylpentanamide, N-ethylformamide, N-ethylacetamide, N-ethylpropanamide, N-ethylbutane Amide, 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-butylisobutyramide, 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-dibutylpropanamide, N,N-dibutylbutanamide, N,N-dibutylisobutylamide, N,N-dibutylpentane amides, 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-propylacetamide, 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-ethyl- Examples include N-propylbutanamide, N-ethyl-N-propylisobutyramide, N-ethyl-N-propylpentanamide, and those having alkyl groups with different numbers of carbon atoms or having branched carbon chains.
 また、前記式(1)のR、Rがアルコキシ基や、水酸基、ヒドロキシアルキル基となったものの例としては、N-エチル-N-(2-メトキシエチル)ホルムアミド、N-メトキシメチルホルムアミド、N-ヒドロキシメチル-N-メチルアセトアミド、N-(2-ヒドロキシエチル)-N-メチルアセトアミド、N-メトキシメチル-N-メチルホルムアミド、あるいはこれらの炭素数違いや炭素鎖が分岐構造を有するものなどが挙げられる。この中でも、本発明の効果を特に奏するという観点から、N-エチル-N-メチルホルムアミド、N-メチル-N-プロピルホルムアミド、N,N-ジエチルホルムアミド、N-エチル-N-プロピルホルムアミド、N,N-ジメチルアセトアミド、N-エチル-N-メチルアセトアミド、N-メチル-N-プロピルアセトアミド、N,N-ジエチルアセトアミド、N,N-ジメチルプロパンアミド、及びN-エチル-N-メチルプロパンアミドからなる群より選択されるアルキルアミド系溶剤が特に好ましい。 Examples of those in which R 2 and R 3 in formula (1) are alkoxy groups, hydroxyl groups, and hydroxyalkyl groups include N-ethyl-N-(2-methoxyethyl)formamide and N-methoxymethylformamide. , N-hydroxymethyl-N-methylacetamide, N-(2-hydroxyethyl)-N-methylacetamide, N-methoxymethyl-N-methylformamide, or those having a different carbon number or a branched carbon chain structure etc. Among these, N-ethyl-N-methylformamide, N-methyl-N-propylformamide, N,N-diethylformamide, N-ethyl-N-propylformamide, N, N-dimethylacetamide, N-ethyl-N-methylacetamide, N-methyl-N-propylacetamide, N,N-diethylacetamide, N,N-dimethylpropanamide, and N-ethyl-N-methylpropanamide Alkylamide solvents selected from the group are particularly preferred.
 ((アルコキシアルキルアミド系溶剤))
 アルコキシアルキルアミド系溶剤とは、アルコキシアルキル基(C2n+1-O-C2n-)と-C(=O)-N-基(アミド結合)を有する化合物からなる溶剤である。アルコキシアルキルアミド系溶剤は、例えば式(2)のアルキルアミド系構造を有するアルキルアミド系溶剤のうち沸点が230℃以下のものを好ましく用いることができる。
((Alkoxyalkylamide-based solvent))
An alkoxyalkylamide-based solvent is a solvent composed of a compound having an alkoxyalkyl group (C n H 2n+1 -O-C n H 2n -) and a -C(=O)-N- group (amide bond). As the alkoxyalkylamide-based solvent, for example, among alkylamide-based solvents having an alkylamide-based structure represented by formula (2), those having a boiling point of 230° C. or lower can be preferably used.
Figure JPOXMLDOC01-appb-C000004
(式(2)中、R12は、それぞれ独立して炭素数1以上4以下のアルキル基であり、R13は、炭素数1以上4以下のアルキレン基であり、R10、R11はそれぞれ独立してもよい官能基である。)
Figure JPOXMLDOC01-appb-C000004
(In Formula (2), R 12 is each independently an alkyl group having 1 to 4 carbon atoms, R 13 is an alkylene group having 1 to 4 carbon atoms, and R 10 and R 11 are each independently It is a functional group that may be independent.)
 R12は、炭素数1以上2以下のアルキル基であることが好ましく、炭素数1以上2以下のアルキル基であることがより好ましい。R13は、炭素数1以上3以下のアルキレン基であることが好ましく、炭素数1以上2以下のアルキレン基であることがより好ましい。 R 12 is preferably an alkyl group having 1 or more and 2 or less carbon atoms, more preferably an alkyl group having 1 or more and 2 or less carbon atoms. R 13 is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms.
 R10、R11は官能基であれば特に限定されないが、例えば、R10、R11は、水素、アルキル基、アルコキシ基、ヒドロキシアルキル基、水酸基であることが好ましく、水素、あるいはアルキル基であることがより好ましく、水素、あるいは炭素数1~4のアルキル基であることがさらに好ましく、水素、あるいは炭素数1~2のアルキル基であることがさらになお好ましい。 R 10 and R 11 are not particularly limited as long as they are functional groups. For example, R 10 and R 11 are preferably hydrogen, an alkyl group, an alkoxy group, a hydroxyalkyl group, or a hydroxyl group. is more preferred, hydrogen or an alkyl group having 1 to 4 carbon atoms is more preferred, and hydrogen or an alkyl group having 1 to 2 carbon atoms is even more preferred.
 アルコキシアルキルアミド系溶剤としては、3-メトキシ-N,N-ジメチルプロパンアミド、3-プロポキシ-N,N-ジメチルプロパンアミド、あるいはこれらのアルコキシ基やアルキル基の炭素数違いや炭素鎖が分岐構造を有するもののうち沸点が230℃以下のものが好ましい。この中でも、本発明の効果を特に奏するという観点から、3-メトキシ-N,N-ジメチルプロパンアミドが特に好ましい。 As the alkoxyalkylamide-based solvent, 3-methoxy-N,N-dimethylpropanamide, 3-propoxy-N,N-dimethylpropanamide, or the difference in the number of carbon atoms in the alkoxy group or alkyl group or the branched structure of the carbon chain. of those having a boiling point of 230° C. or lower are preferred. Among these, 3-methoxy-N,N-dimethylpropanamide is particularly preferable from the viewpoint of exhibiting the effects of the present invention.
 ((環状アミド系溶剤))
 環状アミド系溶剤とは、環状構造を有し、その環状構造に-C(=O)-N-基を有する化合物からなる溶剤である。環状アミド系溶剤は、例えば式(3)~(5)の環状アミド系溶剤のうち沸点が230℃以下のものを好ましく用いることができる。
((Cyclic amide solvent))
A cyclic amide solvent is a solvent composed of a compound having a cyclic structure and a -C(=O)-N- group in the cyclic structure. As the cyclic amide-based solvent, for example, among the cyclic amide-based solvents represented by formulas (3) to (5), those having a boiling point of 230° C. or less can be preferably used.
Figure JPOXMLDOC01-appb-C000005
(式(3)中、Rは、炭素数3以上5以下の分岐しても良いアルキレン基であり、Rは、水素若しくは炭素数1以上4以下のアルキル基または不飽和炭化水素基を表す。)
Figure JPOXMLDOC01-appb-C000005
(In formula (3), R 4 is an optionally branched alkylene group having 3 to 5 carbon atoms, and R 5 is hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group. represent.)
 Rは、炭素数3以上4以下のアルキレン基であることが好ましい。Rは、水素若しくは炭素数1以上2以下のアルキル基または不飽和炭化水素基であることが好ましい。 R 4 is preferably an alkylene group having 3 or more and 4 or less carbon atoms. R5 is preferably hydrogen, an alkyl group having 1 to 2 carbon atoms, or an unsaturated hydrocarbon group.
Figure JPOXMLDOC01-appb-C000006
(式(4)中、R14は水素若しくは炭素数1以上4以下の分岐しても良いアルキル基または不飽和炭化水素基であり、R15は炭素数1以上4以下のアルキレン基を表す。)
Figure JPOXMLDOC01-appb-C000006
(In formula (4), R 14 is hydrogen, an optionally branched alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group, and R 15 represents an alkylene group having 1 to 4 carbon atoms. )
Figure JPOXMLDOC01-appb-C000007
(式(5)中、R16、R17はそれぞれ独立して、水素若しくは炭素数1以上4以下の分岐しても良いアルキル基または不飽和炭化水素基でありR18は炭素数1以上4以下の分岐しても良いアルキレン基を表す。
Figure JPOXMLDOC01-appb-C000007
(In Formula (5), R 16 and R 17 are each independently hydrogen, an optionally branched alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group, and R 18 is 1 to 4 carbon atoms. represents the following optionally branched alkylene group.
 環状アミド系溶剤としては、N-ビニルメチルオキサゾリジノン、1,3-ジメチル-2-ピロリドン、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、β-ラクタム、4-メトキシ-1-メチル-2-ピロリジノン、N-プロピル-2-ピロリドン、N-メチル-2-ピペリジノン、あるいはこれらのアルコキシ基やアルキル基の炭素数違いや炭素鎖が分岐構造を有するもののうち沸点が230℃以下のものが好ましい。この中でも、本発明の効果を特に奏するという観点から、N-メチル-2-ピロリドンが特に好ましい。 Cyclic amide solvents include N-vinylmethyloxazolidinone, 1,3-dimethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, β-lactam, 4-methoxy-1-methyl -2-pyrrolidinone, N-propyl-2-pyrrolidone, N-methyl-2-piperidinone, or those having a branched carbon chain structure or differences in the number of carbon atoms in their alkoxy or alkyl groups, those having a boiling point of 230°C or less is preferred. Among these, N-methyl-2-pyrrolidone is particularly preferable from the viewpoint of exhibiting the effects of the present invention.
 沸点が230℃以下のアミド系溶剤の含有量は、とくに限定されるものではないが、インク組成物全量中2質量%以上の範囲であることが好ましく、5質量%以上の範囲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、乾燥性がより高いインク組成物となる。 The content of the amide-based solvent having a boiling point of 230° C. or lower is not particularly limited, but is preferably in the range of 2% by mass or more, and preferably in the range of 5% by mass or more, based on the total amount of the ink composition. More preferably, it is 10% by mass or more. As a result, the ink composition has a higher drying property.
 沸点が230℃以下のアミド系溶剤の含有量は、インク組成物全量中40質量%以下であることが好ましく、35質量%以下であることがより好ましく、30質量%以下であることがさらに好ましい。これにより、他の成分との相溶性が良く、インクの保存安定性が良いインク組成物となる。 The content of the amide-based solvent having a boiling point of 230° C. or less is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less in the total amount of the ink composition. . As a result, an ink composition having good compatibility with other components and good ink storage stability can be obtained.
 沸点が230℃以下のアミド系溶剤は、少なくとも2種以上のアミド系溶剤を含有することが好ましい。2種以上のアミド系溶剤を含有することで、着弾後に濡れ広がり易くなり、ドット径が大きくなることで画質を向上させることができる。また、少なくとも2種以上のアミド系溶剤を含有する場合、少なくとも1種のアミド系溶剤が200℃以下のアミド系溶剤であることが好ましい。これにより乾燥性が高く、得られる記録物の生産性がさらに高いインク組成物となる。 The amide-based solvent having a boiling point of 230°C or lower preferably contains at least two or more amide-based solvents. By containing two or more kinds of amide-based solvents, it becomes easy to wet and spread after landing, and the image quality can be improved by increasing the dot diameter. Moreover, when at least two or more amide solvents are contained, it is preferable that at least one amide solvent is an amide solvent of 200° C. or lower. As a result, the ink composition has a high drying property and the productivity of the obtained recorded matter is further increased.
 (その他の水溶性有機溶剤)
 本実施の形態に係るインク組成物には、沸点が230℃以下のアミド系溶剤とは異なるその他の水溶性有機溶剤を含有してもよい。
(Other water-soluble organic solvents)
The ink composition according to the present embodiment may contain a water-soluble organic solvent other than the amide-based solvent having a boiling point of 230° C. or less.
 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、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、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、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、3-メチル-2-ピロリジノン、2-ピロリドン、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、3-ブトキシ-N,N-ジメチルプロパンアミド、β-ラクタム、δ-ラクタム、ε-カプロラクタム、N-2-ヒドロキシエチル-2-ピロリドン、エチレン尿素、N-ヒドロキシエチレン尿素等のアミド系溶剤、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-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、アセトン、ジアセトンアルコ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、1,3-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、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;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-メチルモルホリン、N-エチルモルホリン、N-ヒドロキシエチルモルホリン、4-アセチルモルホリン、N-ホルミルモルホリンなどのモルホリン類、テルペン系溶剤など、一般的な有機溶剤であって、230℃以下のアミド系溶剤に該当しないものを挙げることができる。組み合わせる樹脂や分散剤などに応じて、適切なHSP値の溶剤を選択することが好ましい。 Ethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) ether, diethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t -butyl, pentyl, 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, 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 Dialkyl ethers of polyhydric alcohols such as glycol 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, Dipropylene 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) , isobutyl, t-butyl, pentyl, n-hexyl, 2-ethylhexyl) acetates such as 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-clotolactone, 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, 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, 3-methyl-2 -pyrrolidinone, 2-pyrrolidone, N-methyl-N-(1-methylethyl)formamide, N-hydroxypropyl-N-methylacetamide, 3-butoxy-N,N-dimethylpropanamide, β-lactam, δ-lactam , ε-caprolactam, N-2-hydroxyethyl-2-pyrrolidone, ethylene urea, amide solvents such as N-hydroxyethylene urea, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec -Butyl alcohol, tert-butyl alcohol, isobutyl alcohol, alkyl alcohols having 1 to 5 carbon atoms such as n-pentanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1- monohydric alcohols such as methoxy-2-propanol and 3-methoxy-n-butanol; ketones or ketoalcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; Ethylene or oxypropylene copolymer; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, 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-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5- diols such as pentanediol and 2-methyl-2,4-pentanediol; triols such as glycerin, trimethylolethane, trimethylolpropane and 1,2,6-hexanetriol; tetravalents such as mesoerythritol and pentaerythritol Alcohols; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine ; Morpholines such as N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, 4-acetylmorpholine, N-formylmorpholine, terpene solvents, etc., general organic solvents, amides at 230 ° C. or less Those not applicable to the system solvent can be mentioned. It is preferable to select a solvent with an appropriate HSP value according to the resin, dispersant, etc. to be combined.
 その中でも、ジオール系溶剤であることが好ましく、アルカンジオール系溶剤であることがより好ましく、1,2-アルカンジオール系溶剤であることがさらに好ましい。ジオール系溶剤は、インク組成物に含まれる他の含有成分との混和性が高く、かつ沸点が230℃以下のアミド系溶剤に比べて揮発性が低いため、ヘッドノズル面での乾燥を防ぐことが可能となり、吐出安定性を高めることができる。 Among them, diol-based solvents are preferred, alkanediol-based solvents are more preferred, and 1,2-alkanediol-based solvents are even more preferred. Diol-based solvents are highly miscible with other components contained in the ink composition, and have lower volatility than amide-based solvents with a boiling point of 230° C. or less. is possible, and the ejection stability can be improved.
 また、その他の水溶性有機溶剤として、環状エステル系溶剤、及びグリコールエーテル系溶剤からなる群より選択される少なくとも1以上の有機溶剤Bを含むことも好ましい。沸点が230℃以下のアミド系溶剤とともに、有機溶剤Bを含有させることで、乾燥性に加え着弾後に濡れ広がり易くなり、ドット径が大きくなることで画質を向上させることができる。 In addition, as other water-soluble organic solvents, it is also preferable to include at least one or more organic solvents B selected from the group consisting of cyclic ester-based solvents and glycol ether-based solvents. By containing the organic solvent B together with the amide-based solvent having a boiling point of 230° C. or less, the ink is dried and spreads easily after landing, and the dot diameter increases, thereby improving the image quality.
 なお、有機溶剤Bは、沸点は230℃以下であり、且つ水/1-オクタノールでの分配係数(LogP)が-0.4以上1.5以下であることが特に好ましい。 It is particularly preferable that the organic solvent B has a boiling point of 230° C. or lower and a water/1-octanol partition coefficient (LogP) of −0.4 or more and 1.5 or less.
 その他の水溶性有機溶剤を含有する場合、その他の水溶性有機溶剤の含有量は、特に限定されないが、例えば、インク組成物全量中1質量%以上であることが好ましく、5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く、15質量%以上であることがさらになお好ましい。インク組成物全量中35質量%以下であることが好ましく、30質量%以下であることがより好ましく、25質量%以下であることがさらに好ましい。 When the other water-soluble organic solvent is contained, the content of the other water-soluble organic solvent is not particularly limited. is more preferably 10% by mass or more, and even more preferably 15% by mass or more. It is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less, based on the total amount of the ink composition.
 [水]
 本実施の形態に係るインク組成物は、水を含有してもよい。水の含有量は、とくに限定されないが、水の含有量の下限は、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、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。
[water]
The ink composition according to this embodiment may contain water. The water content is not particularly limited, but the lower limit of the water content is preferably in the range of 30% by mass or more, more preferably in the range of 45% by mass or more, based on the total amount of the ink composition. , 50% by mass or more. The upper limit of the water content is preferably within the range of 85% by mass or less, more preferably within the range of 80% by mass or less, and within the range of 75% by mass or less in the total amount of the ink composition. is more preferred.
 特に、水を含有する場合、保存安定性の面からインク組成物の水以外の溶媒は親水性が高い溶剤で構成する必要があり、必然的にジオール系溶剤に代表される比較的高沸点の水溶性溶媒が選択される。溶媒が水と親水性が高い溶剤だけで構成される水性インク組成物の場合、特に低温乾燥においては乾燥性が悪化する傾向があり、乾燥性が悪化するという本発明の課題がより顕著に発生することになる。所定沸点以下のアミド系溶剤を含有する本実施の形態に係るインク組成物であれば、水を含有する水性インク組成物であっても、乾燥性を高くすることができるようになり、得られる記録物の生産性を高くすることが可能となる。 In particular, when water is contained, the solvent other than water in the ink composition must be composed of a highly hydrophilic solvent from the standpoint of storage stability. A water-soluble solvent is selected. In the case of an aqueous ink composition in which the solvent is composed of only water and a highly hydrophilic solvent, the drying property tends to deteriorate particularly in low-temperature drying, and the problem of the present invention that the drying property deteriorates occurs more remarkably. will do. As long as the ink composition according to the present embodiment contains an amide-based solvent having a predetermined boiling point or less, even if it is an aqueous ink composition containing water, it becomes possible to improve the drying property, and it is possible to obtain It is possible to increase the productivity of printed matter.
 [樹脂]
 本実施の形態に係るインク組成物は、樹脂を含有してもよい。本実施の形態に係るインク組成物は、樹脂を含有することは必須の構成ではないが、樹脂を含有することで塗膜の耐擦過性を向上させることができる。さらに本実施の形態に係るインク組成物に含まれる沸点が230℃以下のアミド系溶剤が造膜助剤として作用するので、例えば樹脂のTg以下の温度のような低温での乾燥温度であっても、樹脂を基材上で融着させることが可能となり、十分に耐擦過性の有する塗膜を形成することが可能となる。特に、本実施の形態に係るインク組成物をオーバーコートインクとする場合、樹脂を含有することで、記録物に好適な耐擦過性を付与することが可能となる。
[resin]
The ink composition according to this embodiment may contain a resin. The ink composition according to the present embodiment does not necessarily contain a resin, but the resin can improve the abrasion resistance of the coating film. Furthermore, since the amide-based solvent having a boiling point of 230° C. or less contained in the ink composition according to the present embodiment acts as a film-forming aid, the drying temperature at a low temperature such as a temperature not higher than the Tg of the resin, for example, Also, the resin can be fused on the base material, and a coating film having sufficient abrasion resistance can be formed. In particular, when the ink composition according to the present embodiment is used as an overcoat ink, it is possible to impart suitable scratch resistance to a recorded matter by containing a resin.
 樹脂としては、定着性に優れ、インクの層の耐水性に優れる点から分散性樹脂が好ましい。また、分散性樹脂を形成することによって、樹脂が静電反発力や立体反発力によって樹脂微粒子としてインク中に分散することができ、分散安定性を向上させることが可能となる。なお、分散性樹脂とは、インク組成物中に粒子状に分散した樹脂であり、粒子状の樹脂がインク組成物中に分散可能な樹脂を意味する。 As the resin, a dispersible resin is preferable from the viewpoint of excellent fixability and excellent water resistance of the ink layer. Further, by forming a dispersible resin, the resin can be dispersed in the ink as fine resin particles by electrostatic repulsion or steric repulsion, and dispersion stability can be improved. The dispersible resin is a resin that is dispersed in the ink composition in the form of particles, and means a resin that can be dispersed in the ink composition in the form of particles.
 具体的には、アクリル系樹脂、スチレン-アクリル系樹脂、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。これらのものは耐水性に加えて耐溶剤性も向上させることができる点で好ましい。中でも、吐出安定性、耐水性及び耐溶剤性に優れたものとすることができることから、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アクリル系樹脂又はアクリル系樹脂との共重合体を含むものであることが好ましい。 Specifically, acrylic resins, styrene-acrylic resins, polyurethane resins, polyester resins, vinyl chloride resins, vinyl acetate resins, polyether resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, One or more resins selected from the group consisting of acrylamide-based resins, epoxy-based resins, polycarbonate-based resins, silicone-based resins, and polystyrene-based resins, or copolymer resins, or mixtures thereof can be used. . These are preferable because they can improve not only water resistance but also solvent resistance. Among them, since it can be excellent in ejection stability, water resistance and solvent resistance, at least one of the constituent monomers contains an acrylic resin or a copolymer with an acrylic resin having an acrylic skeleton. is preferred.
 本実施の形態に係るインク組成物に含まれる樹脂のTg(ガラス転移温度)は、とくに限定されるものではないが、インク組成物の乾燥温度よりも高いことが好ましい。具体的には、樹脂のTgは50℃以上であることが好ましく、55℃以上であることがより好ましく、60℃以上であることがさらに好ましい。本来であれば、インク組成物に含まれる樹脂のTgが高くなると乾燥温度を高くしなければ樹脂を基材上に融着させることができず、記録物に好適な耐擦過性を付与することが難しくなる。造膜助剤として作用する230℃以下のアミド系溶剤を含有する本実施の形態に係るインク組成物であれば、高いTgを有する樹脂を含有していても低温乾燥で樹脂を基材上で融着させることが可能となり、記録物に好適な耐擦過性を付与することが可能となる。 Although the Tg (glass transition temperature) of the resin contained in the ink composition according to the present embodiment is not particularly limited, it is preferably higher than the drying temperature of the ink composition. Specifically, the Tg of the resin is preferably 50° C. or higher, more preferably 55° C. or higher, and even more preferably 60° C. or higher. Originally, when the Tg of the resin contained in the ink composition becomes high, the resin cannot be fused onto the base material unless the drying temperature is increased, thereby imparting suitable scratch resistance to the recorded matter. becomes difficult. If the ink composition according to the present embodiment contains an amide-based solvent of 230° C. or less that acts as a film-forming aid, even if it contains a resin having a high Tg, the resin can be dried on the substrate at a low temperature. It is possible to fuse and impart suitable scratch resistance to the recorded matter.
 市販の分散性樹脂としては、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-ウレタン分散性樹脂)、AKW107、RKW-500(大成ファインケミカル(株)製、アクリル分散性樹脂)、LUBRIJET N240(ルーブリゾール製、アクリル分散性樹脂)、スーパーフレックス150、210、470、500M、E2000、E4800、R5002(第一工業製薬(株)製、ウレタン分散性樹脂)、ビニブラン700、701、711、737、747(日信化学(株)製、塩化ビニル-アクリル分散性樹脂)、ビニブラン2706、2685(日信化学(株)製、アクリル分散性樹脂)、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、アクリル分散性樹脂)、PRIMAL AC-261P、 AC-818(ダウ・ケミカル社製 アクリル樹脂)、NeoCryl A2091、A2092、A639、A655、A662(DSM Coating Resin社製 スチレン-アクリル樹脂)、QE-1042、KE-1062(星光PMC社製 スチレン-アクリル分散性樹脂)、JE-1056(星光PMC社製 アクリル樹脂)、JONCRYL7199、PDX-7630A(BASFジャパン社製 スチレン-アクリル分散性樹脂)、シャリーヌR170BX(日信化学工業社製 シリコーン-アクリル分散性樹脂)、タケラックW-6010(三井化学社製 ウレタン分散性樹脂)、エリーテル KA-5071S(ユニチカ社製 ポリエステル分散性樹脂)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 dispersible resins include, for example, ACRYT WEM-031U, WEM-200U, WEM-321, WEM-3000, WEM-202U, WEM-3008 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic-urethane dispersible resin). , AKW107, RKW-500 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic dispersible resin), LUBRIJET N240 (manufactured by Lubrizol, acrylic dispersible resin), Superflex 150, 210, 470, 500M, E2000, E4800, R5002 (No. Ichi Kogyo Pharmaceutical Co., Ltd., urethane dispersing resin), Vinyblan 700, 701, 711, 737, 747 (manufactured by Nissin Chemical Co., Ltd., vinyl chloride-acrylic dispersing resin), Vinyblan 2706, 2685 (Nissin Chemical Co., Ltd., acrylic dispersion resin), Movinyl 743N, 6520, 6600, 6820, 7470, 7720, (Japan Coating Resin Co., acrylic dispersion resin), PRIMAL AC-261P, AC-818 (Dow Chemical Company) acrylic resin), NeoCryl A2091, A2092, A639, A655, A662 (styrene-acrylic resin manufactured by DSM Coating Resin), QE-1042, KE-1062 (styrene-acrylic dispersion resin manufactured by Seiko PMC), JE-1056 (manufactured by Seiko PMC, acrylic resin), JONCRYL7199, PDX-7630A (manufactured by BASF Japan, styrene-acrylic dispersible resin), Charine R170BX (manufactured by Nissin Chemical Industry Co., Ltd., silicone-acrylic dispersible resin), Takelac W-6010 (Mitsui Kagaku Co., Ltd. urethane dispersing resin), Elitel KA-5071S (Unitika Co., Ltd. polyester dispersing resin), etc. can be exemplified, but are not limited to these.
 インク組成物に樹脂を含有させる場合、インク組成物に含まれる樹脂(分散性樹脂)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、インク全量中0.05質量%以上であることが好ましく、0.1質量%以上であることが好ましく、更に0.5質量%以上であることが好ましく、1質量%以上がより好ましい。これにより、塗膜の耐擦過性をさらに向上させることができる。樹脂の含有量の上限は、インク全量中25質量%以下であることが好ましく、中でも、20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。これにより、インク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。 When the ink composition contains a resin, the content of the resin (dispersible resin) contained in the ink composition is not particularly limited, but the lower limit of the resin content is 0.05 in the total amount of the ink. It is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and more preferably at least 1% by mass. Thereby, the scratch resistance of the coating film can be further improved. The upper limit of the resin content is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total amount of the ink. This makes it possible to improve the ejection stability when the ink is ejected onto the surface of the substrate by an inkjet method.
 分散性樹脂の平均粒子径は、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、30nm以上が好ましく、40nm以上がより好ましく、50nm以上がさらに好ましい。分散性樹脂の平均粒子径は、300nm以下が好ましく、270nm以下がより好ましく、250nm以下がさらに好ましい。これにより、インク組成物の吐出安定性がさらに向上する。さらに、樹脂は少なくとも一部が分散性樹脂を含むものであると、インク組成物の製膜時で水溶性有機溶剤が徐々に揮発するにつれて、インク組成物に含まれる樹脂粒子同士がより密に充填されることとなるが、分散性樹脂の平均粒子径が300nm以下であることにより、密に充填された樹脂粒子同士の接触面積が大きくなり、融着が進行し易くなる。これにより、基材上でより効果的に粒子樹脂同士を融着させることができるようになり、より耐擦性の高い塗膜を形成することが可能である。しかも、本実施の形態に係るインク組成物は、造膜助剤として作用する沸点が230℃以下であるアミド系溶剤を含有するため、例えば樹脂のTg以下の温度のような低温での乾燥温度であっても、樹脂を基材上で融着させることが可能となって、塗膜の耐擦過性や耐水摩擦性をさらに高めることが可能となる。なお、本実施形態において、分散性樹脂の平均粒子径は、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。 The average particle size of the dispersible resin is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more, from the viewpoint of dispersion stability in the ink composition and inkjet dischargeability. The average particle size of the dispersible resin is preferably 300 nm or less, more preferably 270 nm or less, and even more preferably 250 nm or less. This further improves the ejection stability of the ink composition. Further, when at least a portion of the resin contains a dispersible resin, the resin particles contained in the ink composition are more densely packed as the water-soluble organic solvent gradually volatilizes during film formation of the ink composition. However, when the average particle diameter of the dispersible resin is 300 nm or less, the contact area between the densely packed resin particles is increased, and fusion is facilitated. As a result, the resin particles can be more effectively fused together on the substrate, and a coating film with higher abrasion resistance can be formed. Moreover, since the ink composition according to the present embodiment contains an amide-based solvent having a boiling point of 230° C. or less that acts as a film-forming aid, the drying temperature at a low temperature such as a temperature not higher than the Tg of the resin, for example, Even so, the resin can be fused onto the base material, and the abrasion resistance and water abrasion resistance of the coating film can be further enhanced. In the present embodiment, the average particle size of the dispersible resin 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.
 分散性樹脂の質量平均分子量は、塗膜の耐水性の観点から、10000以上が好ましく、50000以上がより好ましく、100000以上がさらに好ましい。分散性樹脂の質量平均分子量は、インク組成物での分散安定性の観点から、2000000以下が好ましく、1500000以下がより好ましく、1000000以下がより好ましい。なお、本実施形態において樹脂の分子量は、質量平均分子量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 the water resistance of the coating film, the mass average molecular weight of the dispersible resin is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more. From the viewpoint of dispersion stability in the ink composition, the mass average molecular weight of the dispersible resin is preferably 2,000,000 or less, more preferably 1,500,000 or less, and more preferably 1,000,000 or less. In the present embodiment, the molecular weight of the resin indicates the mass 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 a calibration curve as a standard.
 [レベリング剤]
 本実施の形態に係るインク組成物にはレベリング剤を含有してもよい。本実施の形態に係るインク組成物は、レベリング剤を含有することは必須の構成ではないが、レベリング剤を含有することで、基材上に塗布されたインク組成物がより濡れ広がるようになり、得られる記録物のドット径が大きくなるとともに、インク組成物と外気との界面の表面積が増えるようになり、沸点が230℃以下のアミド系溶剤を含有する本実施の形態に係るインク組成物がより効果的に乾燥するようになり、本発明の効果を特に効果的に奏するようになる。
[Leveling agent]
The ink composition according to this embodiment may contain a leveling agent. Although it is not essential that the ink composition according to the present embodiment contains a leveling agent, the inclusion of the leveling agent allows the ink composition applied on the substrate to spread more wetly. The ink composition according to the present embodiment contains an amide-based solvent having a boiling point of 230° C. or less, so that the dot diameter of the obtained recorded matter increases and the surface area of the interface between the ink composition and the outside air increases. is dried more effectively, and the effects of the present invention are particularly effective.
 本実施の形態に係るインク組成物にレベリング剤を含有する場合、レベリング剤の種類は特に限定されない。例えば、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、アルカングリコール系界面活性剤等の界面活性剤を挙げることができる。本実施の形態に係るインク組成物は、この中でもシリコーン(シリコン)系界面活性剤を含有することが好ましい。これにより、塗膜表面の滑り性が良好となって塗膜の耐擦過性が向上する。 When the ink composition according to the present embodiment contains a leveling agent, the type of leveling agent is not particularly limited. Examples include surfactants such as anionic surfactants, nonionic surfactants, silicone (silicon) surfactants, fluorine surfactants, acetylene glycol surfactants, and alkane glycol surfactants. be able to. Among these, the ink composition according to the present embodiment preferably contains a silicone surfactant. As a result, the lubricating property of the coating film surface is improved, and the abrasion resistance of the coating film is improved.
 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、3456、3451、3455(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 Emal, Latemul, Pelex, Neoperex, Demol (all of which are anionic surfactants; manufactured by Kao Corporation), Sunol, Liporan, Lipon, and Ripal (all of which are anionic surfactants; Lion Co., Ltd. company), Noigen, Epan, Solgen (all nonionic surfactants; Daiichi Kogyo Seiyaku Co., Ltd.) Emulgen, Amit, Emsol (all nonionic surfactants; Kao Corporation), Naloacty , Emalmin, Sannonic (both nonionic surfactants; manufactured by Sanyo Chemical Industries, Ltd.), Surfynol 104, 82, 420, 440, 465, 485, TG, 2502, SE-F, 107L, Dynol 360, Dynol 604, Dynol 607 (both are acetylene glycol-based surfactants; manufactured by Evonik), Dynol 960 (mixture of acetylene glycol-based and silicon-based surfactants; manufactured by Evonik), Surfynol AD01 (alkane glycol-based surfactant agent; manufactured by Evonik), Olfine E1004, E1010, PD004, EXP4300 (all of which are acetylene glycol-based surfactants; manufactured by Nissin Chemical Industry Co., Ltd.), Megafac (fluorine-based surfactant; 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, 3456, 3451, 3455 (all silicone )-based surfactant; manufactured by BYK Chemie), KP-110, 112, 323, 341, 6004 (all silicone (silicon)-based surfactants; manufactured by Shin-Etsu Chemical Co., Ltd.), Silface SAG002, Silface SAG005, Sil Face SAG008, Silface SAG014, Silface SAG503A, Silface SJM-002, Silface SJM-003 (all silicone (silicon) 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 , 270, 280 (all silicone surfactants; manufactured by Evonik), TEGO Wet 500, 505, 510, 520 (all nonionic surfactants; manufactured by Evonik).
 そのなかでもHLB値が15以下であるレベリング剤であることが好ましい。HLB値が15以下であるレベリング剤であれば、基材上に塗布されたインク組成物と外気との界面にレベリング剤が配向しやすくなり、インク組成物がより濡れ広がるようになるので、得られる記録物のドット径がより大きくなるとともに、インク組成物がさらに効果的に乾燥するようになる。 Among them, a leveling agent with an HLB value of 15 or less is preferable. If the leveling agent has an HLB value of 15 or less, the leveling agent tends to be oriented at the interface between the ink composition applied on the substrate and the outside air, and the ink composition spreads more easily. The ink composition dries more effectively as the dot diameter of the recorded matter becomes larger.
 また、本実施の形態に係るインク組成物にレベリング剤を含有する場合、レベリング剤の含有量は、本実施の形態に係るインク組成物に含まれる沸点が230℃以下のアミド系溶剤の含有量に応じて制御することが好ましい。沸点が230℃以下のアミド系溶剤は水溶性有機溶剤のなかでも比較的疎水性の水溶性有機溶剤であるので、特にHLB値が低いレベリング剤がインク組成物に含まれると沸点が230℃以下のアミド系溶剤に溶け込みやすくなり、外気との界面にレベリング剤が配向し難くなる場合がある。そのため、沸点が230℃以下のアミド系溶剤の含有量に応じて適切に含有量を制御することでインク組成物が濡れ広がるようになるので、インク組成物が効果的に乾燥するようになる。 Further, when the ink composition according to the present embodiment contains a leveling agent, the content of the leveling agent is the content of the amide-based solvent having a boiling point of 230° C. or less contained in the ink composition according to the present embodiment. It is preferable to control according to Amide-based solvents having a boiling point of 230° C. or less are relatively hydrophobic water-soluble organic solvents among water-soluble organic solvents. It becomes easy to dissolve in the amide-based solvent, and it may become difficult for the leveling agent to be oriented at the interface with the outside air. Therefore, by appropriately controlling the content of the amide-based solvent having a boiling point of 230° C. or less, the ink composition spreads out and dries effectively.
 レベリング剤の含有量は、前記インク組成物に含まれる前記アミド系溶剤100質量部に対して0.1質量部以上の範囲であることが好ましい。これにより、インク組成物がさらに濡れ広がるようになるので、インク組成物がさらに効果的に乾燥するようになる。なお、0.3質量部以上の範囲であることがより好ましく、0.6質量部以上の範囲であることがさらに好ましく、1.0質量部以上の範囲であることがさらになお好ましい。 The content of the leveling agent is preferably in the range of 0.1 parts by mass or more with respect to 100 parts by mass of the amide solvent contained in the ink composition. As a result, the ink composition is further wetted and spread, so that the ink composition dries more effectively. The range of 0.3 parts by mass or more is more preferable, the range of 0.6 parts by mass or more is even more preferable, and the range of 1.0 parts by mass or more is even more preferable.
 また、レベリング剤の含有量は、インク組成物に含まれる前記アミド系溶剤100質量部に対して50質量部以下の範囲であることが好ましい。これにより、レベリング剤のアミド系溶剤に対する相溶性が向上する。なお、49質量部以下の範囲であることがより好ましく、48質量部以下の範囲であることがさらに好ましい。 Also, the content of the leveling agent is preferably in the range of 50 parts by mass or less with respect to 100 parts by mass of the amide solvent contained in the ink composition. This improves the compatibility of the leveling agent with the amide solvent. The range of 49 parts by mass or less is more preferable, and the range of 48 parts by mass or less is even more preferable.
 [色材]
 本実施の形態に係る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 ink composition according to this embodiment may contain a coloring material. The ink composition according to the present embodiment does not necessarily contain a coloring material. It is possible to use white ink or metallic ink that will serve as a base layer. The colorant may be either a dye or a pigment.
 本実施の形態に係るインク組成物において、用いることのできる顔料は特に限定されず、従来の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。 The pigment that can be used in the ink composition according to the present embodiment is not particularly limited, and examples thereof include organic pigments and inorganic pigments used in conventional ink compositions. These may be used individually by 1 type, or may be used in combination of 2 or more type. Note that the ink composition according to the present embodiment may not contain a coloring material. When a pigment is used in the ink composition according to this embodiment, the dispersion stability of the pigment can be improved by using a dispersant or a dispersing aid (pigment derivative).
 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。 Specific organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine-based organic pigments, quinacridone-based organic pigments, perylene-based organic pigments, perinone-based organic pigments, azomethine-based organic pigments, and anthraquinone-based pigments. Organic pigments (anthrone-based organic pigments), xanthene-based organic pigments, diketopyrrolopyrrole-based organic pigments, dioxazine-based organic pigments, nickel azo-based pigments, isoindolinone-based organic pigments, pyranthrone-based organic pigments, thioindigo-based organic pigments, condensed azo organic solid solution pigments such as organic pigments, 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. 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。 When organic pigments are exemplified by color index (C.I.) numbers, 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. 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. I. pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 16, 22, 60, 64, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, C.I. I. Pigment Brown 23, 25, 26, C.I. I. Pigment Black 7 and the like.
 本実施の形態に係るインク組成物において、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。 Specific examples of dyes that can be used in the ink composition according to the present embodiment include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, Merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes such as indigoids, fulgide dyes, nickel complex dyes, and azulene dyes dyes.
 本実施の形態に係るインク組成物において、用いることのできる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、アルミニウム、チタン、インジウム、合成鉄黒、無機固溶体顔料等を挙げることができる。 Specific examples of inorganic pigments that can be used in the ink composition according to the present embodiment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, alumina, and zinc. Flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron (III)), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, titanium black, aluminum, titanium, indium, synthetic iron black, Inorganic solid solution pigments and the like can be mentioned.
 これらの有機顔料又は無機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、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、得られる印刷物の耐光性を良好なものとすることができる。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 these organic pigments or inorganic pigments is not particularly limited as long as the desired color development is possible. Although it varies depending on the type of pigment, the lower limit of the average dispersed particle diameter of the pigment is preferably in the range of 10 nm or more, preferably 20 nm or more, from the viewpoint of obtaining sufficient coloring power with good dispersion stability of the pigment. It is more preferably within the range, and even more preferably within the range of 30 nm or more. The upper limit of the average dispersed particle size of the pigment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less. If the average dispersed particle size is 500 nm or less, nozzle clogging of an inkjet head is unlikely to occur, and a uniform image with high reproducibility can be obtained. When the average dispersed particle diameter is 10 nm or more, the light resistance of the resulting printed matter can be improved. In the present embodiment, the average dispersed particle diameter of the pigment is the average particle diameter ( D50).
 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 the present embodiment may contain a luster pigment as a pigment. Luminous pigments include metal-containing luster 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; Pearl pigments having pearl luster or interference luster such as mica, fish scale foil, bismuth oxychloride, silicon dioxide, metal oxides, metal compounds, and laminates thereof may be mentioned.
 本実施の形態に係る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 ink composition according to the present embodiment contains a glitter pigment, the glitter pigment preferably has a plate-like shape (also referred to as a fine plate-like shape, a scale-like shape, or the like). This makes it possible to impart a more suitable metallic luster to the subject.
 本実施の形態に係るインク組成物に色材を含有する場合、色材の含有量は、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インク組成物に色材を含有する場合、色材の含有量は、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。 When the ink composition according to the present embodiment contains a coloring material, the content of the coloring material is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, based on the total amount of the ink composition. is more preferable, and 0.1% by mass or more is even more preferable. When the 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 ink composition. is more preferable, and 15.0% by mass or less is even more preferable.
 [顔料分散剤]
 本実施の形態に係るインク組成物には顔料分散剤を含有してもよい。本実施の形態に係るインク組成物は、顔料分散剤を含有することは必須の構成ではないが、顔料とともに顔料分散剤を含有することで、顔料の分散性を向上させることができる。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組成物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 ink composition according to this embodiment may contain a pigment dispersant. The ink composition according to the present embodiment does not necessarily contain a pigment dispersant, but by containing the pigment dispersant together with the pigment, the dispersibility of the pigment can be improved. Here, the term "pigment dispersant" means a resin or surfactant that adheres to a part of the pigment surface and has a function of improving the dispersibility of the pigment in the ink composition.
 本実施の形態に係るインク組成物において、用い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 ink composition according to the present embodiment is not particularly limited. For example, cationic, anionic, nonionic, amphoteric, silicone (silicon), and fluorine surfactants can be used. Among surfactants, polymer surfactants (polymer dispersants) such as those exemplified below are preferable.
 本実施の形態に係る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)アクリル系樹脂を含有する水溶性高分子分散剤が、インク組成物の分散安定性と、印刷物の画像鮮明性の観点から好ましい。 A water-soluble polymer dispersant can be preferably used as a pigment dispersant that can be used in the ink composition according to the present embodiment. Examples of water-soluble polymer dispersants include polyester-, polyacrylic-, polyurethane-, polyamine-, and polycaptolactone-based main chains, and side chains containing amino, carboxy, sulfo, and hydroxy groups. and dispersing agents having polar groups such as For example, (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene and unsaturated carboxylic acid esters such as acrylic acid 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 acid esters Polyurethanes; Unsaturated polyamides; Polysiloxanes; Long-chain polyaminoamide phosphates; Polyethyleneimine derivatives (poly (lower alkylene imine) and free carboxyl group-containing polyester amides obtained by reaction and their bases); polyallylamine derivatives (polyallylamine and polyester having a free carboxyl group, polyamide or co-condensation product of ester and amide (polyesteramide)) reaction products obtained by reacting with one or more compounds) and the like. Among them, a water-soluble polymer dispersant containing a (meth)acrylic resin is preferable from the viewpoint of the dispersion stability of the ink composition and the image clarity of the 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-2055、DISPERBYK-2060、DISPERBYK-2061、DISPERBYK-2081、DISPERBYK-2096、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。 Specific examples of the water-soluble polymer dispersant include Cray Valley's SMA1440, SMA2625, SMA17352, SMA3840, SMA1000, SMA2000, SMA3000, BASF Japan's JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL690, JONCRYL819, JONCRYL -JDX5050, EFKA4550, EFKA4560, EFKA4585, EFKA5220, EFKA6230, Dispex Ultra PX4575, Lubrizol SOLSPERSE20000, SOLSPERSE27000, SOLSPERSE40000, SOLSPERSE410 00, SOLSPERSE41090, SOLSPERSE43000, SOLSPERSE44000, SOLSPERSE45000, SOLSPERSE46000, SOLSPERSE47000, SOLSPERSE53095, SOLSPERSE54000, SOLSPERSE64000, SOLSPERSE65000, SOLSPERSE66000 , SOLSPERSE J400, SOLSPERSE W100, SOLSPERSE W200, SOLSPERSE W320, SOLSPERSE WV400, BYK-Chemie ANTI-TERRA-250, BYKJET-9150, BYKJET-9151, BYKJET-9152, BYKJET-917 0, DISPERBYK-102, DISPERBYK-168, DISPERBYK -180, DISPERBYK-184, DISPERBYK-185, DISPERBYK-187, DISPERBYK-190, DISPERBYK-191, DISPERBYK-193, DISPERBYK-194N, DISPERBYK-198, DISPERBYK-199, DISPERBYDIK-2010, DISPERBY K-2012, DISPERBYK-2013 , DISPERBYK-2014, DISPERBYK-2015, DISPERBYK-2018, DISPERBYK-2019, DISPERBYK-2055, DISPERBYK-2060, DISPERBYK-2061, DISPERBYK-2081, DISPERBYK-2096, Evonik TEGO DISPER S650, TEGO DISPERS651, TEGO DISPERS652, TEGO DISPERS 655, TEGO DISPERS 660C, TEGO DISPERS 670, TEGO DISPERS 715W, TEGO DISPERS 740W, TEGO DISPERS 741W, TEGO DISPERS 750W, TEGO DISPERS 752W, TEGO DISPERS 755W, TEGO DISPERS 75 7W, TEGO DISPERS760W, TEGO DISPERS761W, TEGO DISPERS765W, ZETASPERSE170, ZETASPERSE179, ZETASPERSE182, ZETASPERSE3100, ZETASPERSE3400, ZETASPERSE3700, ZETASPERSE 3800, 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, NOPCOSANT K, NOPCOSANT R, NOPCOSPERS 44-C, Nopcos Perth 6100, Nopcos Perth 6150 and the like.
 [カチオン性の化合物]
 本実施の形態に係るインクにはカチオン性の化合物を含有してもよい。本実施の形態に係るインク組成物は、カチ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、カチオン性の化合物を含有することで、本実施の形態に係るインク組成物を受理溶液にすることができる。一般的に色材を含む着色インク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。
[Cationic compound]
The ink according to this embodiment may contain a cationic compound. The ink composition according to the present embodiment does not necessarily contain a cationic compound. can do. In general, the coloring ink containing the coloring material is anionic. By applying a receiving solution containing a cationic compound to the substrate prior to applying the coloring ink to the substrate, the cationic compound can color the ink. It becomes possible to agglomerate the material, and it is possible to suppress the bleeding of the colored ink.
 カチオン性の化合物としては、多価金属塩(多価金属のイオン)やカチオン性の樹脂を挙げることができる。 Examples of cationic compounds include polyvalent metal salts (polyvalent metal ions) and cationic resins.
 多価金属塩は、主に多価金属のイオンと、陰イオンと、を含有する。なお、「多価金属塩を含有する」という概念は、受理溶液作製時において多価金属塩を添加するもののみならず、多価金属イオンを生成し得る化合物と、陰イオンを生成し得る化合物と、を受理溶液作製時に添加することにより多価金属塩を構成する多価金属のイオンと、陰イオンと、を含有することとなった態様も含む概念である。 Polyvalent metal salts mainly contain ions and anions of polyvalent metals. The concept of "containing a polyvalent metal salt" includes not only those to which a polyvalent metal salt is added during preparation of the receiving solution, but also compounds capable of generating polyvalent metal ions and compounds capable of generating anions. and are added at the time of preparation of the receiving solution to contain the polyvalent metal ions and the anions constituting the polyvalent metal salt.
 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。陰イオンの分散性、及び受理溶液の保存安定性及び吐出安定性の観点から、陰イオンは、有機物の陰イオンを含むことが好ましい。 The anion may be an anion of an inorganic substance or an anion of an organic substance. From the viewpoint of the dispersibility of the anions and the storage stability and discharge stability of the receiving solution, the anions preferably include organic anions.
 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。 Specific examples of inorganic anions include chloride ions, bromide ions, nitrate ions, and sulfate ions.
 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。 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, methylmalonic acid.
 多価金属イオンとは、価数が少なくとも2価以上の金属のイオンをいう。多価金属イオンを用いることでインク組成物のにじみを抑制することができる。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、滲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。 A polyvalent metal ion is an ion of a metal with a valence of at least two. Bleeding of the ink composition can be suppressed by using polyvalent metal ions. 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, and the like. is mentioned. Among them, one selected from calcium ions, magnesium ions, nickel ions, zinc ions, and aluminum ions, because it has a large interaction with the colorant in the ink composition and has a high effect of suppressing bleeding and unevenness. It is preferable to contain the above.
 また、カチオン性の化合物は、多価金属塩の代わりにカチオン基を有するカチオン性の樹脂を含有したものであってもよい。カチオン性の樹脂としては、アミノ基、アンモニウム基、アミド基、-NHCONH基等のカチオン基を有する樹脂が挙げられる。 Moreover, the cationic compound may contain a cationic resin having a cationic group instead of the polyvalent metal salt. Examples of cationic resins include resins having cationic groups such as amino groups, ammonium groups, amide groups, and --NHCONH2 groups.
 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、アクリットUW-550CS、UW-223SX(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)、スーパーフレックス620、650(第一工業製薬社製)、ビニブラン701FE50(日信化学社製)、ポリゾールAP-1350(昭和電工社製)などとなる。なお、カチオン性の樹脂は、インク組成物(受理溶液)中に溶解した状態で存在していても、樹脂微粒子として分散された状態で存在していてもよい。  The cationic resin can be synthesized by a known method, or a commercially available product can be used. Examples of commercially available products are as follows: APC-810, 815; D-6010, 6020, 6030, 6040, 6050, 6060, 6080, 6310; 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; Myriogen P- 20; Unisense FPA100L, FPA101L, FPA102L, FPA1000L, FPA1001L, FPA100LU, FPA102LU, FPA1000LU; Unisense FCA1000L, FCA1001L, FCA1002L, FCA1003L, FCA5000L; Unisense KCA100L, KCA1 00LU, 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, PD7 00, PD714L, PD714S, P600, (manufactured by Asada Chemical Co., Ltd.), violet resin 650 (30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Co., Ltd.), EP-1137; MZ-477, 480; 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 Nittobo Medical), PP-17 ( Meisei Chemical Co., Ltd.); Catiomaster PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Gosei Co., Ltd.), Jetfix 36N, 38A, 5052 (manufactured by Satoda Kako), Movinyl 3500, 6910, 6940, 6950, 6951, 7820 (manufactured by Japan Coating Resin), CTW-113S, WEM-505C, WBR-2122C, Acryt UW-550CS, UW -223SX (manufactured by Taisei Fine Chemical Co., Ltd.), AP-1350, AE-803, AE-821, AM-3500 (manufactured by Resonac), Hydran CP-7050, CP-7520 (manufactured by DIC), Superflex 620, 650 ( Daiichi Kogyo Seiyaku Co., Ltd.), Vinyblan 701FE50 (Nissin Chemical Co., Ltd.), Polysol AP-1350 (Showa Denko Co., Ltd.), and the like. The cationic resin may be present in the ink composition (receiving solution) in a dissolved state or in a dispersed state as fine resin particles.
 カチオン性の樹脂は、水や水溶性有機溶剤に溶解する水溶性のカチオン性の樹脂であっても、水や水溶性有機溶剤中で分散する分散性のカチオン性の樹脂であってもよい。この中でも、カチオン性の樹脂が分散性のカチオン性の樹脂であることが好ましい。分散性のカチオン性の樹脂を含有することにより、インク組成物の層の塗膜耐性(耐擦過性)を向上させることができる。この中でも、カチオン性の化合物として、多価金属イオン及び分散性のカチオン性の樹脂を含有するか、またはカチオン性の化合物として、水溶性のカチオン性の樹脂及び分散性のカチオン性の樹脂を含有することがさらに好ましい。このように多価金属イオン(若しくは水溶性のカチオン性の樹脂)及び分散性のカチオン性の樹脂を併用することで、着色インクのにじみをより効果的に抑制しつつインク組成物の層の塗膜耐性(耐擦過性)を向上させることができる。 The cationic resin may be a water-soluble cationic resin that dissolves in water or a water-soluble organic solvent, or a dispersible cationic resin that disperses in water or a water-soluble organic solvent. Among these, the cationic resin is preferably a dispersible cationic resin. By containing a dispersible cationic resin, the coating film resistance (scratch resistance) of the ink composition layer can be improved. Among them, the cationic compound contains a polyvalent metal ion and a dispersible cationic resin, or the cationic compound contains a water-soluble cationic resin and a dispersible cationic resin. more preferably. By using a polyvalent metal ion (or a water-soluble cationic resin) and a dispersible cationic resin together in this way, the ink composition layer can be coated while suppressing bleeding of the colored ink more effectively. Film resistance (scratch resistance) can be improved.
 インク組成物にカチオン性の化合物を含有させる場合、カチ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、カチオン性の化合物の含有量の下限は、インク組成物全量中0.5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。カチオン性の化合物の含有量が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効果的に抑制することができる。カチオン性の化合物の含有量の上限は、インク組成物全量中9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。カチオン性の化合物の含有量がインク組成物全量中9質量%以下の範囲内であることで、インク組成物の保存安定性が向上する。 When the ink composition contains a cationic compound, the content of the cationic compound is not particularly limited. It is preferably in the range of 5% by mass or more, more preferably in the range of 0.8% by mass or more, and even more preferably in the range of 1.0% by mass or more. When the content of the cationic compound is within the range of 0.5% by mass or more based on the total amount of the ink composition, it becomes possible to fix the coloring material more effectively, and the bleeding of the colored ink is effectively suppressed. can do. The upper limit of the content of the cationic compound is preferably within the range of 9% by mass or less, more preferably within the range of 8% by mass or less, and within the range of 7% by mass or less in the total amount of the ink composition. is more preferable. When the content of the cationic compound is within the range of 9% by mass or less based on the total amount of the ink composition, the storage stability of the ink composition is improved.
 [その他の成分]
 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、防黴剤等が挙げられる。
[Other ingredients]
The ink composition may further contain conventionally known additives, if necessary. Examples of additives include waxes, viscosity modifiers, pH modifiers, antioxidants, preservatives, antifungal agents, and the like.
 <インク組成物の調製方法>
 インク組成物の調製方法は、特に限定されない。例えば、水溶性有機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、水溶性有機溶媒に、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有機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 ink composition>
A method for preparing the ink composition is not particularly limited. For example, a method of adding a self-dispersing pigment, a resin, a surfactant and, if necessary, other components to a water-soluble organic solvent for preparation, a method of adding a pigment and a dispersant to a water-soluble organic solvent, and then dispersing , A method of adding a resin, a surfactant and other ingredients if necessary. After adding the pigment, resin, surfactant and other ingredients if necessary to a water-soluble organic solvent, the pigment is dispersed. and the like.
 インク組成物の表面張力は、特に限定されないが、25℃における静的表面張力の上限は、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。25℃における静的表面張力の下限は、19.0mN/m以上が好ましく、20.0mN/m以上がより好ましく、21.0mN/m以上がさらに好ましい。なお、静的表面張力は、例えば測定温度25℃にてWilhelmy法(協和界面科学製 DY-300)で測定することができる。 The surface tension of the ink composition is not particularly limited, but the upper limit of the static surface tension at 25° C. is preferably 40.0 mN/m or less, more preferably 35.0 mN/m or less, and 32.0 mN/m or less. More preferred. The lower limit of the static surface tension at 25°C is preferably 19.0 mN/m or more, more preferably 20.0 mN/m or more, and even more preferably 21.0 mN/m or more. The static surface tension can be measured, for example, by the Wilhelmy method (DY-300 manufactured by Kyowa Interface Science) at a measurement temperature of 25°C.
 インク組成物の導電率は、特に限定されないが、2500μS/cm以下であることが好ましい。導電率が2500μS/cm以下となるようにインク組成物の成分を制御することで、成分同士の相互作用を抑制することが可能となり、安定性を向上させることが可能となる。 Although the conductivity of the ink composition is not particularly limited, it is preferably 2500 μS/cm or less. By controlling the components of the ink composition so that the electrical conductivity is 2500 μS/cm or less, it is possible to suppress the interaction between the components and improve the stability.
 インク組成物の導電率は、2450μS/cm以下であることが好ましく、2400μS/cm以下であることがより好ましい。なお、導電率は、例えば、Eutech Instruments製、EC Testr 11+で25℃にて測定することができる。 The conductivity of the ink composition is preferably 2450 μS/cm or less, more preferably 2400 μS/cm or less. The electrical conductivity can be measured at 25° C. with EC Testr 11+ manufactured by Eutech Instruments, for example.
 <インクセット>
 上記のインク組成物は、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。
<Ink set>
The above ink composition may be a colored ink, a metallic ink or the like, a receiving solution containing a cationic compound, or a clear ink containing no coloring material, and may be an overcoat ink. may be The ink set according to the present embodiment may be an ink set in which these ink compositions are combined.
 その中でも、例えば、インクセットに含まれる1のインク組成物は、色材を含有する着色インク組成物(C)であり、インクセットに含まれる他のインク組成物は、カチオン性の化合物を含む受理溶液(P)であるインクセットや、インクセットに含まれる1のインク組成物は、被体の表面にオーバーコート層を形成するオーバーコートインク(O)であり、インクセットに含まれる他のインク組成物は、カチオン性の化合物を含む受理溶液(P)であるインクセットや、インクセットに含まれる1のインク組成物は、色材を含有する着色インク組成物(C)であり、インクセットに含まれる他のインク組成物は、被体の表面にオーバーコート層を形成するオーバーコートインク(O)であるインクセットを挙げることができる。 Among them, for example, one ink composition contained in the ink set is a colored ink composition (C) containing a coloring material, and the other ink composition contained in the ink set contains a cationic compound. The ink set that is the receiving solution (P) and one ink composition contained in the ink set are the overcoat inks (O) that form an overcoat layer on the surface of the object, and the other ink compositions contained in the ink set. The ink composition is an ink set that is a receiving solution (P) containing a cationic compound, and one ink composition included in the ink set is a colored ink composition (C) that contains a coloring material, and the ink Other ink compositions included in the set include an ink set that is an overcoat ink (O) that forms an overcoat layer on the surface of a substrate.
 また、色材を含有する着色インク組成物(C)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、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。 Further, the ink set may be a combination of colored ink compositions (C) containing a coloring material. ink, red ink) or light colored ink compositions (for example, light magenta ink, light cyan ink, light black ink). Further, an ink set containing a white ink composition containing a white colorant, 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 colorant and 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, and black. . Furthermore, an ink set containing a metallic ink containing a glitter pigment, a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition, and a metallic ink containing a glitter pigment and a yellow ink composition A magenta ink composition, a cyan ink composition, a black ink composition, and intermediate color ink compositions or light color ink compositions of yellow, magenta, cyan, and black.
 そして、着色インク組成物(C)(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着色インク組成物や白色色材を含む白インク、光輝性顔料を含むメタリックインクを含む。)の導電率は、1000μS/cm以下であることが好ましい。色材を含有する着色インク組成物(C)は、色材を着色インク組成物(C)中で色材(顔料)を含有するため、導電率が高い場合には、色材(顔料)同士が凝集して安定性が低下する傾向がある。着色インク組成物(C)の導電率は、1000μS/cm以下となるように色材(顔料)を分散させる色材分散剤(顔料分散剤)やレベリング剤(界面活性剤)等の成分を含有させることで、成分同士(特に色材同士)の相互作用を抑制することが可能となり、安定性をさらに向上させることが可能となる。 and the colored ink composition (C) (yellow, magenta, cyan, black, and intermediate and light colored ink compositions thereof, white ink containing a white colorant, and metallic ink containing a bright pigment). The conductivity is preferably 1000 μS/cm or less. Since the coloring ink composition (C) containing the coloring material contains the coloring material (pigment) in the coloring ink composition (C), when the conductivity is high, the coloring material (pigment) tends to aggregate and become less stable. The colored ink composition (C) contains components such as a colorant dispersant (pigment dispersant) and a leveling agent (surfactant) that disperse the colorant (pigment) so that the conductivity is 1000 μS/cm or less. By doing so, it is possible to suppress the interaction between the components (especially between the coloring materials), and it is possible to further improve the stability.
 着色インク組成物(C)の導電率は、950μS/cm以下であることがより好ましく、900μS/cm以下であることがさらに好ましい。 The electrical conductivity of the colored ink composition (C) is more preferably 950 μS/cm or less, even more preferably 900 μS/cm or less.
 また、オーバーコートインク(O)の導電率は、1000μS/cm以下であることが好ましい。被体の表面にオーバーコート層を形成するオーバーコートインク(O)は、オーバーコート層を形成するための樹脂を含有するため、オーバーコートインク(O)中で樹脂同士が凝集して安定性が低下する傾向がある。オーバーコートインク(O)の導電率は、1000μS/cm以下となるように色材(顔料)を分散させるレベリング剤(界面活性剤)等の成分を含有させることで、成分同士(特に樹脂同士)の相互作用を抑制することが可能となり、安定性をさらに向上させることが可能となる。 Also, the electrical conductivity of the overcoat ink (O) is preferably 1000 μS/cm or less. The overcoat ink (O) that forms the overcoat layer on the surface of the object contains a resin for forming the overcoat layer. tend to decline. The electrical conductivity of the overcoat ink (O) is 1000 μS/cm or less. interaction can be suppressed, and the stability can be further improved.
 オーバーコートインク(O)の導電率は、950μS/cm以下であることがより好ましく、900μS/cm以下であることがさらに好ましい。 The conductivity of the overcoat ink (O) is more preferably 950 μS/cm or less, even more preferably 900 μS/cm or less.
 また、受理溶液(P)の導電率は、1000μS/cm以上2500μS/cm以下であることが好ましい。受理溶液(P)は、カチオン性の化合物を含むため、受理溶液(P)の導電率が、1000μS/cm以上2500μS/cm以下となるようにカチオン性の化合物を含むことで、受理溶液(P)の保存安定性を維持しつつ、受理溶液(P)の上に着弾される着色インク(C)やオーバーコートインク(O)との反応性を向上させることが可能となり、滲みやムラを抑制することが可能となる。 Also, the electrical conductivity of the receiving solution (P) is preferably 1000 μS/cm or more and 2500 μS/cm or less. Since the receiving solution (P) contains a cationic compound, the receiving solution (P ) while maintaining the storage stability of the receiving solution (P), it is possible to improve the reactivity with the colored ink (C) and the overcoat ink (O) that land on the receiving solution (P), suppressing bleeding and unevenness. It becomes possible to
 受理溶液(P)の導電率は、1050μS/cm以上であることがより好ましく、1100μS/cm以上であることがさらに好ましい。 The electrical conductivity of the receiving solution (P) is more preferably 1050 μS/cm or higher, more preferably 1100 μS/cm or higher.
 <記録方法>
 本実施の形態に係る記録方法は、上述した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方法である。
<Recording method>
The recording method according to the present embodiment is a recording method in which the ink composition described above is applied onto a substrate by an inkjet method.
 このインク組成物は、沸点が230℃以下のアミド系溶剤を含有しており、乾燥性が高いものであるので、本実施の形態に係る記録方法によりインクジェット法により基材上に塗布することにより、高速で記録することが可能となる。 Since this ink composition contains an amide-based solvent having a boiling point of 230° C. or less and is highly drying, it can be applied onto a substrate by an inkjet method according to the recording method according to the present embodiment. can be recorded at high speed.
 さらに、この沸点が230℃以下のアミド系溶剤の水/1-オクタノールでの分配係数(LogP)が-0.6以上である場合には、基材への溶剤浸透性が高くなり、特に吸収性基材や塩ビ基材(塩化ビニル系樹脂基材)での滲みが更に抑制され、鮮明な記録物を作製することが可能となる。 Furthermore, when the partition coefficient (LogP) of water/1-octanol of this amide solvent with a boiling point of 230° C. or less is −0.6 or more, the solvent permeability to the substrate is high, especially the absorption Bleeding on a flexible base material or a vinyl chloride base material (vinyl chloride resin base material) is further suppressed, making it possible to produce clear recorded matter.
 具体的には、本実施の形態に係る記録方法における記録速度における最高速度は、基材の種類やインクジェット記録装置の種類等にもよるが、シリアル方式の場合は7.5m/h以上であることが好ましく、10m/h以上であることがより好ましく、15m/h以上であることがさらに好ましい。シングルパス方式の場合は30m/min以上であることが好ましく、40m/min以上であることがより好ましく、50m/min以上であることがさらに好ましい。 Specifically, the maximum recording speed in the recording method according to the present embodiment is 7.5 m 2 /h or more in the case of the serial method, although it depends on the type of the base material, the type of the ink jet recording apparatus, and the like. It is preferably 10 m 2 /h or more, more preferably 15 m 2 /h or more. In the case of the single pass method, the speed is preferably 30 m/min or more, more preferably 40 m/min or more, and even more preferably 50 m/min or more.
 また、この沸点が230℃以下のアミド系溶剤の水/1-オクタノールでの分配係数(LogP)が-0.6以上である場合には、乾燥温度を比較的低温で記録しても、塗膜中に残留する有機溶剤による耐水摩擦性の低下を抑制することが可能となり、結果として耐水摩擦性の高い塗膜を形成することができる。 In addition, when the partition coefficient (LogP) of water/1-octanol of this amide solvent with a boiling point of 230°C or less is -0.6 or more, even if the drying temperature is recorded at a relatively low temperature, the coating It is possible to suppress deterioration of water rubbing resistance due to the organic solvent remaining in the film, and as a result, a coating film having high water rubbing resistance can be formed.
 具体的には、本実施の形態に係る記録方法における乾燥温度は、80℃以下、好ましくは、70℃以下さらに好ましくは60℃以下であってもよい。 Specifically, the drying temperature in the recording method according to the present embodiment may be 80°C or lower, preferably 70°C or lower, and more preferably 60°C or lower.
 <記録物の製造方法>
 上述した記録方法は、上述した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。
<Manufacturing Method of Recorded Matter>
The above-described recording method can also be defined as a method for producing a recorded matter in which the above-described ink composition is applied onto a substrate by an inkjet method.
 <記録物>
 上述した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、上記のインク組成物、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)やインク組成物の層について説明する。
<Records>
Each layer constituting the recorded matter manufactured by the method for manufacturing the recorded matter of the above-described embodiment will be described. Specifically, it is a recorded matter in which the above ink composition or the ink composition contained in the above ink set is applied onto a substrate. The medium (recording medium) and the ink composition layer constituting the recorded matter will be described below.
 [媒体(記録媒体)]
 本実施の形態に係る記録方法に使用することのできる基材(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。後述する実施の形態に係る記録物の製造方法に使用することのできる基材についても同様である。
[Medium (recording medium)]
The base material (recording medium) that can be used in the recording method according to the present embodiment is not particularly limited. Various substrates can be used, such as an absorbent substrate such as a woven fabric, or a surface-coated substrate such as a substrate having a receiving layer. The same applies to the base material that can be used in the method of manufacturing a recorded matter according to an embodiment described later.
 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。 Examples of non-absorbent substrates include resin substrates such as polyester resins, polypropylene synthetic paper, polypropylene resins, polyethylene resins, acrylic resins, styrene resins, polycarbonate resins, ABS resins, vinyl chloride resins, polyimide resins, Metal, metal foil coated paper, glass, synthetic rubber, natural rubber and the like can be mentioned.
 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 absorbent substrates include dry paper, medium-quality paper, high-quality paper, synthetic paper, cotton, synthetic fiber fabric, silk, hemp, fabric, non-woven fabric, leather, and the like.
 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 surface-coated substrates include coated paper, art paper, cast paper, lightweight coated paper, and lightly coated paper.
 [インク組成物の層]
 インク組成物の層とは、上述したインク組成物に含まれる溶媒が揮発することにより形成される層である。例えば、インク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。
[Ink composition layer]
The layer of the ink composition is a layer formed by volatilization of the solvent contained in the ink composition described above. For example, when a coloring material is contained in the ink, it becomes a decorative layer forming a desired image and its underlying layer.
 また、上述した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、基材上に上述したインク組成物(受理溶液)を塗布し、その上に上述したインク組成物(着色インク)を塗布してもよいし、基材上に上述したインク組成物(受理溶液)を塗布し、その上に上述したインク組成物(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-described ink composition is used as a receiving solution containing a cationic compound, the above-described ink composition (receiving solution) is applied onto a substrate, and the above-described ink composition (coloring ink) is applied thereon. ) may be applied, or the above-described ink composition (receiving solution) is applied on the substrate, and an ink composition (colored ink) different from the above-described ink composition (colored ink) is applied thereon. You may
 また、上述した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、上述したインク組成物であってもよいし、上述したインク組成物とは異なるインク組成物であってもよい。 Also, when the ink composition described above is used as an overcoat ink, it becomes an overcoat layer formed on the surface of a recorded matter. In this case, the ink composition that forms the recording layer of the recorded matter may be the ink composition described above, or may be an ink composition different from the ink composition described above.
 <インクジェット記録装置>
 本実施の形態に係るインクジェット記録装置は、上述したインク組成物、又は上述した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インクジェット記録装置である。上述したインク組成物は乾燥性が高いものであるので、上述したインク組成物、又は上述した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インクジェット記録装置により高速に記録物を製造することが可能となる。
<Inkjet recording device>
The inkjet recording apparatus according to the present embodiment is an inkjet recording apparatus equipped with a container filled with the ink composition described above or the ink composition contained in the ink set described above. Since the above-described ink composition has high drying properties, an inkjet recording apparatus equipped with a container filled with the above-described ink composition or the ink composition contained in the above-described ink set can be used to quickly print a printed matter. can be manufactured.
 なお、インクジェット記録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。 The storage container mounted on the inkjet recording apparatus is not particularly limited, and examples include containers such as ink bottles, pouches, bag-in-boxes, and drums. Also, 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 a conventionally known resin, or a material containing a part of metal material (for example, an aluminum pouch having an aluminum deposition layer). .
 またこの装置には、インク組成物の吐出後に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。これによりそれぞれの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。 In addition, it is preferable that this apparatus include a drying mechanism for drying the ink composition after the ink composition is ejected. This makes it possible to effectively remove volatile components contained in each ink composition.
 インク組成物の吐出後に該インクを乾燥する乾燥機構としては特に制限はされず、ヒーター等であってもよいし、熱風や常温の風を送風する機構であってもよい。 The drying mechanism for drying the ink after ejection of the ink composition is not particularly limited, and may be a heater or the like, or a mechanism for blowing hot air or normal temperature air.
 そのなかでも、インク組成物に含まれる樹脂のTgよりも低い温度で基材上に塗布されたインク組成物を乾燥することが好ましい。上記のインク組成物は乾燥性の高いものであるので、インク組成物に含まれる樹脂のTgよりも低い温度で乾燥させても十分に乾燥させることができる。 Among them, it is preferable to dry the ink composition applied on the substrate at a temperature lower than the Tg of the resin contained in the ink composition. Since the above ink composition is highly drying, it can be sufficiently dried even at a temperature lower than the Tg of the resin contained in the ink composition.
 また、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。 Also, the ejection method in each ejection part 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。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these descriptions.
 1.インク組成物の調製
 各材料を下記表に示す割合(単位は質量%)になるように混合し、室温(20~25℃)にて1時間撹拌した。その後、メンブレンフィルターを用いて濾過を行い、実施例及び比較例のインク組成物を調製した。
1. Preparation of Ink Composition Each material was mixed so that the ratio (unit: % by mass) shown in the table below was obtained, and the mixture was stirred at room temperature (20 to 25° C.) for 1 hour. Thereafter, filtration was performed using a membrane filter to prepare ink compositions of Examples and Comparative Examples.
 2.インク組成物の評価
 (乾燥性)
 実施例及び比較例のインク組成物について乾燥性を評価した。具体的には、インク組成物を塩化ビニル樹脂基材上にバーコーターで5g/m塗布した後、60℃オーブン内に入れ、乾燥するまでの時間を指触評価した。30秒毎に指触し、インク組成物が付着しなくなる時間を測定し、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、「乾燥性」と表記)。
 評価基準
 A:3分で乾燥した。
 B:3.5~4分で乾燥した。
 C:4.5~5分で乾燥した。
 D:5.5~6分で乾燥した。
 E:6分で乾燥しなかった(実用範囲外)。
2. Evaluation of ink composition (drying property)
Drying properties of the ink compositions of Examples and Comparative Examples were evaluated. Specifically, after applying 5 g/m 2 of the ink composition onto a vinyl chloride resin substrate with a bar coater, the ink composition was placed in an oven at 60° C. and the time until drying was evaluated by touch. The surface was touched with a finger every 30 seconds, and the time until the ink composition stopped adhering was measured, and evaluation was performed based on the following evaluation criteria. The evaluation results are shown in the table below (indicated as "drying property" in the table).
Evaluation Criteria A: Dried in 3 minutes.
B: Dried in 3.5 to 4 minutes.
C: Dried in 4.5 to 5 minutes.
D: Dried in 5.5 to 6 minutes.
E: Not dried in 6 minutes (out of practical range).
 (保存安定性)
 実施例及び比較例の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)。
 評価基準
 A:粘度変化率5%以下
 B:粘度変化率5%超10%未満
 C:粘度変化率10%以上20%未満
 D:粘度変化率20%以上(実用範囲外)
(Storage stability)
Storage stability was evaluated for the ink compositions of Examples and Comparative Examples. 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 (indicated as "storage stability" in the table).
Evaluation Criteria A: Viscosity change rate of 5% or less B: Viscosity change rate of more than 5% and less than 10% C: Viscosity change rate of 10% or more and less than 20% D: Viscosity change rate of 20% or more (outside practical range)
 (濃度ムラ)
 実施例及び比較例のインク組成物により得られた記録物について濃度ムラを評価した。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)をシリアルヘッド方式のインクジェット記録装置に搭載し、そのインクジェット記録装置により、解像度600×600dpi、液滴サイズ6pl、印字濃度100%のベタ画像を塩化ビニル樹脂基材上に印刷し、濃度ムラの有無を目視で観察し、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、「濃度ムラ」と表記)。
 評価基準
 A:濃度ムラ無し
 B:濃度ムラ有り
 C:インクの濡れが悪く画像形成できず(実用範囲外)
(Density unevenness)
Density unevenness was evaluated for recorded matter obtained with the ink compositions of Examples and Comparative Examples. Specifically, the ink composition is filled in an ink cartridge (container), and the ink cartridge (container) is mounted on a serial head type inkjet recording apparatus. A solid image with a droplet size of 6 pl and a printing density of 100% was printed on a vinyl chloride resin substrate, and the presence or absence of density unevenness was visually observed, and evaluation was made based on the following evaluation criteria. The evaluation results are shown in the table below (denoted as "density unevenness" in the table).
Evaluation Criteria A: No density unevenness B: Density unevenness C: Image formation not possible due to poor ink wetting (outside practical range)
(滲み)
 実施例及び比較例のインク組成物により得られた記録物について滲みを評価した。具体的には、インク組成物をインクカートリッジに充填し、そのインクカートリッジをシリアルヘッド方式のインクジェット記録装置に搭載し、そのインクジェット記録装置により、解像度600×600dpi、液滴サイズ6plで白抜き文字入りのベタ画像を基材に印刷し、白抜き文字の鮮明さにより滲みを目視で観察し、以下の評価基準に基づき評価を行った。基材はコート紙、塩ビ基材(塩化ビニル系樹脂基材)、PETフィルム基材でそれぞれ評価を行い、評価結果を下記表に記載した(表中、「滲み」と表記)。
 評価基準
 A:4ptサイズまでが鮮明
 B:6ptサイズまでが鮮明
 C:8ptサイズまでが鮮明
 D:10ptサイズまでが鮮明
 E:10ptサイズが不鮮明(実用範囲外)
(blur)
Bleeding was evaluated for the recorded matter obtained with the ink compositions of Examples and Comparative Examples. Specifically, the ink composition is filled in an ink cartridge, and the ink cartridge is mounted on a serial head type inkjet recording apparatus. A solid image was printed on the base material, and blurring was visually observed based on the clarity of the white characters, and evaluation was made based on the following evaluation criteria. The base material used was coated paper, a vinyl chloride base material (vinyl chloride resin base material), and a PET film base material.
Evaluation Criteria A: Clear up to 4pt size B: Clear up to 6pt size C: Clear up to 8pt size D: Clear up to 10pt size E: Unclear up to 10pt size (outside practical range)
 (撥液性)
 実施例及び比較例のインク組成物について撥液性を評価した。具体的には、インクジェット記録装置における600dpiのプリンターヘッドのノズルプレートをインク組成物に浸漬させ、液面から取出した後のプレートに対するインク組成物の露出面積を30秒毎に目視で観察し、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、「撥液性」と表記)。
 評価基準
 A:30秒後のプレートの露出面積が80%以上
 B:1分後のプレートの露出面積が80%以上
 C:1分後でもプレートの露出面積が80%未満(実用範囲外)
(liquid repellency)
Liquid repellency was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, the nozzle plate of a 600 dpi printer head in an inkjet recording apparatus is immersed in the ink composition, and the exposed area of the ink composition on the plate after being removed from the liquid surface is visually observed every 30 seconds. was evaluated based on the evaluation criteria of The evaluation results are shown in the table below (indicated as "liquid repellency" in the table).
Evaluation criteria A: The exposed area of the plate after 30 seconds is 80% or more B: The exposed area of the plate after 1 minute is 80% or more C: The exposed area of the plate is less than 80% even after 1 minute (outside the 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)をシリアルヘッド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、一定時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、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)。
 評価基準
 A:15分静置後にノズル欠け10%以下
 B:10分静置後にノズル欠け10%以下
 C:5分静置後にノズル欠け10%以下
 D:5分静置後にノズル欠け10%超(実用範囲外)
(intermittent discharge)
The intermittent discharge properties of the ink compositions of Examples and Comparative Examples were evaluated. Specifically, the ink composition is filled in an ink cartridge (container), the ink cartridge (container) is mounted in a serial head type inkjet recording apparatus, and a nozzle check pattern is printed by the inkjet recording apparatus. Then, after standing still for a certain period of time, the same printing was performed. The presence or absence of nozzle chipping was checked before and after standing, and evaluation was performed based on the following evaluation criteria. The evaluation results are shown in the table below (indicated as "intermittent discharge property" in the table).
Evaluation Criteria A: 10% or less nozzle missing after standing for 15 minutes B: 10% or less nozzle missing after standing for 10 minutes C: 10% or less nozzle missing after standing for 5 minutes D: more than 10% nozzle missing after standing for 5 minutes (out of practical range)
 (耐擦過性)
 実施例及び比較例のインク組成物について耐擦過性を評価した。具体的には、上記乾燥性評価と同様の方法で60℃で6分乾燥した塗膜を作製し、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、加重500g、当布:金巾3号の条件で塗膜の外観を観察した。評価結果を下記表に記載した(表中、「耐擦過性」と表記)。
 評価基準
 A:100回後に外観変化無し
 B:50回後に外観変化無し・100回後にやや外観変化有り
 C:25回後に外観変化無し・50回後にやや外観変化有り
 D:10回後に外観変化無し・25回後にやや外観変化有り
 E:10回後に外観変化有り(実用範囲外)
(Scratch resistance)
The scratch resistance was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, a coating film was dried at 60° C. for 6 minutes in the same manner as in the above dryness evaluation, and the coating film on the coated surface of the ink composition was subjected to a Gakushin type rubbing fastness tester type II, The appearance of the coating film was observed under the conditions of a weight of 500 g and a cloth of Kanawa No. 3. The evaluation results are shown in the table below (indicated as "scratch resistance" in the table).
Evaluation Criteria A: No change in appearance after 100 times B: No change in appearance after 50 times/Slight change in appearance after 100 times C: No change in appearance after 25 times/Slight change in appearance after 50 times D: No change in appearance after 10 times・There is a slight change in appearance after 25 times E: There is a change in appearance after 10 times (out of practical range)
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
 上記表から分かるように、沸点が230℃以下のアミド系溶剤を含有する実施例のインク組成物であれば、乾燥性に優れることが分かる。 As can be seen from the above table, the ink compositions of Examples containing an amide-based solvent having a boiling point of 230°C or lower are excellent in drying properties.
 この中でも、沸点が230℃以下のアミド系溶剤の種類を変更した実施例1~11のインク組成物において、水/1-オクタノールでの分配係数(LogP)が-0.6以上の沸点が230℃以下のアミド系溶剤を含有する実施例1、3~5、9、10のインク組成物は、実施例2、6~8、11のインク組成物と比較しても特にコート紙、及び塩ビ基材(塩化ビニル系樹脂基材)における「滲み評価」はさらに良好なものであった。 Among them, in the ink compositions of Examples 1 to 11 in which the type of amide solvent having a boiling point of 230° C. or less was changed, the partition coefficient (LogP) in water/1-octanol was −0.6 or more and the boiling point was 230° C. The ink compositions of Examples 1, 3 to 5, 9, and 10 containing amide-based solvents at temperatures below The "bleeding evaluation" of the base material (vinyl chloride resin base material) was even better.
 また、沸点が230℃以下のアミド系溶剤の種類を変更した実施例1~11のインク組成物において、沸点が220℃以下のアミド系溶剤を含有する実施例1~4、6、7、9、11のインク組成物は、実施例5、8、10のインク組成物と比較しても「乾燥性」評価はさらに良好なものであった。 Further, in the ink compositions of Examples 1 to 11 in which the type of amide solvent having a boiling point of 230°C or lower was changed, Examples 1 to 4, 6, 7, and 9 containing an amide solvent having a boiling point of 220°C or lower , and 11, even when compared with the ink compositions of Examples 5, 8, and 10, the "drying property" evaluation was even better.
また、レベリング剤を含まない実施例17のインク組成物と比較してレベリング剤を含む実施例12、16、18~23のインク組成物は得られる記録物の「乾燥性」及び「滲み」評価において良好なものであった。また、レベリング剤のHLB値を変更させた実施例12、16、18、19のインク組成物において、HLB値が15以下であるレベリング剤を含有する実施例12、16のインク組成物は、実施例18、19のインク組成物と比較しても「乾燥性」「滲み」評価はさらに良好なものであった。 In addition, compared with the ink composition of Example 17 containing no leveling agent, the ink compositions of Examples 12, 16, and 18 to 23 containing a leveling agent evaluated the "drying property" and "bleeding" of the obtained recorded matter. was good in Further, in the ink compositions of Examples 12, 16, 18, and 19 in which the HLB value of the leveling agent was changed, the ink compositions of Examples 12 and 16 containing a leveling agent having an HLB value of 15 or less were Even when compared with the ink compositions of Examples 18 and 19, the "drying property" and "bleeding" evaluations were even better.
 また、樹脂を含まない実施例24のインク組成物と比較して樹脂を含む実施例12、25、26のインク組成物は「耐擦過性」は良好なものであった。このなかでもTgが50℃以上の樹脂を含む実施例12、25のインク組成物は、実施例26のインク組成物と比較しても「耐擦過性」評価はさらに良好なものであった。 In addition, the ink compositions of Examples 12, 25, and 26 containing a resin had better "scratch resistance" than the ink composition of Example 24 containing no resin. Among them, the ink compositions of Examples 12 and 25 containing a resin having a Tg of 50° C. or more were even more favorable in the evaluation of "scratch resistance" than the ink composition of Example 26.
 また、カチオン性の化合物を含有する実施例27、28のインク組成物(受理溶液)において、導電率が、1000μS/cm以上2500μS/cm以下の範囲にある実施例27のインク組成物(受理溶液)は、実施例28のインク組成物(受理溶液)と比較しても「保存安定性」評価はさらに良好なものであった。 Further, in the ink compositions (receiving solutions) of Examples 27 and 28 containing cationic compounds, the ink compositions (receiving solutions) of ) had even better "storage stability" evaluations when compared to the ink composition of Example 28 (accepting solution).
 また、沸点が230℃以下のアミド系溶剤の含有量を変更した実施例1、12、32~35のインク組成物において、沸点が230℃以下のアミド系溶剤の含有量が6質量%以上の範囲である実施例1、12、33~35のインク組成物は、実施例32のインク組成物と比較しても「乾燥性」評価はさらに良好なものであった。また、沸点が230℃以下のアミド系溶剤の含有量が35質量%以下の範囲である実施例1、12、32、34のインク組成物は、実施例35のインク組成物と比較しても「保存安定性」評価はさらに良好なものであった。 Further, in the ink compositions of Examples 1, 12, and 32 to 35 in which the content of the amide solvent with a boiling point of 230°C or lower was changed, the content of the amide solvent with a boiling point of 230°C or lower was 6% by mass or more. The ink compositions of Examples 1, 12, and 33 to 35, which are in the range, were even better in the "drying property" evaluation than the ink composition of Example 32. In addition, the ink compositions of Examples 1, 12, 32, and 34, in which the content of the amide-based solvent having a boiling point of 230° C. or less was in the range of 35% by mass or less, were compared with the ink composition of Example 35. The "storage stability" rating was even better.
 また、沸点が230℃以下のアミド系溶剤として、N,N-ジエチルホルムアミドを含有し、さらに1,3-プロパンジオールを含有する実施例12,16,29の「1,3-プロパンジオール」を1,2-アルカンジオール系溶剤である「プロピレングリコール」に変更した実施例46、47、49は、PETフィルムに対する「滲み」評価はさらに良好なものであった。 Further, the "1,3-propanediol" of Examples 12, 16, and 29 containing N,N-diethylformamide as an amide-based solvent having a boiling point of 230°C or less and further containing 1,3-propanediol. In Examples 46, 47, and 49 in which the 1,2-alkanediol solvent "propylene glycol" was changed, the "bleeding" evaluation for the PET film was even better.
 また、カチオン性の化合物として、分散性のカチオン性の樹脂を含有する実施例48のインク組成物(受理溶液)は、実施例27、28のインク組成物(受理溶液)と比較しても「耐擦過性」評価はさらに良好なものであった。 Further, the ink composition (receiving solution) of Example 48 containing a dispersible cationic resin as a cationic compound was " The "scratch resistance" evaluation was even better.
 一方、沸点が230℃以下のアミド系溶剤を含有しない比較例のインク組成物は、本発明の効果を奏するものとなっていない。 On the other hand, the ink composition of the comparative example, which does not contain an amide-based solvent having a boiling point of 230°C or less, does not exhibit the effects of the present invention.
 3.インクセットの評価
 上記のインク組成物を組み合わせたインクセットについて評価を行った。
3. Evaluation of Ink Set An ink set in which the ink compositions described above were combined was evaluated.
 (乾燥性)
 上記のインク組成物を組み合わせたインクセットについて乾燥性を評価した。具体的には、シリアルヘッド方式のインクジェット印刷装置を使用して、基材として塩化ビニル樹脂又は透明塩化ビニル樹脂の表面に受理溶液と、白インクと、シアンインクと、オーバーコートインクと、をこの順に吐出して、解像度600×600dpi、液滴サイズ6pl、印字濃度100%のベタ画像の印刷物を製造した。印刷直後の印刷物を60℃オーブン内に入れ、乾燥するまでの時間を指触評価した。30秒毎に指触し、インク組成物が付着しなくなる時間を測定し、以下の評価基準に基づき評価を行った。
 評価基準
 A:3分で乾燥した。
 B:3.5~4分で乾燥した。
 C:4.5~5分で乾燥した。
 D:5.5~6分で乾燥した。
 E:6分で乾燥しなかった(実用範囲外)。
(dryness)
An ink set in which the above ink compositions were combined was evaluated for drying properties. Specifically, a receiving solution, a white ink, a cyan ink, and an overcoat ink are applied to the surface of a vinyl chloride resin or a transparent vinyl chloride resin as a substrate using a serial head type inkjet printer. By discharging in order, a solid image print having a resolution of 600×600 dpi, a droplet size of 6 pl, and a print density of 100% was produced. Immediately after printing, the printed matter was placed in an oven at 60° C., and the time until drying was evaluated by touch. The surface was touched with a finger every 30 seconds, and the time until the ink composition stopped adhering was measured, and evaluation was performed based on the following evaluation criteria.
Evaluation Criteria A: Dried in 3 minutes.
B: Dried in 3.5 to 4 minutes.
C: Dried in 4.5 to 5 minutes.
D: Dried in 5.5 to 6 minutes.
E: Not dried in 6 minutes (out of practical range).
 (滲み)
 上記のインク組成物を組み合わせたインクセットについて滲みを評価した。具体的には、シリアルヘッド方式のインクジェット印刷装置を使用して、基材としてコート紙、塩ビ基材(塩化ビニル系樹脂基材)、PETフィルム基材それぞれの表面に受理溶液と、白インクと、シアンインクと、オーバーコートインクと、をこの順に吐出して、解像度600×600dpi、液滴サイズ6pl、シアンインク以外のインクは印字濃度100%のベタ画像、シアンインクは4~8ポイントの文字画像の印刷物を製造し、印字の滲みを目視で評価し、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、「滲み」と表記)。
 評価基準
 A:4ptサイズまでが鮮明
 B:6ptサイズまでが鮮明
 C:8ptサイズまでが鮮明
 D:10ptサイズまでが鮮明
 E:10ptサイズが不鮮明(実用範囲外)
(blur)
Bleeding was evaluated for an ink set in which the above ink compositions were combined. Specifically, using a serial head type inkjet printer, a receiving solution and white ink were applied to the surfaces of coated paper, vinyl chloride (vinyl chloride resin), and PET film substrates. , cyan ink and overcoat ink are ejected in this order to form a solid image with a resolution of 600 x 600 dpi, a droplet size of 6 pl, a printing density of 100% for inks other than cyan ink, and 4 to 8 point characters for cyan ink. A printed matter of the image was produced, and the blurring of the printing was visually evaluated, and the evaluation was performed based on the following evaluation criteria. The evaluation results are shown in the table below (indicated as "bleeding" in the table).
Evaluation Criteria A: Clear up to 4pt size B: Clear up to 6pt size C: Clear up to 8pt size D: Clear up to 10pt size E: Unclear up to 10pt size (outside practical range)
 (耐擦過性)
 上記のインク組成物を組み合わせたインクセットについて耐擦過性を評価した。具体的には、上記のインクセットにおける乾燥性と同様に印字濃度100%のベタ画像の印刷物を製造し、60℃オーブンで6分乾燥した塗膜に対して学振型摩擦堅牢度試験機II型、加重500g、当布:金巾3号の条件で塗膜の外観を観察した。評価結果を下記表に記載した(表中、「耐水摩擦性」と表記)。
 A:100回後に外観変化無し
 B:50回後に外観変化無し・100回後にやや外観変化有り
 C:25回後に外観変化無し・50回後にやや外観変化有り
 D:10回後に外観変化無し・25回後にやや外観変化有り
 E:10回後に外観変化有り(実用範囲外)
(Scratch resistance)
An ink set in which the above ink compositions were combined was evaluated for scratch resistance. Specifically, a solid image print with a print density of 100% was produced in the same manner as the drying property of the ink set described above, and the coating film was dried in an oven at 60 ° C. for 6 minutes. The appearance of the coating film was observed under the conditions of a mold, a weight of 500 g, and a cloth of Kanawa No. 3. The evaluation results are shown in the table below (indicated as "water rubbing resistance" in the table).
A: No change in appearance after 100 times B: No change in appearance after 50 times Slight change in appearance after 100 times C: No change in appearance after 25 times Slight change in appearance after 50 times D: No change in appearance after 10 times 25 Slight change in appearance after 10 cycles E: Change in appearance after 10 cycles (outside practical range)
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
 上記表から分かるように、沸点が230℃以下のアミド系溶剤を含有するインク組成物のインクセットであれば、乾燥性に優れることが分かる。 As can be seen from the above table, an ink set containing an amide-based solvent with a boiling point of 230° C. or less has excellent drying properties.
 また、導電率が、1000μS/cm以上2500μS/cm以下の範囲にある実施例27のインク組成物(受理溶液)と、導電率が1000μS/cm以下の範囲にある実施例12のインク組成物と、を含む実施例37のインクセットは、実施例45のインクセットと比較しても、「滲み」評価は良好なものであった。 Further, the ink composition (receiving solution) of Example 27 having a conductivity of 1000 μS/cm or more and 2500 μS/cm or less and the ink composition of Example 12 having a conductivity of 1000 μS/cm or less. The ink set of Example 37 containing .
 また、沸点が230℃以下であるアミド系溶剤を含有する実施例30のインク組成物(オーバーコートインク)と、沸点が230℃以下であるアミド系溶剤を含有しない比較例5のインク組成物と、を含む実施例43のインクセットや、実施例43のインクセットにさらに沸点が230℃以下であるアミド系溶剤を含有する実施例27のインク組成物と、を含む実施例44のインクセットであっても比較例8のインクセットと比較して、「乾燥性」評価が優れていた。これにより、インクセットに含まれる少なくとも1つのインク組成物に沸点が230℃以下であるアミド系溶剤を含有し、インクセットに含まれる少なくとも他のインク組成物に沸点が230℃以下であるアミド系溶剤を含有していなくとも、本発明の効果を奏することが確認された。 Further, the ink composition (overcoat ink) of Example 30 containing an amide solvent having a boiling point of 230° C. or lower and the ink composition of Comparative Example 5 containing no amide solvent having a boiling point of 230° C. or lower. and the ink set of Example 44 containing the ink composition of Example 27, which further contains an amide-based solvent having a boiling point of 230° C. or less in the ink set of Example 43. Even if there was, compared with the ink set of Comparative Example 8, the "drying property" evaluation was excellent. Accordingly, at least one ink composition contained in the ink set contains an amide solvent having a boiling point of 230° C. or less, and at least other ink composition contained in the ink set contains an amide solvent having a boiling point of 230° C. or less. It was confirmed that the effect of the present invention can be obtained even if the solvent is not contained.
 また、実施例46、47のインク組成物を含む実施例50、51、54,55のインクセットにおいて、実施例51,55のインクセットは、実施例50,54のインクセットと比較しても「耐擦過性」が良好となっている。そして、実施例51,55のインクセットは、シリコーン(シリコン)系界面活性剤を含む実験例47のインク組成物を含むものである。このことから、シリコーン(シリコン)系界面活性剤を含有するインク組成物を含むインクセットであれば、耐擦過性の高い塗膜を形成できることが確認された。 Further, in the ink sets of Examples 50, 51, 54, and 55 containing the ink compositions of Examples 46 and 47, the ink sets of Examples 51 and 55 were compared with the ink sets of Examples 50 and 54. "Scratch resistance" is good. The ink sets of Examples 51 and 55 contain the ink composition of Experimental Example 47 containing a silicone surfactant. From this, it was confirmed that an ink set containing an ink composition containing a silicone (silicon)-based surfactant can form a coating film with high scratch resistance.
 また、カチオン性の化合物として、分散性のカチオン性の樹脂を含有する実施例48のインク組成物(受理溶液)を含む実施例52、53、56、57のインクセットは、実施例27のインク組成物(受理溶液)を含む実施例50、54のインクセットと比較しても「耐擦過性」評価はさらに良好なものであった。 Further, the ink sets of Examples 52, 53, 56, and 57 containing the ink composition (receiving solution) of Example 48 containing a dispersible cationic resin as a cationic compound were the inks of Example 27. Even when compared to the ink sets of Examples 50 and 54 containing the composition (receiving solution), the "scratch resistance" rating was even better.

Claims (22)

  1.  インクジェット用のインク組成物であって、
     水溶性有機溶剤を含有し、
     前記水溶性有機溶剤は、沸点が230℃以下のアミド系溶剤を含有する
     インク組成物。
    An ink composition for inkjet,
    containing a water-soluble organic solvent,
    The ink composition, wherein the water-soluble organic solvent contains an amide-based solvent having a boiling point of 230° C. or lower.
  2.  前記アミド系溶剤は、以下式(1)のアルキルアミド系構造を有する
     請求項1に記載のインク組成物。
    Figure JPOXMLDOC01-appb-C000001
    (式(1)中、Rは水素、若しくは炭素数1~4のアルキル基であり、R,Rは官能基である。)
    The ink composition according to claim 1, wherein the amide-based solvent has an alkylamide-based structure represented by formula (1) below.
    Figure JPOXMLDOC01-appb-C000001
    (In formula (1), R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 are functional groups.)
  3.  前記アミド系溶剤は、N-エチル-N-メチルホルムアミド、N-メチル-N-プロピルホルムアミド、N,N-ジエチルホルムアミド、N-エチル-N-プロピルホルムアミド、N,N-ジメチルアセトアミド、N-エチル-N-メチルアセトアミド、N-メチル-N-プロピルアセトアミド、N,N-ジエチルアセトアミド、N,N-ジメチルプロパンアミド、及びN-エチル-N-メチルプロパンアミドからなる群より選択される
     請求項1又は2に記載のインク組成物。
    The amide solvent includes N-ethyl-N-methylformamide, N-methyl-N-propylformamide, N,N-diethylformamide, N-ethyl-N-propylformamide, N,N-dimethylacetamide, N-ethyl -N-methylacetamide, N-methyl-N-propylacetamide, N,N-diethylacetamide, N,N-dimethylpropanamide, and N-ethyl-N-methylpropanamide. 3. or the ink composition according to 2.
  4.  さらに、アルカンジオール系溶剤を含む
     請求項1から3のいずれかに記載のインク組成物。
    4. The ink composition according to any one of Claims 1 to 3, further comprising an alkanediol solvent.
  5.  前記アルカンジオール系溶剤は沸点が230℃以下のアルカンジオール系溶剤を含有する
     請求項4に記載のインク組成物。
    The ink composition according to claim 4, wherein the alkanediol-based solvent contains an alkanediol-based solvent having a boiling point of 230°C or less.
  6.  前記アミド系溶剤は、少なくとも2種以上のアミド系溶剤を含有する
     請求項1から4のいずれかに記載のインク組成物。
    The ink composition according to any one of claims 1 to 4, wherein the amide solvent contains at least two or more amide solvents.
  7.  前記アミド系溶剤は、沸点が200℃以下のアミド系溶剤を少なくとも1種含有する
     請求項6に記載のインク組成物。
    The ink composition according to claim 6, wherein the amide solvent contains at least one amide solvent having a boiling point of 200°C or less.
  8.  さらに、環状エステル系溶剤、及びグリコールエーテル系溶剤からなる群より選択される少なくとも1以上の有機溶剤Bを含む
     請求項1から7のいずれかに記載のインク組成物。
    8. The ink composition according to any one of claims 1 to 7, further comprising at least one organic solvent B selected from the group consisting of cyclic ester solvents and glycol ether solvents.
  9.  前記有機溶剤Bは、沸点は230℃以下の有機溶剤Bを含有する
     請求項8に記載のインク組成物。
    The ink composition according to claim 8, wherein the organic solvent B has a boiling point of 230°C or less.
  10.  さらにレベリング剤を含有し、
     前記レベリング剤の含有量は、前記インク組成物に含まれる前記アミド系溶剤100質量部に対して0.1質量部以上50質量部以下の範囲である
     請求項1から9のいずれかに記載のインク組成物。
    Furthermore, it contains a leveling agent,
    The content of the leveling agent is in the range of 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the amide solvent contained in the ink composition. ink composition.
  11.  さらに樹脂を含有し、
     前記樹脂の少なくとも一部を分散性樹脂として含有する、
     請求項1から10のいずれかに記載のインク組成物。
    Furthermore, it contains a resin,
    containing at least part of the resin as a dispersible resin;
    The ink composition according to any one of claims 1 to 10.
  12.  前記分散性樹脂のTgは、インク組成物の乾燥温度よりも高い
     請求項11に記載のインク組成物。
    The ink composition according to claim 11, wherein the Tg of the dispersible resin is higher than the drying temperature of the ink composition.
  13.  前記分散性樹脂のTgは、50℃以上である
     請求項11又は12に記載のインク組成物。
    The ink composition according to claim 11 or 12, wherein the dispersible resin has a Tg of 50°C or higher.
  14.  前記分散性樹脂は、アクリル系樹脂、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
     請求項11から13のいずれかに記載のインク組成物。
    The dispersible resins include acrylic resins, polyurethane resins, polyester resins, vinyl chloride resins, vinyl acetate resins, polyether resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, acrylamide resins, epoxy resins. 14. The ink composition according to any one of Claims 11 to 13, comprising one or more resins or copolymer resins selected from the group consisting of polystyrene-based resins, polycarbonate-based resins, silicone-based resins, and polystyrene-based resins.
  15.  前記分散性樹脂は、少なくともアクリル系樹脂、又はアクリル系共重合樹脂を含む
     請求項14に記載のインク組成物。
    15. The ink composition according to claim 14, wherein the dispersible resin contains at least an acrylic resin or an acrylic copolymer resin.
  16.  導電率が2500μS/cm以下である
     請求項1から15のいずれかに記載のインク組成物。
    16. The ink composition according to any one of claims 1 to 15, which has a conductivity of 2500 [mu]S/cm or less.
  17.  請求項1から16のいずれかに記載のインク組成物を含む
     インクセット。
    An ink set comprising the ink composition according to claim 1 .
  18.  請求項1から16のいずれかに記載のインク組成物、又は請求項17に記載のインクセットに含まれるインク組成物が基材上に塗布された
     記録物。
    18. A recorded matter, wherein the ink composition according to any one of claims 1 to 16 or the ink composition contained in the ink set according to claim 17 is applied onto a substrate.
  19.  請求項1から16のいずれかに記載のインク組成物、又は請求項17に記載のインクセットに含まれる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
     記録方法。
    A recording method comprising applying the ink composition according to any one of claims 1 to 16 or the ink composition contained in the ink set according to claim 17 onto a substrate by an inkjet method.
  20.  請求項11から15のいずれかに記載のインク組成物をインクジェット法により基材上に塗布し、その後、該インク組成物に含まれる樹脂のTgよりも低い温度で基材上に塗布されたインク組成物を乾燥する
     記録方法。
    The ink composition according to any one of claims 11 to 15 is applied onto a substrate by an inkjet method, and then the ink is applied onto the substrate at a temperature lower than the Tg of the resin contained in the ink composition. A recording method for drying the composition.
  21.  請求項1から16のいずれかに記載のインク組成物、又は請求項17に記載のインクセットに含まれる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。
    18. A method for producing recorded matter, comprising applying the ink composition according to any one of claims 1 to 16 or the ink composition contained in the ink set according to claim 17 onto a substrate by an inkjet method.
  22.  請求項1から16のいずれかに記載のインク組成物、又は請求項17に記載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
     インクジェット記録装置。
    An inkjet recording apparatus equipped with a container filled with the ink composition according to any one of claims 1 to 16 or the ink composition contained in the ink set according to claim 17.
PCT/JP2023/006538 2022-02-22 2023-02-22 Ink composition, ink set, recorded product having ink composition applied on base material, recording method, manufacturing method for recorded product, and inkjet recording device equipped with accommodation container filled with ink composition WO2023163063A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-026124 2022-02-22
JP2022026124 2022-02-22

Publications (1)

Publication Number Publication Date
WO2023163063A1 true WO2023163063A1 (en) 2023-08-31

Family

ID=87766036

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/006538 WO2023163063A1 (en) 2022-02-22 2023-02-22 Ink composition, ink set, recorded product having ink composition applied on base material, recording method, manufacturing method for recorded product, and inkjet recording device equipped with accommodation container filled with ink composition

Country Status (1)

Country Link
WO (1) WO2023163063A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015672A (en) * 2003-06-27 2005-01-20 Toyo Ink Mfg Co Ltd Nonaqueous inkjet ink for polyvinyl chloride resin sheet
JP2006045450A (en) * 2004-08-09 2006-02-16 Konica Minolta Holdings Inc Inkjet ink and method for inkjet recording
JP2008216866A (en) * 2007-03-07 2008-09-18 Seiko Epson Corp Composition for forming liquid crystal alignment layer and method for manufacturing liquid crystal display device
JP2012224658A (en) * 2011-04-15 2012-11-15 Konica Minolta Ij Technologies Inc Inkjet ink and inkjet recording method
JP2013091711A (en) * 2011-10-25 2013-05-16 Konica Minolta Ij Technologies Inc Functional inkjet ink and method for forming functional coating film
JP2014185207A (en) * 2013-03-22 2014-10-02 Seiko Epson Corp Nonaqueous ink composition for inkjet recording and inkjet recording method
WO2021201149A1 (en) * 2020-03-31 2021-10-07 株式会社Dnpファインケミカル Non-aqueous ink composition, inkjet recording method, and method for manufacturing printed matter
JP2021187095A (en) * 2020-06-02 2021-12-13 セイコーエプソン株式会社 White ink composition and recording method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015672A (en) * 2003-06-27 2005-01-20 Toyo Ink Mfg Co Ltd Nonaqueous inkjet ink for polyvinyl chloride resin sheet
JP2006045450A (en) * 2004-08-09 2006-02-16 Konica Minolta Holdings Inc Inkjet ink and method for inkjet recording
JP2008216866A (en) * 2007-03-07 2008-09-18 Seiko Epson Corp Composition for forming liquid crystal alignment layer and method for manufacturing liquid crystal display device
JP2012224658A (en) * 2011-04-15 2012-11-15 Konica Minolta Ij Technologies Inc Inkjet ink and inkjet recording method
JP2013091711A (en) * 2011-10-25 2013-05-16 Konica Minolta Ij Technologies Inc Functional inkjet ink and method for forming functional coating film
JP2014185207A (en) * 2013-03-22 2014-10-02 Seiko Epson Corp Nonaqueous ink composition for inkjet recording and inkjet recording method
WO2021201149A1 (en) * 2020-03-31 2021-10-07 株式会社Dnpファインケミカル Non-aqueous ink composition, inkjet recording method, and method for manufacturing printed matter
JP2021187095A (en) * 2020-06-02 2021-12-13 セイコーエプソン株式会社 White ink composition and recording method

Similar Documents

Publication Publication Date Title
EP3382093B1 (en) Pretreatment liquid, ink set, and recording method
JP7156430B2 (en) Reaction liquid, inkjet recording method, and setting of ink and reaction liquid
JP7110512B1 (en) ink set
WO2014058029A2 (en) Aqueous inkjet acceptor solution, ink set including acceptor solution, and inkjet recording method using ink set
JP2012184376A (en) Inkjet ink and inkjet recording method
JP2019064159A (en) Image forming method and inkjet recording apparatus
US20200040207A1 (en) Receptive solution, ink set containing said receptive solution and method for producing printed material using ink set
JP7169481B1 (en) Aqueous ink and ink set containing the same
WO2023163063A1 (en) Ink composition, ink set, recorded product having ink composition applied on base material, recording method, manufacturing method for recorded product, and inkjet recording device equipped with accommodation container filled with ink composition
WO2023163065A1 (en) Ink composition, ink set, recorded matter having ink composition applied on base material, recording method, recorded matter manufacturing method, and inkjet recording device equipped with housing container filled with ink composition
WO2023163064A1 (en) Ink composition, ink set, recorded matter in which ink composition is applied to base material, recording method, method for producing recorded matter, and inkjet recording device equipped with storage container filled with ink composition
JP2023133065A (en) Non-aqueous ink composition, ink set, recording method using the same, method for producing recorded matter, recorded matter and inkjet recording device
WO2023163062A1 (en) Ink set, record obtained by applying ink compositions included in ink set to substrate, recording method, method for producing record, and ink-jet recording device including mounted container filled with ink compositions
JP2023133066A (en) Non-aqueous ink composition, ink set, recording method using the same, method for producing recorded matter, recorded matter and inkjet recording device
JP7256954B2 (en) DISPERSION, INK COMPOSITION FOR INKJET RECORDING, AND INKJET RECORDING METHOD
JP5755207B2 (en) Ink jet receiving solution, ink set containing the receiving solution, and ink jet recording method using the ink set
JP7145356B1 (en) Pretreatment ink and ink set containing the same
JP7175417B1 (en) Overcoat ink and ink set containing the same
WO2023276974A1 (en) Overcoat ink and ink set including same
WO2023120150A1 (en) Maintenance liquid and ink set
WO2023120521A1 (en) Non-aqueous ink composition
JP2024050444A (en) Ink, ink set, image forming method, and image forming apparatus
JP2022157934A (en) Nonaqueous ink composition, inkjet recording method, and method for producing printed matter
JP2024007410A (en) Aqueous ink composition, recording method, recorded article manufacturing method, recorded article, and inkjet recording device
JP2023080839A (en) Non-white textile printing inkjet ink composition, ink set, and recording method

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23760062

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024503232

Country of ref document: JP

Kind code of ref document: A