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WO2024204751A1 - Non-aqueous ink composition, non-aqueous ink set, and printing method - Google Patents

Non-aqueous ink composition, non-aqueous ink set, and printing method Download PDF

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Publication number
WO2024204751A1
WO2024204751A1 PCT/JP2024/013138 JP2024013138W WO2024204751A1 WO 2024204751 A1 WO2024204751 A1 WO 2024204751A1 JP 2024013138 W JP2024013138 W JP 2024013138W WO 2024204751 A1 WO2024204751 A1 WO 2024204751A1
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WO
WIPO (PCT)
Prior art keywords
mass
organic solvent
containing compound
aqueous ink
ink composition
Prior art date
Application number
PCT/JP2024/013138
Other languages
French (fr)
Japanese (ja)
Inventor
康寛 河合
宏紀 松本
裕也 神田
Original Assignee
大日本塗料株式会社
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.)
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Application filed by 大日本塗料株式会社 filed Critical 大日本塗料株式会社
Publication of WO2024204751A1 publication Critical patent/WO2024204751A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to a non-aqueous ink composition, a non-aqueous ink set including the non-aqueous ink composition, and a printing method using the non-aqueous ink composition, and in particular to a non-aqueous ink composition for inkjet printing that produces printed images that are less likely to bleed and have excellent gloss, and that is less likely to cause blocking of roll media when printed on and wound up, and is less likely to corrode the print head.
  • JP 2005-15672 A describes a non-aqueous inkjet ink for polyvinyl chloride resin sheets, which is characterized in that the inkjet ink is made of an organic solvent, a pigment, and a resin, and contains 1 to 30% by weight of an organic solvent in which the polyvinyl chloride resin is soluble, while the organic solvent does not dissolve the polyvinyl chloride resin at all or barely dissolves the polyvinyl chloride resin.
  • Patent Document 2 JP 2005-200469 A (Patent Document 2) describes an oil-based ink for a piezoelectric inkjet printer, which contains a fixing resin, a pigment, and a solvent, the solvent contains a compound represented by general formula (1) and a cyclic ester, and the amount of the cyclic ester is 1 to 60 parts by weight per 100 parts by weight of the compound represented by general formula (1).
  • Lactone solvents particularly gamma-butyrolactone, are often used as solvents to dissolve polyvinyl chloride resin, but inks containing gamma-butyrolactone have the problem of easily corroding printer heads.
  • a method is being considered in which an ingredient with an anti-rust effect is added to the ink, preventing head corrosion while still taking advantage of the benefits of using lactone solvents.
  • JP 2008-247967 A (Patent Document 3) describes that in a non-aqueous inkjet ink composition containing a pigment, a resin, a pigment dispersant, and an organic solvent such as ⁇ -butyrolactone, by using an amino group-containing alcohol, and preferably by further adjusting the pH of the water extract of the ink to 6.0 to 10.0, no clogging occurs in the nozzles of the printer head when printing with an inkjet printer, and printed matter of excellent print quality can be obtained.
  • Patent Document 3 describes that in a non-aqueous inkjet ink composition containing a pigment, a resin, a pigment dispersant, and an organic solvent such as ⁇ -butyrolactone, by using an amino group-containing alcohol, and preferably by further adjusting the pH of the water extract of the ink to 6.0 to 10.0, no clogging occurs in the nozzles of the printer head when printing with an inkjet printer, and printed matter of excellent print quality can be obtained.
  • Patent Document 4 JP 2009-235383 A (Patent Document 4) describes that in a non-aqueous inkjet ink composition containing a pigment, a resin, a pigment dispersant, and an organic solvent such as ⁇ -butyrolactone, by using an imidazole compound, and preferably by further adjusting the pH of the water extract of the ink to 6.0 to 10.0, no clogging occurs in the nozzles of the printer head when printing with an inkjet printer, and printed matter of excellent print quality can be obtained.
  • Patent Document 5 describes that in a non-aqueous inkjet ink composition containing a pigment, a resin, a pigment dispersant, and an organic solvent such as gamma-butyrolactone, by using a volatile rust inhibitor, and preferably further adjusting the pH of the water extract of the ink to 6.0 to 10.0, it is possible to obtain printed matter of excellent print quality without causing clogging of the nozzles of the printer head when printing with an inkjet printer.
  • a volatile rust inhibitor preferably further adjusting the pH of the water extract of the ink to 6.0 to 10.0
  • an object of the present invention is to provide a non-aqueous ink composition for inkjet printing that produces printed images that are less likely to bleed, have excellent image gloss, and are less likely to cause media blocking when printed on roll media and then wound up, and is less likely to corrode the print head.
  • Another object of the present invention is to provide a non-aqueous ink set that includes such a non-aqueous ink composition, and a printing method that uses such a non-aqueous ink composition.
  • the present inventors first investigated the use of a glycol ether-based solvent, which has low viscosity and excellent drying properties, in combination with a lactone-based solvent as a solvent for a non-aqueous ink composition for inkjet printing.
  • ⁇ -butyrolactone a suitable lactone-based solvent
  • a mixture of, for example, 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of ⁇ -butyrolactone has an acidic pH of 5.4.
  • the inventors focused on an amide bond- or urea bond-containing compound, whose mixture in such a composition has a pH of 7.0 or higher. If the mixture in such a composition has a pH of 7.0 or higher, it is possible to prevent head corrosion.
  • the amide bond or urea bond-containing compound has a high ability to dissolve the resin used in the substrate and the resin contained in the ink, and by using it in a specific ratio together with a glycol ether-based solvent with a boiling point of less than 200°C, it was discovered that it is possible to obtain a printed matter that is less prone to bleeding, has excellent image gloss, and is less prone to media blocking when printed on roll media and wound up, leading to the completion of the present invention.
  • a first non-aqueous ink composition of the present invention is a non-aqueous ink composition for ink-jet printing, comprising (A) an organic solvent and (B) a resin, (A)
  • the organic solvent is The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C.
  • the non-aqueous ink composition is characterized in that the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 4.0 to 30% by mass.
  • a second non-aqueous ink composition of the present invention is a non-aqueous ink composition for ink-jet printing, comprising (A) an organic solvent and (B) a resin, the non-aqueous ink composition is an orange ink, (A)
  • the organic solvent is The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C.
  • the non-aqueous ink composition is characterized in that the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 1.0 to 30% by mass.
  • the organic solvent further contains (A-3) a glycol or glycol ether solvent having a boiling point of 220°C or higher and lower than 300°C.
  • the amide bond or urea bond-containing compound (A-2) contains at least one solvent selected from alkylamide solvents, cyclic amide solvents, aromatic amide solvents, alkylurea solvents, and cyclic urea solvents.
  • the non-aqueous ink composition is a black ink
  • the pH of the aqueous extract of the non-aqueous ink composition is within the range of 3.0 to 7.0.
  • the non-aqueous ink composition is a white ink
  • the amount of water contained in the non-aqueous ink composition is less than 10,000 ppm by mass.
  • the non-aqueous ink set of the present invention is a non-aqueous ink set for ink-jet printing comprising at least a cyan ink, a magenta ink, and a yellow ink,
  • the cyan ink, the magenta ink, and the yellow ink each contain (A) an organic solvent, (B) a resin, and (C) a pigment;
  • (A) The organic solvent is
  • the present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C.
  • the non-aqueous ink set is characterized in that the amount of the amide bond or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 4.0 to 30 mass %.
  • the non-aqueous ink set comprises an orange ink, the orange ink comprises (A) an organic solvent, (B) a resin, and (C) a pigment;
  • the organic solvent is The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, (A-1)
  • the amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %, The amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent
  • a first printing method of the present invention is a printing method for forming a printed layer using a non-aqueous ink composition for inkjet printing, which comprises (A) an organic solvent and (B) a resin, the method comprising the steps of: (A) The organic solvent is The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C.
  • the printing method is characterized in that the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 4.0 to 30 mass %.
  • a second printing method of the present invention is a printing method for forming a printing layer using a non-aqueous ink composition for inkjet printing, which contains (A) an organic solvent and (B) a resin, comprising the steps of: the non-aqueous ink composition is an orange ink, (A)
  • the organic solvent is The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C.
  • the printing method is characterized in that the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 1.0 to 30% by mass.
  • the non-aqueous ink composition of the present invention can provide a non-aqueous ink composition for inkjet printing that produces printed images that are less likely to bleed, have excellent image gloss, and is less likely to cause media blocking when printed on roll media and then wound up, and is less likely to corrode the print head.
  • the non-aqueous ink set of the present invention can provide a non-aqueous ink set that includes such a non-aqueous ink composition.
  • the printing method of the present invention can provide a printing method that uses such a non-aqueous ink composition.
  • the present invention is described in detail below.
  • the present invention relates to a non-aqueous ink composition, a non-aqueous ink set, and a printing method.
  • the non-aqueous ink composition of the present invention is a non-aqueous ink composition for inkjet printing that contains an organic solvent and a resin.
  • the organic solvent is the (A) component, and is also referred to as the "(A) organic solvent.”
  • the resin is the (B) component, and is also referred to as the "(B) resin.”
  • a non-aqueous ink composition means an ink composition that does not contain water as a solvent and is not miscible with water in any proportion.
  • an ink composition for inkjet printing means an ink composition that can be used for printing with an inkjet printer.
  • the non-aqueous ink composition of the present invention contains an organic solvent (A), and the amount of the organic solvent (A) in the non-aqueous ink composition of the present invention is preferably 80 to 99% by mass, and more preferably 90 to 95% by mass.
  • the organic solvent (A) is The composition comprises (A-1) a glycol ether solvent having a boiling point of less than 200°C, and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of (A-2) the amide bond- or urea bond-containing compound has a pH of 7.0 or higher.
  • the "glycol ether-based solvent with a boiling point of less than 200°C” is defined as component (A-1), and is also referred to as "(A-1) glycol ether-based solvent with a boiling point of less than 200°C” as described above.
  • the "amide bond- or urea bond-containing compound, in which a mixture of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of an amide bond- or urea bond-containing compound has a pH of 7.0 or higher” is defined as component (A-2), and is also referred to as "(A-2) amide bond- or urea bond-containing compound" as described above.
  • the glycol ether solvent of component (A-1) is an organic solvent that has a low viscosity, a relatively high tag closed flash point, and good drying properties, and is preferably used as the main solvent for the non-aqueous ink composition of the present invention.
  • the preferred flash point of the glycol ether solvent of component (A-1) is 50°C or higher and 75°C or lower. In this specification, the flash point is the flash point measured by the tag closed flash point method.
  • glycol ether solvents refer to compounds that have an alkyl ether structure based on glycols such as ethylene glycol and propylene glycol.
  • Glycol ether solvents include those in which both ends of the molecule are hydroxyl groups, and those in which the hydrogen of the hydroxyl group at one or both ends of the molecule is replaced with a substituent such as an alkyl group or an acyl group.
  • the glycol ether solvent of component (A-1) has a boiling point of less than 200°C, preferably 150 to 200°C, and more preferably 160 to 190°C.
  • the boiling point refers to the boiling point at 1 atmospheric pressure.
  • the glycol ether solvent of the component (A-1) preferably contains a glycol ether solvent represented by the following general formula (1): R1-(OR2)n-O-R3 (1)
  • n is an integer of 1 to 4
  • R1 is an alkyl group having 1 to 8 carbon atoms which may be branched or an acyl group having 1 to 4 carbon atoms
  • R2 is an optionally branched alkylene group having 1 to 4 carbon atoms
  • R3 is hydrogen, an alkyl group having 1 to 4 carbon atoms which may be branched, or an acyl group having 1 to 4 carbon atoms.
  • the glycol ether solvent of component (A-1) preferably contains a dialkylene glycol dialkyl ether or a dialkylene glycol monoalkyl ether acetate, and more preferably contains at least one selected from diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate.
  • the amount of component (A-1) in the organic solvent (A) is preferably within the range of 60 to 95% by mass, and more preferably within the range of 75 to 95% by mass.
  • the component (A-1) may be used alone or in combination of two or more types.
  • the amide bond- or urea bond-containing compound of component (A-2) is an organic solvent that does not corrode the head because the pH of a mixture consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) is higher than 7.0 and is not in the acidic range, and has a high ability to dissolve resins such as polyvinyl chloride resin (in other words, has excellent resin solubility).
  • component (A-2) is used as a solvent, it has the effect of allowing the ink on the substrate to penetrate without spreading.
  • the amide bond- or urea bond-containing compound of component (A-2) is used in combination with the glycol ether-based solvent of component (A-1) described above, it is possible to provide a printed matter in which the image is less likely to bleed and the media is less likely to block when printed on roll media and wound up.
  • the reason why the pH of the mixture consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of an amide bond- or urea bond-containing compound is set to 7.0 or more is due to the idea that the head can be protected from corrosion by not making the pH of the ink acidic.
  • Diethylene glycol ethyl methyl ether is a glycol ether-based solvent of component (A-1), and in the present invention, it is considered important that the pH of the aqueous solution containing this glycol ether (A-1), water, and the amide bond- or urea bond-containing compound of component (A-2) does not fall into a strongly acidic range, and the pH of the aqueous solution at a specific mixing ratio that is close to the actual ink mixing ratio is specified to be 7.0 or more.
  • the amide bond or urea bond-containing compound of component (A-2) is a mixture of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of an amide bond or urea bond-containing compound, the pH of which is 7.0 or higher, preferably 7.0 to 10.0, and more preferably 7.0 to 9.5.
  • the amide bond or urea bond-containing compound of component (A-2) preferably contains at least one solvent selected from alkylamide solvents, cyclic amide solvents, aromatic amide solvents, alkylurea solvents, and cyclic urea solvents.
  • alkylamide solvents include 3-methoxy-N,N-dimethylpropanamide.
  • cyclic amide solvents include 2-pyrrolidone and ⁇ -caprolactam.
  • aromatic amide solvents include benzamide.
  • alkylurea solvents include N-methylurea.
  • cyclic urea solvents include 1,3-dimethyl-2-imidazolidinone.
  • amide bond or urea bond-containing compound of component (A-2) cyclic urea solvents are preferred, imidazolidinone solvents are more preferred, and 1,3-dimethyl-2-imidazolidinone is particularly preferred.
  • the amount of component (A-2) in organic solvent (A) is preferably within the range of 4.0 to 30% by mass, more preferably within the range of 5 to 30% by mass, and even more preferably within the range of 5 to 15% by mass.
  • the component (A-2) may be used alone or in combination of two or more types. When the amount of component (A-2) in organic solvent (A) is 30% by mass or less, the glossiness of the image can be improved.
  • the inventors have also found that when the non-aqueous ink composition of the present invention is an orange ink, the effect of the (A-2) component can be fully exhibited even when the amount of the (A-2) component in the (A) organic solvent is less than 4.0% by mass.
  • the amount of the (A-2) component in the (A) organic solvent is preferably in the range of 1.0 to 30% by mass, more preferably in the range of 1.5 to 20% by mass, even more preferably in the range of 2.0 to 15% by mass, and particularly preferably in the range of 2.0 to 12% by mass.
  • the ratio of the amount of component (A-1) in organic solvent (A) to the amount of component (A-2) in organic solvent (A) is preferably 2 to 10, and more preferably 4 to 8.
  • the ratio of the amount of component (A-1) in organic solvent (A) to the amount of component (A-2) in organic solvent (A) may be expressed as "(A-1)/(A-2)."
  • the ratio of the amount of component (A-1) in organic solvent (A) to the amount of component (A-2) in organic solvent (A) is based on mass.
  • the organic solvent (A) further comprises, in addition to the above-mentioned components (A-1) and (A-2), It is preferable to contain (A-3) a glycol or glycol ether solvent having a boiling point of 220° C. or more and less than 300° C.
  • the component (A-3) is preferably a glycol having a boiling point of 220° C. or more and less than 300° C. and both terminals being hydroxyl groups.
  • a glycol or glycol ether-based solvent having a boiling point of 220°C or higher and lower than 300°C is defined as component (A-3), and as described above, is also referred to as "(A-3) a glycol or glycol ether-based solvent having a boiling point of 220°C or higher and lower than 300°C.”
  • the glycol or glycol ether-based solvent in component (A-3) prevents the ink from drying out in the head, improving re-ejection properties and contributing to improved gloss of the printed material.
  • Examples of the (A-3) component include diethylene glycol, triethylene glycol, tripropylene glycol, polypropylene glycol, diethylene glycol-2-ethylhexyl ether, diethylene glycol monohexyl ether, diethylene glycol monobutyl ether, dipropylene glycol, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, etc. It is preferable that the (A-3) component has excellent compatibility with the (A-1) component and the (A-2) component.
  • the amount of component (A-3) in the organic solvent (A) is preferably within the range of 0.1 to 5.0% by mass, more preferably 0.1 to 2.0% by mass, even more preferably 0.1 to 1.0% by mass, and most preferably within the range of 0.1 to 0.7% by mass.
  • the component (A-3) may be used alone or in combination of two or more types.
  • the organic solvent (A) further comprises (A-4)
  • An organic solvent having a boiling point of less than 150° C. and not corresponding to the components (A-1) and (A-2) may be included.
  • component (A-4) an organic solvent that has a boiling point of less than 150°C and does not fall under either component (A-1) or component (A-2)
  • component (A-4) an organic solvent that has a boiling point of less than 150°C and does not fall under either component (A-1) or component (A-2).
  • the organic solvent in component (A-4) has a low boiling point, which can improve the drying properties of the ink.
  • Examples of the (A-4) component include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclopentanone. It is preferable that the (A-4) component has excellent compatibility with the (A-1) and (A-2) components.
  • the amount of component (A-4) in the organic solvent (A) is preferably within the range of 0.5 to 2.0% by mass, and more preferably within the range of 0.5 to 1.0% by mass.
  • the component (A-2) may be used alone or in combination of two or more types.
  • the non-aqueous ink composition of the present invention preferably does not contain gamma-butyrolactone.
  • the non-aqueous ink composition of the present invention contains a (B) resin, and the amount of the (B) resin in the non-aqueous ink composition of the present invention is preferably 1 to 5 mass %, and more preferably 1 to 3 mass %.
  • the (B) resin may be used alone or in combination of two or more types.
  • (B) resins include, for example, polyvinyl chloride (vinyl chloride resin), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer (vinyl chloride/vinyl acetate copolymer resin), vinyl chloride resin, chlorinated rubber, chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated ethylene-vinyl acetate resin, acrylic resin, acrylic silicone resin, styrene-acrylic copolymer resin, polystyrene resin, polyamide resin, polyurethane resin, polyolefin resin, silicone resin, fluororesin, epoxy resin, polyester resin, ketone resin, phenol resin, polyvinyl alcohol, polyvinyl alcohol derivatives (anion-modified polyvinyl alcohol, etc.), cellulose, cellulose derivatives (hydroxymethylcellulose, hydroxyethylcellulose, cellulose acetate, etc.), rosin resin, oil-based resin, petroleum resin, alkyd resin, alginic
  • Modified products of these resins are also included, such as hydroxyalkyl etherification modifications and carboxylic acid modifications.
  • acrylic resins, vinyl chloride resins, and vinyl chloride/vinyl acetate copolymer resins are preferred from the viewpoints of adhesion to the substrate and durability of the printed film.
  • the non-aqueous ink composition of the present invention may contain a colorant such as a dye or pigment, but in this case, it is preferable for the composition to contain a pigment from the viewpoint of weather resistance.
  • a metallic ink can be produced by using a metal pigment.
  • the content of the colorant in the ink composition is, for example, 0.1 to 15 mass %.
  • the colorant may be used alone or in combination of two or more types.
  • the pigment is referred to as component (C) and is also referred to as "pigment (C)".
  • colorants include: C. I. Pigment Yellow 1,2,3,4,5,6,7,9,10,12,13,14,15,16,17,24,32,34,35,36,37,41,42,43,49,53,55,60,61,62,63,65,73,74,75,77,81,83 , 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120,123,124,126,127,128,129,130,133,138,139,150,151,152,153,154,155,165,167,168,169,170,172,173,174,175,176,179,180,181,1 82, 183, 184, 185, 191, 193, 194, 199, 205, 206, 209, 212, 213, 214, 215, 219, C.
  • I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28, Examples include aluminum flakes, glass flakes, pearl pigments, and hollow particles.
  • C. I. Pigment Black 7, C. I. Pigment Blue 15:3, 15:4, 28, C. I. Pigment Red 101, 122, 202, 254, 282, C. I. Pigment Violet 19, C. I. Pigment White 6, C. I. Pigment Yellow 42, 120, 138, 139, 150, 151, 155, 213, C. I. Pigment Orange 43, 64, 71, 73, 83 are preferred.
  • the pigment particles dispersed in the ink composition have a volume average particle diameter of 0.05 to 0.4 ⁇ m and a volume maximum particle diameter of 0.2 to 1 ⁇ m. If the volume average particle diameter is greater than 0.4 ⁇ m and the volume maximum particle diameter is greater than 1 ⁇ m, it tends to be difficult to eject the ink composition stably.
  • the volume average particle diameter and volume maximum particle diameter can be measured using a measuring device that uses a dynamic light scattering method.
  • the non-aqueous ink composition of the present invention may further contain a pigment dispersant as necessary to disperse the pigment.
  • the content of the pigment dispersant in the ink composition is, for example, 0.1 to 5 mass %.
  • the pigment dispersant may be used alone or in combination of two or more types.
  • pigment dispersants include: ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-
  • the non-aqueous ink composition of the present invention may contain additives such as ultraviolet absorbers, radical scavengers, surface conditioners, antioxidants, plasticizers, rust inhibitors, solvents, fillers, defoamers, charge control agents, stress relaxation agents, penetrating agents, light-guiding materials, glittering materials, magnetic materials, fluorescent materials, antibacterial agents, antiviral agents, and anti-algae agents as other components as necessary.
  • additives such as ultraviolet absorbers, radical scavengers, surface conditioners, antioxidants, plasticizers, rust inhibitors, solvents, fillers, defoamers, charge control agents, stress relaxation agents, penetrating agents, light-guiding materials, glittering materials, magnetic materials, fluorescent materials, antibacterial agents, antiviral agents, and anti-algae agents as other components as necessary.
  • the non-aqueous ink composition of the present invention can be used as inks of various colors.
  • examples include light cyan ink, light magenta ink, light yellow ink, light black ink, orange ink, and white ink.
  • the pH of the water extract of the non-aqueous ink composition is preferably in the range of 3.0 to 7.0.
  • an acidic carbon black pigment is used in a conventional non-aqueous ink, it is preferable to adjust the pH using a basic compound such as an amino group-containing alcohol to prevent head corrosion.
  • the non-aqueous ink composition of the present invention contains a specific amount of component (A-2) that makes the pH of a mixture of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of an amide bond or urea bond-containing compound 7.0 or higher, so that head corrosion can be prevented.
  • the resolubility of the ink in the ejection head can be improved.
  • the pH of the water extract of the black ink can be adjusted by the type of pigment and the amount of solvent, and from the viewpoint of setting the pH of the water extract of the non-aqueous ink composition in the range of 3.0 to 7.0, it is preferable that the black ink does not contain an amino group-containing alcohol.
  • Amino group-containing alcohols are compounds that have an amino group and a hydroxyl group in the molecule, and are sometimes used to prevent nozzle clogging in the ejection head of a printer.
  • Examples of amino group-containing alcohols include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and tris(hydroxymethyl)aminomethane.
  • the amount of water contained in the non-aqueous ink composition is preferably less than 10,000 ppm by mass.
  • the stability of the ink can be improved.
  • Methods for setting the moisture content in the ink to less than 10,000 ppm by mass include a method of reducing the moisture content of the materials before preparing the ink, and a method of reducing the moisture content of the ink after preparation. From the viewpoint of suppressing an increase in the viscosity of the ink, it is preferable to prepare the ink after reducing the moisture content in the pigment beforehand.
  • the moisture content in the white ink is preferably less than 9,000 ppm by mass, and more preferably less than 8,000 ppm by mass.
  • the amount of pigment contained in the white ink is preferably 1 to 20% by mass, and more preferably 5 to 18% by mass.
  • White inks often contain a larger amount of pigment than other pigment inks in order to increase the hiding power when printed on transparent substrates, and inorganic pigments such as titanium oxide are prone to absorbing water, so keeping the moisture content in the white ink below 10,000 ppm by mass is particularly important in terms of improving the storage stability of the ink.
  • the non-aqueous ink composition of the present invention can be prepared by mixing various components appropriately selected as needed, and, if necessary, filtering the resulting mixture using a filter having a pore size of about 1/10 or less of the nozzle diameter of the inkjet printhead to be used.
  • the non-aqueous ink composition of the present invention preferably has a viscosity at 25°C of 2.5 mPa ⁇ s or more and less than 7.0 mPa ⁇ s, more preferably 2.8 to 6.5 mPa ⁇ s, and even more preferably 3.0 to 6.0 mPa ⁇ s.
  • a viscosity at 25°C of 2.5 mPa ⁇ s or more and less than 7.0 mPa ⁇ s, more preferably 2.8 to 6.5 mPa ⁇ s, and even more preferably 3.0 to 6.0 mPa ⁇ s.
  • the ink viscosity can be measured using a cone-plate viscometer. In this specification, the ink viscosity is also referred to as "viscosity (R)".
  • the non-aqueous ink composition of the present invention preferably has a surface tension at 25°C of 20 to 35 mN/m, more preferably 23 to 33 mN/m, and even more preferably 25 to 30 mN/m. If the ink surface tension at 25°C is within the above specified range, good ejection stability is obtained and the ink has good wettability on the printed surface, leading to improved ink drying properties and gloss of the printed material.
  • the surface tension of the ink can be measured by the plate method.
  • the non-aqueous ink set of the present invention is a non-aqueous ink set for ink-jet printing comprising at least a cyan ink, a magenta ink, and a yellow ink,
  • the cyan ink, the magenta ink, and the yellow ink each contain (A) an organic solvent, (B) a resin, and (C) a pigment;
  • (A) The organic solvent is
  • the non-aqueous ink set includes (A-1) a glycol ether solvent having a boiling point of less than 200°C, and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the (A-2) amide bond- or urea bond-containing compound has a pH of 7.0 or higher.
  • the amount of (A-1) glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %
  • the amount of (A-2) the amide bond- or urea bond-containing compound in the organic solvent (A) is within a range of 4.0 to 30 mass %.
  • a non-aqueous ink set for inkjet printing means a non-aqueous ink set that can be used for printing with an inkjet printer, and a non-aqueous ink set means an ink set that is composed of a non-aqueous ink composition.
  • the inks that constitute the non-aqueous ink set of the present invention are non-aqueous ink compositions.
  • the inks constituting the non-aqueous ink set of the present invention are at least cyan ink, magenta ink, and yellow ink, but it is also possible to include an ink that emits a different color, such as black ink.
  • examples of inks constituting the non-aqueous ink set of the present invention include light cyan ink, light magenta ink, light yellow ink, light black ink, orange ink, and white ink.
  • all of the inks constituting the non-aqueous ink set of the present invention are the non-aqueous ink compositions of the present invention described above.
  • the orange ink contains (A) an organic solvent, (B) a resin, and (C) a pigment, (A)
  • the organic solvent is The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C.
  • the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is preferably within a range of 1.0 to 30 mass %.
  • the orange ink is preferably the non-aqueous ink composition of the present invention described above.
  • the additional ink contains (A) an organic solvent, (B) a resin, and (C) a pigment, (A)
  • the organic solvent is The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C.
  • the amount of the amide bond or urea bond-containing compound (A-2) in the organic solvent (A) is preferably within a range of 4.0 to 30 mass %.
  • the further ink is preferably the non-aqueous ink composition of the present invention described above.
  • the ratio of the (A-2) amide bond or urea bond-containing compound in each color ink is approximately the same, and that the pH of a mixture of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the (A-2) amide bond or urea bond-containing compound is 7.0 or higher.
  • the viscosity of each color ink is also preferable to make the viscosity of each color ink the same, and the difference in viscosity (R) at 25°C is preferably 0.5 mPa ⁇ s or less, and the viscosity (R) of each ink at 25°C is preferably within the range of 3.0 to 6.0 mPa ⁇ s.
  • the printing method of the present invention is a printing method for forming a printed layer using a non-aqueous ink composition for inkjet printing, which contains (A) an organic solvent and (B) a resin, comprising the steps of: (A)
  • the organic solvent is
  • the present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher, The ratio of (A-1) glycol ether solvent having a boiling point of less than 200° C.
  • the printing method is characterized in that the ratio of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 4.0 to 30 mass %.
  • the inventors have also found that in the printing method of the present invention, when the non-aqueous ink composition is an orange ink, the effect of the component (A-2) can be fully exhibited even when the amount of the component (A-2) in the organic solvent (A) is less than 4.0% by mass.
  • the amount of the component (A-2) in the organic solvent (A) is preferably within the range of 1.0 to 30% by mass.
  • non-aqueous ink composition for inkjet printing "(A) organic solvent,” “(A-1) glycol ether solvent with a boiling point of less than 200°C,” “(A-2) amide bond or urea bond-containing compound with an aqueous solution having a pH of 7.0 or higher,” and "(B) resin” are as described in the description of the non-aqueous ink composition of the present invention.
  • the printed layer refers to a layer formed by printing with ink.
  • the non-aqueous ink composition is preferably the non-aqueous ink composition of the present invention described above. Furthermore, when forming a printed layer from multiple non-aqueous ink compositions, it is preferable to form the printed layer using the non-aqueous ink set of the present invention described above.
  • the substrate on which the printing layer is formed is not particularly limited, but substrates used in industrial lines are suitable.
  • the substrate may be in the form of a film, sheet, plate, etc.
  • the substrate material include epoxy resin, ABS resin, polycarbonate, polyvinyl chloride, polystyrene, acrylic resin, particularly plastics such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), and polypropylene (PP), metals such as iron, stainless steel, and aluminum, wood, cement, concrete, gypsum, calcium silicate, calcium carbonate, and glass.
  • substrates include PVC sheets, tarpaulin, plastic cardboard, acrylic boards, flexible boards, calcium silicate boards, gypsum slag bar light boards, calcium carbonate boards, wood chip cement boards, precast concrete boards, lightweight foamed concrete (ALC) boards, gypsum boards, tiles, and glass boards.
  • polyvinyl chloride substrates and tarpaulin substrates are preferred.
  • Component (A-2) has high penetration into polyvinyl chloride and tarpaulin substrates, and produces a printed layer that is less prone to bleeding and has excellent blocking resistance.
  • printing is performed by an inkjet printing method.
  • Various inkjet printers can be used for inkjet printing. Examples of inkjet printers include inkjet printers that eject ink compositions using a charge control method or a piezoelectric method. Large inkjet printers, specifically inkjet printers designed for printing on items produced on industrial lines, can also be suitably used.
  • the pigments used were yellow pigment: Comalix Yellow 150 (Zeyah Chemicals), cyan pigment: Chromophie Blue A-220JC (Dainichiseika Color & Chemicals), black pigment: Monarch 1000 (Cabot), magenta pigment: Fastogen Super Magenta RG (DIC), the dispersant used was DISPERBYK-2150 (BYK) or SOLSPERSE32000 (Lubrizol), and the resin used was VINNOL H15/42 (vinyl chloride-vinyl acetate copolymer resin, Wacker Chemie) or Dianall BR-87 (acrylic resin, Mitsubishi Chemical).
  • ⁇ Head corrosion resistance> The printer head was filled with inks 1 to 104 and immersed at room temperature for 100 hours, after which the presence or absence of rust around the nozzles was observed with a digital microscope and evaluated according to the following criteria. The results are shown in Table 14. (standard) ⁇ : No rust was observed in any of the cases of magenta ink, yellow ink, cyan ink, and black ink. x: Rust occurred in the case of one or more of magenta ink, yellow ink, cyan ink, and black ink.
  • ⁇ Discharge stability> A large format inkjet printer was filled with the black inks shown in Table 14. After printing a test pattern image, a 100% solid image was printed for 1000 hours. After printing, the test pattern was printed again and evaluated according to the following criteria. The results are shown in Table 14. (standard) ⁇ : Test pattern loss and test pattern disorder are less than 1%. ⁇ : Test pattern loss and test pattern disorder are less than 5%. ⁇ : Test pattern loss and test pattern disorder of 5% to 10%. x: The test pattern is missing or distorted by more than 10%.
  • ⁇ Dot diameter> A test pattern was printed by a large format inkjet printer using the black ink shown in Table 14, and the dot diameter was observed by a digital microscope. The evaluation results according to the following criteria are shown in Table 14. Printed images with dot diameters of 80 ⁇ m or more have high gloss. (standard) ⁇ : Dot diameter is 80 ⁇ m or more ⁇ : Dot diameter is less than 80 ⁇ m
  • (A-1)/organic solvent indicates the amount (mass %) of (A-1) glycol ether-based solvent with a boiling point of less than 200°C in (A) organic solvent
  • “(A-2)/organic solvent” indicates the amount (mass %) of (A-2) amide bond- or urea bond-containing compound in (A) organic solvent
  • “(A-3)/organic solvent” indicates the amount (mass %) of (A-3) glycol or glycol ether-based solvent with a boiling point of 220°C or more and less than 300°C in (A) organic solvent
  • “(A-1)/(A-2)” indicates the mass ratio of the amount of (A-1) component in (A) organic solvent to the amount of (A-2) component in (A) organic solvent.
  • ⁇ Head corrosion resistance> The printer head was filled with black ink and immersed at room temperature for 100 hours, after which the presence or absence of rust around the nozzles was observed with a digital microscope and evaluated according to the following criteria. (standard) ⁇ : No rust is formed. ⁇ : Rust is observed.
  • Continuous ejection stability evaluation The continuous ejection stability when a 100% solid image was printed for 5 m was evaluated based on the following criteria. ⁇ : Even after printing for 5 m, the ejected ink droplets were ejected without any change in droplet shape or deflection in flight. ⁇ : After printing for 5 m, slight changes in droplet shape and flight deviation were observed in the flight state of the ejected ink droplets, but these were at a level that did not cause any practical problems. x: After printing for 5 m, significant changes in droplet shape and flight deviation were observed in the flight state of the ejected ink droplets, which is problematic for practical use.
  • ⁇ Discharge stability> The orange inks shown in Table 16 were filled into a large format inkjet printer. After printing a test pattern image, a 100% solid image was printed for 1000 hours. After printing, the test pattern was printed again and evaluated according to the following criteria. The results are shown in Table 16. (standard) ⁇ : Test pattern loss and test pattern disorder are less than 1%. ⁇ : Test pattern loss and test pattern disorder are less than 5%. ⁇ : Test pattern loss and test pattern disorder of 5% to 10%. x: The test pattern is missing or distorted by more than 10%.
  • (A-1)/organic solvent indicates the amount (mass %) of (A-1) glycol ether-based solvent with a boiling point of less than 200°C in (A) organic solvent
  • “(A-2)/organic solvent” indicates the amount (mass %) of (A-2) amide bond- or urea bond-containing compound in (A) organic solvent
  • “(A-3)/organic solvent” indicates the amount (mass %) of (A-3) glycol or glycol ether-based solvent with a boiling point of 220°C or more and less than 300°C in (A) organic solvent
  • “(A-1)/(A-2)” indicates the mass ratio of the amount of (A-1) component in (A) organic solvent to the amount of (A-2) component in (A) organic solvent.
  • Examples 25 to 30>> ⁇ Preparation of White Inks W1 to W6> Using titanium oxide pigment that had been dehydrated in advance using a dehydrating agent, mixtures containing each component in the amounts (parts by mass) shown in Table 17 were kneaded in a bead mill for 3 hours to prepare white inks W1 to W6. The viscosity of the resulting inks at 25°C was measured using a cone-plate viscometer, and this was taken as the initial viscosity. The moisture content of inks W1 to W6 was also measured using a moisture meter (Karl Fischer method).
  • ⁇ Head corrosion resistance> The printer head was filled with white ink W1 to W6, and after immersion at room temperature for 100 hours, the presence or absence of rust around the nozzles was observed with a digital microscope and evaluated according to the following criteria. The results are shown in Table 17. (standard) ⁇ : No rust is formed. ⁇ : Rust is observed.
  • ⁇ Discharge stability> For the white inks W1 to W6, the ink was filled into a large format inkjet printer. After printing a test pattern image, a 100% solid image was printed for 1000 hours. After printing, the test pattern was printed again and evaluated according to the following criteria. The results are shown in Table 17. (standard) ⁇ : Test pattern loss and test pattern disorder are less than 1%. ⁇ : Test pattern loss and test pattern disorder are less than 5%. ⁇ : Test pattern loss and test pattern disorder of 5% to 10%. x: The test pattern is missing or distorted by more than 10%.
  • ⁇ Storage stability> The white inks W1 to W6 were stored at 50° C. for 28 days, and the viscosity of the inks was measured before and after storage to determine the rate of change in viscosity from the initial viscosity, and the storage stability was evaluated according to the following criteria. The results are shown in Table 17. (standard) ⁇ : Viscosity change rate is 0 to 0.9% ⁇ : Viscosity change rate is 1.0% to 2.9% ⁇ : Viscosity change rate is 3.0% to 14.9% ⁇ : Viscosity change rate is 15.0% or more
  • (A-1)/organic solvent indicates the amount (mass %) of (A-1) glycol ether-based solvent with a boiling point of less than 200°C in (A) organic solvent
  • “(A-2)/organic solvent” indicates the amount (mass %) of (A-2) amide bond- or urea bond-containing compound in (A) organic solvent
  • “(A-3)/organic solvent” indicates the amount (mass %) of (A-3) glycol or glycol ether-based solvent with a boiling point of 220°C or more and less than 300°C in (A) organic solvent
  • “(A-1)/(A-2)” indicates the mass ratio of the amount of (A-1) component in (A) organic solvent to the amount of (A-2) component in (A) organic solvent.

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Abstract

The present invention relates to a non-aqueous ink composition for inkjet printing, which is unlikely to cause bleeding of an image on a printed object, gives excellent image glossiness, is unlikely to cause media blocking when printed on roll media and wound, and is unlikely to cause corrosion of a printing head. More specifically, the present invention relates to a non-aqueous ink composition for inkjet printing, which contains an organic solvent (A) and a resin (B) and which is characterized in that the organic solvent (A) contains (A-1) a glycol ether-based solvent having a boiling point of lower than 200°C and (A-2) an amide bond-containing or urea bond-containing compound for which a specific mixed liquid has a pH of 7.0 or more, the amount of the glycol ether-based solvent (A-1) having a boiling point of lower than 200°C in the organic solvent (A) is within a range of 60 to 95 mass%, and the amount of the amide bond-containing or urea bond-containing compound (A-2) for which a specific mixed liquid has a pH of 7.0 or more in the organic solvent (A) is within a range of 4.0 to 30 mass% (here, in the case of an orange ink, the amount of the amide bond-containing or urea bond-containing compound (A-2) for which a specific mixed liquid has a pH of 7.0 or more in the organic solvent (A) is within a range of 1.0 to 30 mass%).

Description

非水系インク組成物、非水系インクセットおよび印刷方法Non-aqueous ink composition, non-aqueous ink set and printing method
　本発明は、非水系インク組成物、非水系インク組成物を備える非水系インクセットおよび非水系インク組成物を用いた印刷方法に関し、特には、印刷物の画像が滲みにくく、画像の光沢性に優れるとともに、ロールメディアに印刷して巻き取る際にもメディアがブロッキングしにくく、印刷ヘッドが腐食しにくいインクジェット印刷用の非水系インク組成物に関するものである。 The present invention relates to a non-aqueous ink composition, a non-aqueous ink set including the non-aqueous ink composition, and a printing method using the non-aqueous ink composition, and in particular to a non-aqueous ink composition for inkjet printing that produces printed images that are less likely to bleed and have excellent gloss, and that is less likely to cause blocking of roll media when printed on and wound up, and is less likely to corrode the print head.
　従来、塩ビシート等への印刷には、ポリ塩化ビニル樹脂を溶解しない溶媒と溶解する溶媒を組み合わせて用い、基材と画像間の密着性に優れる印刷物を得る方法が検討されてきた。 　Traditionally, when printing on PVC sheets and the like, methods have been considered that involve combining a solvent that does not dissolve polyvinyl chloride resin with a solvent that does, resulting in a print with excellent adhesion between the substrate and the image.
　例えば、特開２００５－１５６７２号公報（特許文献１）には、有機溶剤、顔料および樹脂からなる非水性インクジェットインキにおいて、該有機溶剤がポリ塩化ビニル樹脂を全く溶解しないか、ほとんど溶解しない有機溶剤に対し、ポリ塩化ビニル樹脂が可溶な有機溶剤を１～３０重量％含有することを特徴とするポリ塩化ビニル樹脂シート用非水性インクジェットインキが記載されている。また、特開２００５－２００４６９号公報（特許文献２）には、定着樹脂と顔料と溶媒とを含有し、上記溶媒が、一般式（１）で表わされる化合物と環状エステルとを含有し、該環状エステルの量が一般式（１）で表わされる化合物１００質量部当たり１～６０質量部であることを特徴とするピエゾ式インクジェットプリンター用油性インクが記載されている。 For example, JP 2005-15672 A (Patent Document 1) describes a non-aqueous inkjet ink for polyvinyl chloride resin sheets, which is characterized in that the inkjet ink is made of an organic solvent, a pigment, and a resin, and contains 1 to 30% by weight of an organic solvent in which the polyvinyl chloride resin is soluble, while the organic solvent does not dissolve the polyvinyl chloride resin at all or barely dissolves the polyvinyl chloride resin. JP 2005-200469 A (Patent Document 2) describes an oil-based ink for a piezoelectric inkjet printer, which contains a fixing resin, a pigment, and a solvent, the solvent contains a compound represented by general formula (1) and a cyclic ester, and the amount of the cyclic ester is 1 to 60 parts by weight per 100 parts by weight of the compound represented by general formula (1).
　ポリ塩化ビニル樹脂を溶解する溶媒としてラクトン系溶剤、特にγ－ブチロラクトンが使用されることが多いが、γ－ブチロラクトンを含むインクはプリンターのヘッドを腐食しやすいといった課題がある。この課題に対しては、インクに防錆効果を有する成分を添加して、ラクトン系溶剤を用いる利点を生かしつつヘッドの腐食を防止する方法が検討されている。 Lactone solvents, particularly gamma-butyrolactone, are often used as solvents to dissolve polyvinyl chloride resin, but inks containing gamma-butyrolactone have the problem of easily corroding printer heads. To address this issue, a method is being considered in which an ingredient with an anti-rust effect is added to the ink, preventing head corrosion while still taking advantage of the benefits of using lactone solvents.
　例えば、特開２００８－２４７９６７号公報（特許文献３）では、顔料、樹脂、顔料分散剤、及びγ－ブチロラクトン等の有機溶媒を含有する非水系インクジェット用インク組成物において、アミノ基含有アルコールを用いることで、好ましくは更にインクの水抽出物のｐＨを６．０～１０．０に調整することで、インクジェットプリンタにより印刷する際にプリンタヘッド部のノズルへの詰まりが生じることがなく優れた印字品質の印刷物が得られることが記載されている。特開２００９－２３５３８３号公報（特許文献４）では、顔料、樹脂、顔料分散剤、及びγ－ブチロラクトン等の有機溶媒を含有する非水系インクジェット用インク組成物において、イミダゾール化合物を用いることで、好ましくは更にインクの水抽出物のｐＨを６．０～１０．０に調整することで、インクジェットプリンタにより印刷する際にプリンタヘッド部のノズルへの詰まりが生じることがなく優れた印字品質の印刷物が得られることが記載されている。特開２００９－２４２６４９号公報（特許文献５）では、顔料、樹脂、顔料分散剤、及びγ－ブチロラクトン等の有機溶媒を含有する非水系インクジェット用インク組成物において、気化性防錆剤を用いることで、好ましくは更にインクの水抽出物のｐＨを６．０～１０．０に調整することで、インクジェットプリンタにより印刷する際にプリンタヘッド部のノズルへの詰まりが生じることがなく優れた印字品質の印刷物が得られることが記載されている。 For example, JP 2008-247967 A (Patent Document 3) describes that in a non-aqueous inkjet ink composition containing a pigment, a resin, a pigment dispersant, and an organic solvent such as γ-butyrolactone, by using an amino group-containing alcohol, and preferably by further adjusting the pH of the water extract of the ink to 6.0 to 10.0, no clogging occurs in the nozzles of the printer head when printing with an inkjet printer, and printed matter of excellent print quality can be obtained. JP 2009-235383 A (Patent Document 4) describes that in a non-aqueous inkjet ink composition containing a pigment, a resin, a pigment dispersant, and an organic solvent such as γ-butyrolactone, by using an imidazole compound, and preferably by further adjusting the pH of the water extract of the ink to 6.0 to 10.0, no clogging occurs in the nozzles of the printer head when printing with an inkjet printer, and printed matter of excellent print quality can be obtained. Japanese Patent Laid-Open Publication No. 2009-242649 (Patent Document 5) describes that in a non-aqueous inkjet ink composition containing a pigment, a resin, a pigment dispersant, and an organic solvent such as gamma-butyrolactone, by using a volatile rust inhibitor, and preferably further adjusting the pH of the water extract of the ink to 6.0 to 10.0, it is possible to obtain printed matter of excellent print quality without causing clogging of the nozzles of the printer head when printing with an inkjet printer.
特開２００５－１５６７２号公報JP 2005-15672 A 特開２００５－２００４６９号公報JP 2005-200469 A 特開２００８－２４７９６７号公報JP 2008-247967 A 特開２００９－２３５３８３号公報JP 2009-235383 A 特開２００９－２４２６４９号公報JP 2009-242649 A
　このような状況下、本発明の目的は、印刷物の画像が滲みにくく、画像の光沢性に優れるとともに、ロールメディアに印刷して巻き取る際にもメディアがブロッキングしにくく、印刷ヘッドが腐食しにくいインクジェット印刷用の非水系インク組成物を提供することにある。また、本発明の他の目的は、かかる非水系インク組成物を備える非水系インクセットおよびかかる非水系インク組成物を用いた印刷方法を提供することにある。 Under these circumstances, an object of the present invention is to provide a non-aqueous ink composition for inkjet printing that produces printed images that are less likely to bleed, have excellent image gloss, and are less likely to cause media blocking when printed on roll media and then wound up, and is less likely to corrode the print head. Another object of the present invention is to provide a non-aqueous ink set that includes such a non-aqueous ink composition, and a printing method that uses such a non-aqueous ink composition.
　本発明者らは、上記目的を達成するために、まず、インクジェット印刷用の非水系インク組成物の溶媒として、粘度が低く乾燥性に優れるグリコールエーテル系溶剤と、ラクトン系溶剤を併用することについて検討したところ、好適なラクトン系溶剤であるγ－ブチロラクトンは、例えば５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部のγ－ブチロラクトンとからなる混合液のｐＨが５．４の酸性となることから、非水系インク組成物に用いた場合であっても周囲環境中の水分によってヘッドが腐食する要因となることを確認した。そこで、このような組成での混合液のｐＨが酸性領域とならずに、かつ、ポリ塩化ビニル樹脂等の樹脂を溶解する能力が高い（言い換えれば、樹脂溶解性に優れる）溶媒として、かかる組成での混合液のｐＨが７．０以上であるアミド結合またはウレア結合含有化合物に着目した。かかる組成での混合液のｐＨが７．０以上であるアミド結合またはウレア結合含有化合物であれば、ヘッドの腐食を防止することが可能である。また、アミド結合またはウレア結合含有化合物は、基材に使用される樹脂及びインク中に含まれる樹脂を溶解する能力が高く、沸点２００℃未満のグリコールエーテル系溶剤とともに特定の割合で用いることによって、画像が滲みにくく、画像の光沢性に優れるとともに、ロールメディアに印刷して巻き取る際にもメディアがブロッキングしにくい印刷物が得られることを見出し、本発明を完成させるに至った。 In order to achieve the above object, the present inventors first investigated the use of a glycol ether-based solvent, which has low viscosity and excellent drying properties, in combination with a lactone-based solvent as a solvent for a non-aqueous ink composition for inkjet printing. As a result, it was confirmed that γ-butyrolactone, a suitable lactone-based solvent, is a cause of head corrosion due to moisture in the surrounding environment even when used in a non-aqueous ink composition, because a mixture of, for example, 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of γ-butyrolactone has an acidic pH of 5.4. Therefore, as a solvent that does not have an acidic pH in the mixture in such a composition and has a high ability to dissolve resins such as polyvinyl chloride resin (in other words, has excellent resin solubility), the inventors focused on an amide bond- or urea bond-containing compound, whose mixture in such a composition has a pH of 7.0 or higher. If the mixture in such a composition has a pH of 7.0 or higher, it is possible to prevent head corrosion. In addition, the amide bond or urea bond-containing compound has a high ability to dissolve the resin used in the substrate and the resin contained in the ink, and by using it in a specific ratio together with a glycol ether-based solvent with a boiling point of less than 200°C, it was discovered that it is possible to obtain a printed matter that is less prone to bleeding, has excellent image gloss, and is less prone to media blocking when printed on roll media and wound up, leading to the completion of the present invention.
　従って、本発明の第１の非水系インク組成物は、（Ａ）有機溶媒と（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物であって、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が４．０～３０質量％の範囲内であることを特徴とする、非水系インク組成物である。 Therefore, a first non-aqueous ink composition of the present invention is a non-aqueous ink composition for ink-jet printing, comprising (A) an organic solvent and (B) a resin,
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
(A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The non-aqueous ink composition is characterized in that the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 4.0 to 30% by mass.
　また、本発明の第２の非水系インク組成物は、（Ａ）有機溶媒と（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物であって、
前記非水系インク組成物が、オレンジインクであり、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が１．０～３０質量％の範囲内であることを特徴とする、非水系インク組成物である。 A second non-aqueous ink composition of the present invention is a non-aqueous ink composition for ink-jet printing, comprising (A) an organic solvent and (B) a resin,
the non-aqueous ink composition is an orange ink,
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
(A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The non-aqueous ink composition is characterized in that the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 1.0 to 30% by mass.
　本発明の第１および第２の非水系インク組成物の好適例においては、（Ａ）有機溶媒が、さらに（Ａ－３）沸点が２２０℃以上３００℃未満であるグリコールまたはグリコールエーテル系溶剤を含む。 In a preferred embodiment of the first and second non-aqueous ink compositions of the present invention, (A) the organic solvent further contains (A-3) a glycol or glycol ether solvent having a boiling point of 220°C or higher and lower than 300°C.
　本発明の第１および第２の非水系インク組成物の他の好適例においては、（Ａ－２）アミド結合またはウレア結合含有化合物が、アルキルアミド系溶剤、環状アミド系溶剤、芳香族アミド系溶剤、アルキルウレア系溶剤、および環状ウレア系溶剤より選ばれる少なくとも１種を含む。 In another preferred embodiment of the first and second non-aqueous ink compositions of the present invention, the amide bond or urea bond-containing compound (A-2) contains at least one solvent selected from alkylamide solvents, cyclic amide solvents, aromatic amide solvents, alkylurea solvents, and cyclic urea solvents.
　本発明の第１の非水系インク組成物の他の好適例においては、前記非水系インク組成物が、ブラックインクであり、
前記非水系インク組成物の水抽出物のｐＨが３．０～７．０の範囲内である。 In another preferred embodiment of the first non-aqueous ink composition of the present invention, the non-aqueous ink composition is a black ink,
The pH of the aqueous extract of the non-aqueous ink composition is within the range of 3.0 to 7.0.
　本発明の第１の非水系インク組成物の他の好適例においては、前記非水系インク組成物が、ホワイトインクであり、
前記非水系インク組成物中に含まれる水の量が１０，０００質量ｐｐｍ未満である。 In another preferred embodiment of the first non-aqueous ink composition of the present invention, the non-aqueous ink composition is a white ink,
The amount of water contained in the non-aqueous ink composition is less than 10,000 ppm by mass.
　また、本発明の非水系インクセットは、シアンインク、マゼンタインク、およびイエローインクを少なくとも備えるインクジェット印刷用の非水系インクセットであって、
シアンインク、マゼンタインク、およびイエローインクが、（Ａ）有機溶媒、（Ｂ）樹脂、および（Ｃ）顔料を含み、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が４．０～３０質量％の範囲内であることを特徴とする、非水系インクセットである。 The non-aqueous ink set of the present invention is a non-aqueous ink set for ink-jet printing comprising at least a cyan ink, a magenta ink, and a yellow ink,
The cyan ink, the magenta ink, and the yellow ink each contain (A) an organic solvent, (B) a resin, and (C) a pigment;
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
(A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The non-aqueous ink set is characterized in that the amount of the amide bond or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 4.0 to 30 mass %.
　本発明の非水系インクセットの好適例においては、前記非水系インクセットが、オレンジインクを備え、
オレンジインクが、（Ａ）有機溶媒、（Ｂ）樹脂、および（Ｃ）顔料を含み、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が１．０～３０質量％の範囲内である。 In a preferred embodiment of the non-aqueous ink set of the present invention, the non-aqueous ink set comprises an orange ink,
the orange ink comprises (A) an organic solvent, (B) a resin, and (C) a pigment;
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
(A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 1.0 to 30% by mass.
　また、本発明の第１の印刷方法は、（Ａ）有機溶媒および（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物を用いて印刷層を形成する印刷方法であって、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が４．０～３０質量％の範囲内であることを特徴とする、印刷方法である。 A first printing method of the present invention is a printing method for forming a printed layer using a non-aqueous ink composition for inkjet printing, which comprises (A) an organic solvent and (B) a resin, the method comprising the steps of:
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
(A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The printing method is characterized in that the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 4.0 to 30 mass %.
　本発明の第２の印刷方法は、（Ａ）有機溶媒および（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物を用いて印刷層を形成する印刷方法であって、
前記非水系インク組成物が、オレンジインクであり、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が１．０～３０質量％の範囲内であることを特徴とする、印刷方法である。 A second printing method of the present invention is a printing method for forming a printing layer using a non-aqueous ink composition for inkjet printing, which contains (A) an organic solvent and (B) a resin, comprising the steps of:
the non-aqueous ink composition is an orange ink,
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
(A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The printing method is characterized in that the amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 1.0 to 30% by mass.
　本発明の非水系インク組成物によれば、印刷物の画像が滲みにくく、画像の光沢性に優れるとともに、ロールメディアに印刷して巻き取る際にもメディアがブロッキングしにくく、印刷ヘッドが腐食しにくいインクジェット印刷用の非水系インク組成物を提供することができる。また、本発明の非水系インクセットによれば、かかる非水系インク組成物を備える非水系インクセットを提供することができる。本発明の印刷方法によれば、かかる非水系インク組成物を用いた印刷方法を提供することができる。 The non-aqueous ink composition of the present invention can provide a non-aqueous ink composition for inkjet printing that produces printed images that are less likely to bleed, have excellent image gloss, and is less likely to cause media blocking when printed on roll media and then wound up, and is less likely to corrode the print head. Furthermore, the non-aqueous ink set of the present invention can provide a non-aqueous ink set that includes such a non-aqueous ink composition. The printing method of the present invention can provide a printing method that uses such a non-aqueous ink composition.
　以下に、本発明を詳細に説明する。本発明は、非水系インク組成物、非水系インクセットおよび印刷方法に関する。 The present invention is described in detail below. The present invention relates to a non-aqueous ink composition, a non-aqueous ink set, and a printing method.
　本発明の非水系インク組成物は、有機溶剤および樹脂を含むインクジェット印刷用の非水系インク組成物である。本明細書では、有機溶媒を（Ａ）成分とし、「（Ａ）有機溶媒」とも称する。また、樹脂を（Ｂ）成分とし、「（Ｂ）樹脂」とも称する。 The non-aqueous ink composition of the present invention is a non-aqueous ink composition for inkjet printing that contains an organic solvent and a resin. In this specification, the organic solvent is the (A) component, and is also referred to as the "(A) organic solvent." The resin is the (B) component, and is also referred to as the "(B) resin."
　本明細書において、非水系インク組成物とは、溶媒として水を含まない、また水と任意の割合で混和しないインク組成物を意味する。 In this specification, a non-aqueous ink composition means an ink composition that does not contain water as a solvent and is not miscible with water in any proportion.
　本明細書において、インクジェット印刷用のインク組成物とは、インクジェットプリンタによる印刷に使用できるインク組成物を意味する。 In this specification, an ink composition for inkjet printing means an ink composition that can be used for printing with an inkjet printer.
　本発明の非水系インク組成物は、（Ａ）有機溶剤を含み、本発明の非水系インク組成物中における（Ａ）有機溶剤の量は、８０～９９質量％であることが好ましく、９０～９５質量％であることがより好ましい。 The non-aqueous ink composition of the present invention contains an organic solvent (A), and the amount of the organic solvent (A) in the non-aqueous ink composition of the present invention is preferably 80 to 99% by mass, and more preferably 90 to 95% by mass.
　本発明の非水系インク組成物において、（Ａ）有機溶剤は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物
を含む。 In the non-aqueous ink composition of the present invention, the organic solvent (A) is
The composition comprises (A-1) a glycol ether solvent having a boiling point of less than 200°C, and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of (A-2) the amide bond- or urea bond-containing compound has a pH of 7.0 or higher.
　本明細書では、「沸点２００℃未満のグリコールエーテル系溶剤」を（Ａ－１）成分とし、上記のように「（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤」とも称する。また、「５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部のアミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、アミド結合またはウレア結合含有化合物」を（Ａ－２）成分とし、上記のように「（Ａ－２）アミド結合またはウレア結合含有化合物」とも称する。 In this specification, the "glycol ether-based solvent with a boiling point of less than 200°C" is defined as component (A-1), and is also referred to as "(A-1) glycol ether-based solvent with a boiling point of less than 200°C" as described above. In addition, the "amide bond- or urea bond-containing compound, in which a mixture of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of an amide bond- or urea bond-containing compound has a pH of 7.0 or higher" is defined as component (A-2), and is also referred to as "(A-2) amide bond- or urea bond-containing compound" as described above.
　（Ａ－１）成分のグリコールエーテル系溶剤は、粘度が低く、タグ密閉式引火点が比較的高く、乾燥性が良好な有機溶媒であり、本発明の非水系インク組成物の主溶媒として使用することが好ましい。（Ａ－１）成分のグリコールエーテル系溶剤の好ましい引火点は５０℃以上７５℃以下である。本明細書において、引火点は、タグ密閉法による引火点である。 The glycol ether solvent of component (A-1) is an organic solvent that has a low viscosity, a relatively high tag closed flash point, and good drying properties, and is preferably used as the main solvent for the non-aqueous ink composition of the present invention. The preferred flash point of the glycol ether solvent of component (A-1) is 50°C or higher and 75°C or lower. In this specification, the flash point is the flash point measured by the tag closed flash point method.
　本明細書において、グリコールエーテル系溶剤は、エチレングリコールやプロピレングリコール等のグリコールに基づくアルキルエーテル構造を有する化合物を意味する。グリコールエーテル系溶剤は、その分子の両末端が水酸基であるものや、その分子の片末端または両末端の水酸基の水素がアルキル基やアシル基等の置換基で置換されているものが含まれる。 In this specification, glycol ether solvents refer to compounds that have an alkyl ether structure based on glycols such as ethylene glycol and propylene glycol. Glycol ether solvents include those in which both ends of the molecule are hydroxyl groups, and those in which the hydrogen of the hydroxyl group at one or both ends of the molecule is replaced with a substituent such as an alkyl group or an acyl group.
　（Ａ－１）成分のグリコールエーテル系溶剤は、沸点が２００℃未満であり、好ましくは沸点が１５０～２００℃であり、より好ましくは沸点が１６０～１９０℃である。本明細書において、沸点は、１気圧のときの沸点を指す。（Ａ－１）成分のグリコールエーテル系溶剤の沸点が２００℃未満であることで、インクの乾燥性が向上することから、耐ブロッキング性に優れた印刷物が得られやすくなる。 The glycol ether solvent of component (A-1) has a boiling point of less than 200°C, preferably 150 to 200°C, and more preferably 160 to 190°C. In this specification, the boiling point refers to the boiling point at 1 atmospheric pressure. By having the glycol ether solvent of component (A-1) have a boiling point of less than 200°C, the drying properties of the ink are improved, making it easier to obtain printed matter with excellent blocking resistance.
　（Ａ－１）成分のグリコールエーテル系溶剤は、下記一般式（１）で表されるグリコールエーテル系溶剤を含むことが好ましい。
　　Ｒ１－（ＯＲ２）ｎ－Ｏ－Ｒ３　　　（１）
　式（１）において、
　ｎは、１以上４以下の整数であり、
　Ｒ１は、炭素数１以上８以下の分岐していてもよいアルキル基又は炭素数１以上４以下のアシル基であり、
　Ｒ２は、炭素数１以上４以下の分岐していてもよいアルキレン基であり、
　Ｒ３は、水素又は炭素数１以上４以下の分岐していてもよいアルキル基又は炭素数１以上４以下のアシル基である。 The glycol ether solvent of the component (A-1) preferably contains a glycol ether solvent represented by the following general formula (1):
R1-(OR2)n-O-R3 (1)
In formula (1),
n is an integer of 1 to 4,
R1 is an alkyl group having 1 to 8 carbon atoms which may be branched or an acyl group having 1 to 4 carbon atoms;
R2 is an optionally branched alkylene group having 1 to 4 carbon atoms,
R3 is hydrogen, an alkyl group having 1 to 4 carbon atoms which may be branched, or an acyl group having 1 to 4 carbon atoms.
　（Ａ－１）成分のグリコールエーテル系溶剤は、ジアルキレングリコールジアルキルエーテルまたはジアルキレングリコールモノアルキルエーテルアセテートを含むことが好ましく、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル、およびプロピレングリコールモノメチルエーテルアセテートから選ばれる少なくとも１種を含むことがより好ましい。 The glycol ether solvent of component (A-1) preferably contains a dialkylene glycol dialkyl ether or a dialkylene glycol monoalkyl ether acetate, and more preferably contains at least one selected from diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate.
　本発明の非水系インク組成物において、（Ａ）有機溶剤中の（Ａ－１）成分の量は、６０～９５質量％の範囲内であることが好ましく、７５～９５質量％の範囲内であることが好ましい。（Ａ－１）成分は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In the non-aqueous ink composition of the present invention, the amount of component (A-1) in the organic solvent (A) is preferably within the range of 60 to 95% by mass, and more preferably within the range of 75 to 95% by mass. The component (A-1) may be used alone or in combination of two or more types.
　（Ａ－２）成分のアミド結合またはウレア結合含有化合物は、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０より高くなり、酸性領域とならないことからヘッドを腐食せず、かつ、ポリ塩化ビニル樹脂等の樹脂を溶解する能力が高い（言い換えれば、樹脂溶解性に優れる）有機溶媒である。（Ａ－２）成分を溶媒として用いると、基材上のインクを広げずに浸透させる効果が得られる。このため、（Ａ－２）成分のアミド結合またはウレア結合含有化合物は、上述した（Ａ－１）成分のグリコールエーテル系溶剤と併用することによって、画像が滲みにくく、ロールメディアに印刷して巻き取る際にもメディアがブロッキングしにくい印刷物を提供することができる。ここで、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部のアミド結合またはウレア結合含有化合物とからなる混合液のｐＨを７．０以上とした理由としては、インクのｐＨを酸性としないことでヘッドを腐食から守れるのではといった着想によるものである。ジエチレングリコールエチルメチルエーテルは（Ａ－１）成分のグリコールエーテル系溶剤であり、本発明においてはこの（Ａ－１）グリコールエーテルと水と（Ａ－２）成分のアミド結合またはウレア結合含有化合物を含む水溶液のｐＨが強い酸性領域とならないことが重要であると考え、実際のインクの配合割合に近似した特定の混合割合における水溶液のｐＨを７．０以上と規定した。 The amide bond- or urea bond-containing compound of component (A-2) is an organic solvent that does not corrode the head because the pH of a mixture consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) is higher than 7.0 and is not in the acidic range, and has a high ability to dissolve resins such as polyvinyl chloride resin (in other words, has excellent resin solubility). When component (A-2) is used as a solvent, it has the effect of allowing the ink on the substrate to penetrate without spreading. Therefore, when the amide bond- or urea bond-containing compound of component (A-2) is used in combination with the glycol ether-based solvent of component (A-1) described above, it is possible to provide a printed matter in which the image is less likely to bleed and the media is less likely to block when printed on roll media and wound up. Here, the reason why the pH of the mixture consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of an amide bond- or urea bond-containing compound is set to 7.0 or more is due to the idea that the head can be protected from corrosion by not making the pH of the ink acidic. Diethylene glycol ethyl methyl ether is a glycol ether-based solvent of component (A-1), and in the present invention, it is considered important that the pH of the aqueous solution containing this glycol ether (A-1), water, and the amide bond- or urea bond-containing compound of component (A-2) does not fall into a strongly acidic range, and the pH of the aqueous solution at a specific mixing ratio that is close to the actual ink mixing ratio is specified to be 7.0 or more.
　（Ａ－２）成分のアミド結合またはウレア結合含有化合物は、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部のアミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上であり、好ましくは７．０～１０．０であり、より好ましくは７．０～９．５である。 The amide bond or urea bond-containing compound of component (A-2) is a mixture of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of an amide bond or urea bond-containing compound, the pH of which is 7.0 or higher, preferably 7.0 to 10.0, and more preferably 7.0 to 9.5.
　（Ａ－２）成分のアミド結合またはウレア結合含有化合物は、アルキルアミド系溶剤、環状アミド系溶剤、芳香族アミド系溶剤、アルキルウレア系溶剤、および環状ウレア系溶剤より選ばれる少なくとも１種を含むことが好ましい。 The amide bond or urea bond-containing compound of component (A-2) preferably contains at least one solvent selected from alkylamide solvents, cyclic amide solvents, aromatic amide solvents, alkylurea solvents, and cyclic urea solvents.
　アルキルアミド系溶剤の具体例としては、３－メトキシ―Ｎ，Ｎ－ジメチルプロパンアミド等が挙げられる。環状アミド系溶剤の具体例としては、２－ピロリドン、ε－カプロラクタム等が挙げられる。芳香族アミド系溶剤の具体例としては、ベンズアミド等が挙げられる。アルキルウレア系溶剤としてはＮ－メチル尿素等が挙げられる。環状ウレア系溶剤としては１，３－ジメチル－２－イミダゾリジノン等が挙げられる。 Specific examples of alkylamide solvents include 3-methoxy-N,N-dimethylpropanamide. Specific examples of cyclic amide solvents include 2-pyrrolidone and ε-caprolactam. Specific examples of aromatic amide solvents include benzamide. Examples of alkylurea solvents include N-methylurea. Examples of cyclic urea solvents include 1,3-dimethyl-2-imidazolidinone.
　（Ａ－２）成分のアミド結合またはウレア結合含有化合物としては、環状ウレア系溶剤が好ましく、イミダゾリジノン系溶剤がより好ましく、特には、１，３－ジメチル－２－イミダゾリジノンが最も好ましい。 As the amide bond or urea bond-containing compound of component (A-2), cyclic urea solvents are preferred, imidazolidinone solvents are more preferred, and 1,3-dimethyl-2-imidazolidinone is particularly preferred.
　本発明の非水系インク組成物において、（Ａ）有機溶剤中の（Ａ－２）成分の量は、４．０～３０質量％の範囲内であることが好ましく、５～３０質量％の範囲内であることがより好ましく、５～１５質量％の範囲内であることがさらに好ましい。（Ａ－２）成分は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。（Ａ）有機溶剤中の（Ａ－２）成分の量が３０質量％以下であると、画像の光沢性を向上させることができる。 In the non-aqueous ink composition of the present invention, the amount of component (A-2) in organic solvent (A) is preferably within the range of 4.0 to 30% by mass, more preferably within the range of 5 to 30% by mass, and even more preferably within the range of 5 to 15% by mass. The component (A-2) may be used alone or in combination of two or more types. When the amount of component (A-2) in organic solvent (A) is 30% by mass or less, the glossiness of the image can be improved.
　また、本発明者は、本発明の非水系インク組成物がオレンジインクである場合、（Ａ）有機溶剤中の（Ａ－２）成分の量が４．０質量％を下回る場合であっても、（Ａ－２）成分による効果を十分に発揮できることを見出した。すなわち、本発明の非水系インク組成物がオレンジインクである場合、（Ａ）有機溶剤中の（Ａ－２）成分の量は、１．０～３０質量％の範囲内であることが好ましく、１．５～２０質量％の範囲内であることがより好ましく、２．０～１５質量％の範囲内であることがさらに好ましく、２．０～１２質量％の範囲内であることが特に好ましい。 The inventors have also found that when the non-aqueous ink composition of the present invention is an orange ink, the effect of the (A-2) component can be fully exhibited even when the amount of the (A-2) component in the (A) organic solvent is less than 4.0% by mass. In other words, when the non-aqueous ink composition of the present invention is an orange ink, the amount of the (A-2) component in the (A) organic solvent is preferably in the range of 1.0 to 30% by mass, more preferably in the range of 1.5 to 20% by mass, even more preferably in the range of 2.0 to 15% by mass, and particularly preferably in the range of 2.0 to 12% by mass.
　本発明の非水系インク組成物において、（Ａ）有機溶剤中の（Ａ－１）成分の量の（Ａ）有機溶剤中の（Ａ－２）成分の量に対する比は、２～１０であることが好ましく、４～８であることがより好ましい。本明細書では、（Ａ）有機溶剤中の（Ａ－１）成分の量の（Ａ）有機溶剤中の（Ａ－２）成分の量に対する比を「（Ａ－１）／（Ａ－２）」と表現する場合がある。ここで、（Ａ）有機溶剤中の（Ａ－１）成分の量の（Ａ）有機溶剤中の（Ａ－２）成分の量に対する比は、質量基準である。 In the non-aqueous ink composition of the present invention, the ratio of the amount of component (A-1) in organic solvent (A) to the amount of component (A-2) in organic solvent (A) is preferably 2 to 10, and more preferably 4 to 8. In this specification, the ratio of the amount of component (A-1) in organic solvent (A) to the amount of component (A-2) in organic solvent (A) may be expressed as "(A-1)/(A-2)." Here, the ratio of the amount of component (A-1) in organic solvent (A) to the amount of component (A-2) in organic solvent (A) is based on mass.
　本発明の非水系インク組成物において、（Ａ）有機溶剤は、上記（Ａ－１）成分および（Ａ－２）成分に加えて、さらに、
（Ａ－３）沸点が２２０℃以上３００℃未満であるグリコールまたはグリコールエーテル系溶剤
を含むことが好ましい。特に、安全性の観点より、（Ａ－３）成分は沸点が２２０℃以上３００℃未満の両末端が水酸基であるグリコールであることが好ましい。 In the non-aqueous ink composition of the present invention, the organic solvent (A) further comprises, in addition to the above-mentioned components (A-1) and (A-2),
It is preferable to contain (A-3) a glycol or glycol ether solvent having a boiling point of 220° C. or more and less than 300° C. In particular, from the viewpoint of safety, the component (A-3) is preferably a glycol having a boiling point of 220° C. or more and less than 300° C. and both terminals being hydroxyl groups.
　本明細書では、「沸点が２２０℃以上３００℃未満であるグリコールまたはグリコールエーテル系溶剤」を（Ａ－３）成分とし、上記のように「（Ａ－３）沸点が２２０℃以上３００℃未満であるグリコールまたはグリコールエーテル系溶剤」とも称する。 In this specification, "a glycol or glycol ether-based solvent having a boiling point of 220°C or higher and lower than 300°C" is defined as component (A-3), and as described above, is also referred to as "(A-3) a glycol or glycol ether-based solvent having a boiling point of 220°C or higher and lower than 300°C."
　（Ａ－３）成分のグリコールまたはグリコールエーテル系溶剤は、ヘッド部におけるインクの乾燥を防止し、再吐出性を向上させることができるとともに、印刷物の光沢度の向上に寄与する。 The glycol or glycol ether-based solvent in component (A-3) prevents the ink from drying out in the head, improving re-ejection properties and contributing to improved gloss of the printed material.
　（Ａ－３）成分としては、例えば、ジエチレングリコール、トリエチレングリコール、トリプロピレングリコール、ポリプロピレングリコール、ジエチレングリコール－２－エチルヘキシルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノブチルエーテル、ジプロピレングリコール、エチレングリコールモノフェニルエーテル、トリエチレングリコールモノメチルエーテル、ジエチレングリコールジブチルエーテル等が挙げられる。（Ａ－３）成分は、（Ａ－１）成分および（Ａ－２）成分との相溶性に優れることが好ましい。 Examples of the (A-3) component include diethylene glycol, triethylene glycol, tripropylene glycol, polypropylene glycol, diethylene glycol-2-ethylhexyl ether, diethylene glycol monohexyl ether, diethylene glycol monobutyl ether, dipropylene glycol, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, etc. It is preferable that the (A-3) component has excellent compatibility with the (A-1) component and the (A-2) component.
　（Ａ－３）成分の量が多すぎると、印刷物の耐ブロッキング性が低下する場合があることから、本発明の非水系インク組成物において、（Ａ）有機溶媒中における（Ａ－３）成分の量は、０．１～５．０質量％の範囲内であることが好ましく、０．１～２．０質量％であることがより好ましく、０．１～１．０質量％であることがさらに好ましく、０．１～０．７質量％の範囲内であることが最も好ましい。（Ａ－３）成分は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 If the amount of component (A-3) is too large, the blocking resistance of the printed matter may decrease, so in the non-aqueous ink composition of the present invention, the amount of component (A-3) in the organic solvent (A) is preferably within the range of 0.1 to 5.0% by mass, more preferably 0.1 to 2.0% by mass, even more preferably 0.1 to 1.0% by mass, and most preferably within the range of 0.1 to 0.7% by mass. The component (A-3) may be used alone or in combination of two or more types.
　本発明の非水系インク組成物において、（Ａ）有機溶剤は、さらに、
（Ａ－４）沸点が１５０℃未満であり、（Ａ－１）成分または（Ａ－２）成分に該当しない有機溶媒
を含むことができる。 In the non-aqueous ink composition of the present invention, the organic solvent (A) further comprises
(A-4) An organic solvent having a boiling point of less than 150° C. and not corresponding to the components (A-1) and (A-2) may be included.
　本明細書では、沸点が１５０℃未満であって、（Ａ－１）成分にも（Ａ－２）成分にも該当しない有機溶媒を（Ａ－４）成分とし、上記のように「（Ａ－４）沸点が１５０℃未満であり、（Ａ－１）成分または（Ａ－２）成分に該当しない有機溶媒」とも称する。 In this specification, an organic solvent that has a boiling point of less than 150°C and does not fall under either component (A-1) or component (A-2) is referred to as component (A-4), and as described above, is also referred to as "(A-4) an organic solvent that has a boiling point of less than 150°C and does not fall under either component (A-1) or component (A-2)."
　（Ａ－４）成分の有機溶媒は、沸点が低いため、インクの乾燥性を向上させることができる。 The organic solvent in component (A-4) has a low boiling point, which can improve the drying properties of the ink.
　（Ａ－４）成分としては、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、シクロペンタノン等が挙げられる。（Ａ－４）成分は、（Ａ－１）成分および（Ａ－２）成分との相溶性に優れることが好ましい。 Examples of the (A-4) component include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclopentanone. It is preferable that the (A-4) component has excellent compatibility with the (A-1) and (A-2) components.
　本発明の非水系インク組成物において、（Ａ）有機溶剤中における（Ａ－４）成分の量は、０．５～２．０質量％の範囲内であることが好ましく、０．５～１．０質量％の範囲内であることがより好ましい。（Ａ－２）成分は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In the non-aqueous ink composition of the present invention, the amount of component (A-4) in the organic solvent (A) is preferably within the range of 0.5 to 2.0% by mass, and more preferably within the range of 0.5 to 1.0% by mass. The component (A-2) may be used alone or in combination of two or more types.
　本発明の非水系インク組成物は、γ－ブチロラクトンを含まないことが好ましい。 The non-aqueous ink composition of the present invention preferably does not contain gamma-butyrolactone.
　本発明の非水系インク組成物は、（Ｂ）樹脂を含み、本発明の非水系インク組成物中における（Ｂ）樹脂の量は、１～５質量％であることが好ましく、１～３質量％であることがより好ましい。（Ｂ）樹脂は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The non-aqueous ink composition of the present invention contains a (B) resin, and the amount of the (B) resin in the non-aqueous ink composition of the present invention is preferably 1 to 5 mass %, and more preferably 1 to 3 mass %. The (B) resin may be used alone or in combination of two or more types.
　（Ｂ）樹脂としては、例えば、ポリ塩化ビニル（塩化ビニル樹脂）、ポリ酢酸ビニル、塩化ビニル－酢酸ビニル共重合体（塩化ビニル／酢酸ビニル共重合樹脂）、塩化ビニル樹脂、塩化ゴム、塩素化ポリエチレン樹脂、塩素化ポリプロピレン樹脂、塩素化エチレン－ビニルアセテート樹脂、アクリル樹脂、アクリルシリコーン樹脂、スチレンアクリル共重合樹脂、ポリスチレン樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリオレフィン樹脂、シリコーン樹脂、フッ素樹脂、エポキシ樹脂、ポリエステル樹脂、ケトン樹脂、フェノール樹脂、ポリビニルアルコール、ポリビニルアルコール誘導体（アニオン変性ポリビニルアルコール等）、セルロース、セルロース誘導体（ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、酢酸セルロース等）、ロジン系樹脂、油性樹脂、石油樹脂、アルキッド樹脂、アルギン酸、アルギン酸誘導体（アルギン酸プロピレングリコールエステル等）等が挙げられる。また、これら樹脂の変性物も含まれ、例えば、ヒドロキシアルキルエーテル化変性、カルボン酸変性などの変性が挙げられる。これらのうち、基材への付着性や印刷膜の耐久性の観点から、アクリル樹脂、塩化ビニル樹脂および塩化ビニル／酢酸ビニル共重合樹脂が好ましい。 (B) resins include, for example, polyvinyl chloride (vinyl chloride resin), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer (vinyl chloride/vinyl acetate copolymer resin), vinyl chloride resin, chlorinated rubber, chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated ethylene-vinyl acetate resin, acrylic resin, acrylic silicone resin, styrene-acrylic copolymer resin, polystyrene resin, polyamide resin, polyurethane resin, polyolefin resin, silicone resin, fluororesin, epoxy resin, polyester resin, ketone resin, phenol resin, polyvinyl alcohol, polyvinyl alcohol derivatives (anion-modified polyvinyl alcohol, etc.), cellulose, cellulose derivatives (hydroxymethylcellulose, hydroxyethylcellulose, cellulose acetate, etc.), rosin resin, oil-based resin, petroleum resin, alkyd resin, alginic acid, alginic acid derivatives (propylene glycol alginate, etc.), etc. Modified products of these resins are also included, such as hydroxyalkyl etherification modifications and carboxylic acid modifications. Of these, acrylic resins, vinyl chloride resins, and vinyl chloride/vinyl acetate copolymer resins are preferred from the viewpoints of adhesion to the substrate and durability of the printed film.
　本発明の非水系インク組成物は、染料や顔料等の着色剤を含有してもよいが、その場合は、耐候性の観点から、顔料を含有することが好ましい。例えば、金属顔料を用いて、メタリックインクとすることも可能である。着色剤の含有量は、例えばインク組成物中０．１～１５質量％である。着色剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。本明細書では、顔料を（Ｃ）成分とし、「（Ｃ）顔料」とも称する。 The non-aqueous ink composition of the present invention may contain a colorant such as a dye or pigment, but in this case, it is preferable for the composition to contain a pigment from the viewpoint of weather resistance. For example, a metallic ink can be produced by using a metal pigment. The content of the colorant in the ink composition is, for example, 0.1 to 15 mass %. The colorant may be used alone or in combination of two or more types. In this specification, the pigment is referred to as component (C) and is also referred to as "pigment (C)".
　着色剤の具体例としては、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１、２、３、４、５、６、７、９、１０、１２、１３、１４、１５、１６、１７、２４、３２、３４、３５、３６、３７、４１、４２、４３、４９、５３、５５、６０、６１、６２、６３、６５、７３、７４、７５、７７、８１、８３、８７、９３、９４、９５、９７、９８、９９、１００、１０１、１０４、１０５、１０６、１０８、１０９、１１０、１１１、１１３、１１４、１１６、１１７、１１９、１２０、１２３、１２４、１２６、１２７、１２８、１２９、１３０、１３３、１３８、１３９、１５０、１５１、１５２、１５３、１５４、１５５、１６５、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７９、１８０、１８１、１８２、１８３、１８４、１８５、１９１、１９３、１９４、１９９、２０５、２０６、２０９、２１２、２１３、２１４、２１５、２１９、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　１、２、３、４、５、１３、１５、１６、１７、１９、２０、２１、２４、３１、３４、３６、３８、４０、４３、４６、４８、４９、５１、６０、６１、６２、６４、６５、６６、６７、６８、６９、７１、７２、７３、７４、８１、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１、２、３、４、５、６、７、８、９、１０、１１、１２、１４、１５、１６、１７、１８、２１、２２、２３、３１、３２、３８、４１、４８、４８：１、４８：２、４８：３、４８：４、４８：５、４９、５２、５２：１、５２：２、５３：１、５４、５７：１、５８、６０：１、６３、６４：１、６８、８１：１、８３、８８、８９、９５、１０１、１０４、１０５、１０８、１１２、１１４、１１９、１２２、１２３、１３６、１４４、１４６、１４７、１４９、１５０、１６４、１６６、１６８、１６９、１７０、１７１、１７２、１７５、１７６、１７７、１７８、１７９、１８０、１８１、１８２、１８３、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１１、２１３、２１４、２１６、２２０、２２０、２２１、２２４、２２６、２３７、２３８、２３９、２４２、２４５、２４７、２４８、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２６０、２６２、２６３、２６４、２６６、２６８、２６９、２７０、２７１、２７２、２７９、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１、２、３、３：１、３：３、５：１、１３、１５、１６、１７、１９、２３、２５、２７、２９、３１、３２、３６、３７、３８、４２、５０、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１、１５、１５：１、１５：２、１５：３、１５：４、１５：５、１５：６、１６、１７：１、２４、２４：１、２５、２６、２７、２８、２９、３６、５６、６０、６１、６２、６３、７５、７９、８０、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　１、４、７、８、１０、１５、１７、２６、３６、５０、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｒｏｗｎ　５、６、２３、２４、２５、３２、４１、４２、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　１、６、７、９、１０、１１、２０、２６、２８、３１、３２、３４、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｗｈｉｔｅ　１、２、４、５、６、７、１１、１２、１８、１９、２１、２２、２３、２６、２７、２８、
アルミニウムフレーク、ガラスフレーク、パール顔料及び中空粒子等が挙げられる。 Specific examples of colorants include:
C. I. Pigment Yellow 1,2,3,4,5,6,7,9,10,12,13,14,15,16,17,24,32,34,35,36,37,41,42,43,49,53,55,60,61,62,63,65,73,74,75,77,81,83 , 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120,123,124,126,127,128,129,130,133,138,139,150,151,152,153,154,155,165,167,168,169,170,172,173,174,175,176,179,180,181,1 82, 183, 184, 185, 191, 193, 194, 199, 205, 206, 209, 212, 213, 214, 215, 219,
C. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 20, 21, 24, 31, 34, 36, 38, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 38, 41, 48, 48:1, 48:2, 48:3, 48:4, 48:5, 49, 52, 52:1, 52:2, 53:1, 54, 57:1, 5 8, 60:1, 63, 64:1, 68, 81:1, 83, 88, 89, 95, 101, 104, 105, 108, 112, 114, 119, 122, 123, 136, 144, 146, 147, 149, 150, 164, 166, 168, 169, 170, 171,172,175,176,177,178,179,180,181,182,183,184,185,187,188,190,193,194,200,202,206,207,208,209,210,211,213,214,216,220,2 20, 221, 224, 226, 237, 238, 239, 242, 245, 247, 248, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 268, 269, 270, 271, 272, 279,
C. I. Pigment Violet 1, 2, 3, 3:1, 3:3, 5:1, 13, 15, 16, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 42, 50,
C. I. Pigment Blue 1,15,15:1,15:2,15:3,15:4,15:5,15:6,16,17:1,24,24:1,25,26,27,28,29,36,56,60,61,62,63,75,79,80,
C. I. Pigment Green 1, 4, 7, 8, 10, 15, 17, 26, 36, 50,
C. I. Pigment Brown 5, 6, 23, 24, 25, 32, 41, 42,
C. I. Pigment Black 1, 6, 7, 9, 10, 11, 20, 26, 28, 31, 32, 34,
C. I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28,
Examples include aluminum flakes, glass flakes, pearl pigments, and hollow particles.
　これらの中でも、得られる膜の耐候性と色再現性の観点から、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　７、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：３、１５：４、２８、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１０１、１２２、２０２、２５４、２８２、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１９、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｗｈｉｔｅ　６、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　４２、１２０、１３８、１３９、１５０、１５１、１５５、２１３、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　４３、６４、７１、７３、８３が好ましい。 Among these, from the viewpoint of weather resistance and color reproducibility of the obtained film,
C. I. Pigment Black 7,
C. I. Pigment Blue 15:3, 15:4, 28,
C. I. Pigment Red 101, 122, 202, 254, 282,
C. I. Pigment Violet 19,
C. I. Pigment White 6,
C. I. Pigment Yellow 42, 120, 138, 139, 150, 151, 155, 213, C. I. Pigment Orange 43, 64, 71, 73, 83 are preferred.
　吐出安定性の観点から、インク組成物中に分散している顔料粒子は、体積平均粒子径が０．０５～０．４μｍであり且つ体積最大粒子径が０．２～１μｍであることが好ましい。体積平均粒子径が０．４μｍより大きく且つ体積最大粒子径が１μｍよりも大きいと、インク組成物を安定に吐出することが困難となる傾向がある。なお、体積平均粒子径及び体積最大粒子径は、動的光散乱法を用いた測定機器によって測定できる。 From the viewpoint of ejection stability, it is preferable that the pigment particles dispersed in the ink composition have a volume average particle diameter of 0.05 to 0.4 μm and a volume maximum particle diameter of 0.2 to 1 μm. If the volume average particle diameter is greater than 0.4 μm and the volume maximum particle diameter is greater than 1 μm, it tends to be difficult to eject the ink composition stably. The volume average particle diameter and volume maximum particle diameter can be measured using a measuring device that uses a dynamic light scattering method.
　本発明の非水系インク組成物は、顔料を分散させるために、必要に応じて顔料分散剤を更に含有してもよい。顔料分散剤の含有量は、例えばインク組成物中０．１～５質量％である。顔料分散剤は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The non-aqueous ink composition of the present invention may further contain a pigment dispersant as necessary to disperse the pigment. The content of the pigment dispersant in the ink composition is, for example, 0.1 to 5 mass %. The pigment dispersant may be used alone or in combination of two or more types.
　顔料分散剤の具体例としては、
ＡＮＴＩ－ＴＥＲＲＡ－Ｕ、ＡＮＴＩ－ＴＥＲＲＡ－Ｕ１００、
ＡＮＴＩ－ＴＥＲＲＡ－２０４、ＡＮＴＩ－ＴＥＲＲＡ－２０５、
ＤＩＳＰＥＲＢＹＫ－１０１、ＤＩＳＰＥＲＢＹＫ－１０２、
ＤＩＳＰＥＲＢＹＫ－１０３、ＤＩＳＰＥＲＢＹＫ－１０６、
ＤＩＳＰＥＲＢＹＫ－１０８、ＤＩＳＰＥＲＢＹＫ－１０９、
ＤＩＳＰＥＲＢＹＫ－１１０、ＤＩＳＰＥＲＢＹＫ－１１１、
ＤＩＳＰＥＲＢＹＫ－１１２、ＤＩＳＰＥＲＢＹＫ－１１６、
ＤＩＳＰＥＲＢＹＫ－１３０、ＤＩＳＰＥＲＢＹＫ－１４０、
ＤＩＳＰＥＲＢＹＫ－１４２、ＤＩＳＰＥＲＢＹＫ－１４５、
ＤＩＳＰＥＲＢＹＫ－１６１、ＤＩＳＰＥＲＢＹＫ－１６２、
ＤＩＳＰＥＲＢＹＫ－１６３、ＤＩＳＰＥＲＢＹＫ－１６４、
ＤＩＳＰＥＲＢＹＫ－１６６、ＤＩＳＰＥＲＢＹＫ－１６７、
ＤＩＳＰＥＲＢＹＫ－１６８、ＤＩＳＰＥＲＢＹＫ－１７０、
ＤＩＳＰＥＲＢＹＫ－１７１、ＤＩＳＰＥＲＢＹＫ－１７４、
ＤＩＳＰＥＲＢＹＫ－１８０、ＤＩＳＰＥＲＢＹＫ－１８２、
ＤＩＳＰＥＲＢＹＫ－１８３、ＤＩＳＰＥＲＢＹＫ－１８４、
ＤＩＳＰＥＲＢＹＫ－１８５、ＤＩＳＰＥＲＢＹＫ－２０００、
ＤＩＳＰＥＲＢＹＫ－２００１、ＤＩＳＰＥＲＢＹＫ－２００８、
ＤＩＳＰＥＲＢＹＫ－２００９、ＤＩＳＰＥＲＢＹＫ－２０２０、
ＤＩＳＰＥＲＢＹＫ－２０２５、ＤＩＳＰＥＲＢＹＫ－２０５０、
ＤＩＳＰＥＲＢＹＫ－２０７０、ＤＩＳＰＥＲＢＹＫ－２０９６、
ＤＩＳＰＥＲＢＹＫ－２１５０、ＤＩＳＰＥＲＢＹＫ－２１５５、
ＤＩＳＰＥＲＢＹＫ－２１６３、ＤＩＳＰＥＲＢＹＫ－２１６４、
ＢＹＫ－Ｐ１０４、ＢＹＫ－Ｐ１０４Ｓ、ＢＹＫ－Ｐ１０５、
ＢＹＫ－９０７６、ＢＹＫ－９０７７、ＢＹＫ－２２０Ｓ、ＢＹＫＪＥＴ－９１５０、ＢＹＫＪＥＴ－９１５１（以上、ビックケミー・ジャパン社製）、
Ｓｏｌｓｐｅｒｓｅ３０００、Ｓｏｌｓｐｅｒｓｅ５０００、
Ｓｏｌｓｐｅｒｓｅ９０００、Ｓｏｌｓｐｅｒｓｅ１１２００、
Ｓｏｌｓｐｅｒｓｅ１３２４０、Ｓｏｌｓｐｅｒｓｅ１３６５０、
Ｓｏｌｓｐｅｒｓｅ１３９４０、Ｓｏｌｓｐｅｒｓｅ１６０００、
Ｓｏｌｓｐｅｒｓｅ１７０００、Ｓｏｌｓｐｅｒｓｅ１８０００、
Ｓｏｌｓｐｅｒｓｅ２００００、Ｓｏｌｓｐｅｒｓｅ２１０００、
Ｓｏｌｓｐｅｒｓｅ２４０００ＳＣ、Ｓｏｌｓｐｅｒｓｅ２４０００ＧＲ、
Ｓｏｌｓｐｅｒｓｅ２６０００、Ｓｏｌｓｐｅｒｓｅ２７０００、
Ｓｏｌｓｐｅｒｓｅ２８０００、Ｓｏｌｓｐｅｒｓｅ３２０００、
Ｓｏｌｓｐｅｒｓｅ３２５００、Ｓｏｌｓｐｅｒｓｅ３２５５０、
Ｓｏｌｓｐｅｒｓｅ３２６００、Ｓｏｌｓｐｅｒｓｅ３３０００、
Ｓｏｌｓｐｅｒｓｅ３４７５０、Ｓｏｌｓｐｅｒｓｅ３５１００、
Ｓｏｌｓｐｅｒｓｅ３５２００、Ｓｏｌｓｐｅｒｓｅ３６０００、
Ｓｏｌｓｐｅｒｓｅ３６６００、Ｓｏｌｓｐｅｒｓｅ３７５００、
Ｓｏｌｓｐｅｒｓｅ３８５００、Ｓｏｌｓｐｅｒｓｅ３９０００、
Ｓｏｌｓｐｅｒｓｅ４１０００、Ｓｏｌｓｐｅｒｓｅ５４０００、
Ｓｏｌｓｐｅｒｓｅ５５０００、Ｓｏｌｓｐｅｒｓｅ５６０００、
Ｓｏｌｓｐｅｒｓｅ７１０００、Ｓｏｌｓｐｅｒｓｅ７６５００、
ＳｏｌｓｐｅｒｓｅＸ３００（以上、ルブリゾール社製）、
ディスパロンＤＡ－７３０１、ディスパロンＤＡ－３２５、ディスパロンＤＡ－３７５、ディスパロンＤＡ－２３４（以上、楠本化成社製）、
フローレンＡＦ－１０００、フローレンＤＯＰＡ－１５Ｂ、フローレンＤＯＰＡ－１５ＢＨＦＳ、フローレンＤＯＰＡ－１７ＨＦ、フローレンＤＯＰＡ－２２、フローレンＤＯＰＡ－３３、フローレンＧ－６００、フローレンＧ－７００、フローレンＧ－７００ＡＭＰ、フローレンＧ－７００ＤＭＥＡ、フローレンＧ－８２０、フローレンＧ－９００、フローレンＧＷ－１５００、フローレンＫＤＧ－２４００、フローレンＮＣ－５００、フローレンＷＫ－１３Ｅ、（以上、共栄社化学社製）、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６１０、ＴＥＧＯ　Ｄｉｓｐｅｒｓ６１０Ｓ、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６３０、ＴＥＧＯ　Ｄｉｓｐｅｒｓ６５０、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６５２、ＴＥＧＯ　Ｄｉｓｐｅｒｓ６５５、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６６２Ｃ、ＴＥＧＯ　Ｄｉｓｐｅｒｓ６７０、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ６８５、ＴＥＧＯ　Ｄｉｓｐｅｒｓ７００、
ＴＥＧＯ　Ｄｉｓｐｅｒｓ７１０、ＴＥＧＯ　Ｄｉｓｐｅｒｓ７４０Ｗ、
ＬＩＰＯＴＩＮ　Ａ、ＬＩＰＯＴＩＮ　ＢＬ、
ＬＩＰＯＴＩＮ　ＤＢ、ＬＩＰＯＴＩＮ　ＳＢ（以上、エボニック・デグサ社製）、
ＰＢ８２１、ＰＢ８２２、ＰＮ４１１、ＰＡ１１１（以上、味の素ファインテクノ社製）、
テキサホール９６３、テキサホール９６４、テキサホール９８７、テキサホールＰ６０、テキサホールＰ６１、テキサホールＰ６３、テキサホール３２５０、テキサホールＳＦ７１、テキサホールＵＶ２０、テキサホールＵＶ２１（以上、コグニス社製）、
ＢｏｒｃｈｉＧｅｎＳＮ８８、ＢｏｒｃｈｉＧｅｎ０４５１（以上、ボーシャス社製）等が挙げられる。 Specific examples of pigment dispersants include:
ANTI-TERRA-U, ANTI-TERRA-U100,
ANTI-TERRA-204, ANTI-TERRA-205,
DISPERBYK-101, DISPERBYK-102,
DISPERBYK-103, DISPERBYK-106,
DISPERBYK-108, DISPERBYK-109,
DISPERBYK-110, DISPERBYK-111,
DISPERBYK-112, DISPERBYK-116,
DISPERBYK-130, DISPERBYK-140,
DISPERBYK-142, DISPERBYK-145,
DISPERBYK-161, DISPERBYK-162,
DISPERBYK-163, DISPERBYK-164,
DISPERBYK-166, DISPERBYK-167,
DISPERBYK-168, DISPERBYK-170,
DISPERBYK-171, DISPERBYK-174,
DISPERBYK-180, DISPERBYK-182,
DISPERBYK-183, DISPERBYK-184,
DISPERBYK-185, DISPERBYK-2000,
DISPERBYK-2001, DISPERBYK-2008,
DISPERBYK-2009, DISPERBYK-2020,
DISPERBYK-2025, DISPERBYK-2050,
DISPERBYK-2070, DISPERBYK-2096,
DISPERBYK-2150, DISPERBYK-2155,
DISPERBYK-2163, DISPERBYK-2164,
BYK-P104, BYK-P104S, BYK-P105,
BYK-9076, BYK-9077, BYK-220S, BYKJET-9150, BYKJET-9151 (all manufactured by BYK Japan),
Solsperse3000, Solsperse5000,
Solsperse9000, Solsperse11200,
Solsperse13240, Solsperse13650,
Solsperse13940, Solsperse16000,
Solsperse17000, Solsperse18000,
Solsperse20000, Solsperse21000,
Solsperse24000SC, Solsperse24000GR,
Solsperse26000, Solsperse27000,
Solsperse28000, Solsperse32000,
Solsperse32500, Solsperse32550,
Solsperse32600, Solsperse33000,
Solsperse34750, Solsperse35100,
Solsperse35200, Solsperse36000,
Solsperse36600, Solsperse37500,
Solsperse38500, Solsperse39000,
Solsperse41000, Solsperse54000,
Solsperse55000, Solsperse56000,
Solsperse71000, Solsperse76500,
SolsperseX300 (manufactured by Lubrizol Corporation),
Disparlon DA-7301, Disparlon DA-325, Disparlon DA-375, Disparlon DA-234 (all manufactured by Kusumoto Chemical Industries, Ltd.),
FLOWLEN AF-1000, FLOWLEN DOPA-15B, FLOWLEN DOPA-15BHFS, FLOWLEN DOPA-17HF, FLOWLEN DOPA-22, FLOWLEN DOPA-33, FLOWLEN G-600, FLOWLEN G-700, FLOWLEN G-700AMP, FLOWLEN G-700DMEA, FLOWLEN G-820, FLOWLEN G-900, FLOWLEN GW-1500, FLOWLEN KDG-2400, FLOWLEN NC-500, FLOWLEN WK-13E, (all manufactured by Kyoeisha Chemical Co., Ltd.),
TEGO Dispers610, TEGO Dispers610S,
TEGO Dispers630, TEGO Dispers650,
TEGO Dispers652, TEGO Dispers655,
TEGO Dispers662C, TEGO Dispers670,
TEGO Dispers685, TEGO Dispers700,
TEGO Dispers710, TEGO Dispers740W,
LIPOTIN A, LIPOTIN BL,
LIPOTIN DB, LIPOTIN SB (both manufactured by Evonik Degussa),
PB821, PB822, PN411, PA111 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.),
Texahole 963, Texahole 964, Texahole 987, Texahole P60, Texahole P61, Texahole P63, Texahole 3250, Texahole SF71, Texahole UV20, Texahole UV21 (all manufactured by Cognis),
BorchiGenSN88, BorchiGen0451 (both manufactured by Borchius Pharmaceuticals), and the like.
　本発明の非水系インク組成物は、その他の成分として、紫外線吸収剤、ラジカル捕捉剤、表面調整剤、酸化防止剤、可塑剤、防錆剤、溶剤、充填剤、消泡剤、荷電制御剤、応力緩和剤、浸透剤、導光材、光輝材、磁性材、蛍光体、抗菌剤、抗ウイルス剤、防藻剤等の添加剤を必要に応じて使用してもよい。 The non-aqueous ink composition of the present invention may contain additives such as ultraviolet absorbers, radical scavengers, surface conditioners, antioxidants, plasticizers, rust inhibitors, solvents, fillers, defoamers, charge control agents, stress relaxation agents, penetrating agents, light-guiding materials, glittering materials, magnetic materials, fluorescent materials, antibacterial agents, antiviral agents, and anti-algae agents as other components as necessary.
　本発明の非水系インク組成物は、様々な色のインクとして使用することが可能である。例えば、シアンインク、マゼンタインク、イエローインク、ブラックインクといった基本色インクの他、ライトシアンインク、ライトマゼンタインク、ライトイエローインク、ライトブラックインク、オレンジインク、ホワイトインク等が挙げられる。 The non-aqueous ink composition of the present invention can be used as inks of various colors. For example, in addition to basic color inks such as cyan ink, magenta ink, yellow ink, and black ink, examples include light cyan ink, light magenta ink, light yellow ink, light black ink, orange ink, and white ink.
　本発明の非水系インク組成物がブラックインクである場合、当該非水系インク組成物の水抽出物のｐＨは３．０～７．０の範囲内であることが好ましい。従来の非水系インクは酸性のカーボンブラック顔料を用いる際、ヘッドの腐食を防止するためにアミノ基含有アルコール等の塩基性化合物を用いてｐＨを調整することが好ましかったが、本発明の非水系インク組成物は、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部のアミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上となる（Ａ－２）成分を特定量含んでいることから、ヘッドの腐食が防止でき、また、さらに非水系インク組成物の水抽出物のｐＨを３．０～７．０の範囲内とすることで、吐出ヘッド部分でのインクの再溶解性を向上させることができる。ブラックインクの水抽出物のｐＨは顔料の種類や溶剤量によって調整でき、非水系インク組成物の水抽出物のｐＨを３．０～７．０の範囲内とする観点から、ブラックインクはアミノ基含有アルコールを含んでいないことが好ましい。 When the non-aqueous ink composition of the present invention is a black ink, the pH of the water extract of the non-aqueous ink composition is preferably in the range of 3.0 to 7.0. When an acidic carbon black pigment is used in a conventional non-aqueous ink, it is preferable to adjust the pH using a basic compound such as an amino group-containing alcohol to prevent head corrosion. However, the non-aqueous ink composition of the present invention contains a specific amount of component (A-2) that makes the pH of a mixture of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of an amide bond or urea bond-containing compound 7.0 or higher, so that head corrosion can be prevented. Furthermore, by setting the pH of the water extract of the non-aqueous ink composition in the range of 3.0 to 7.0, the resolubility of the ink in the ejection head can be improved. The pH of the water extract of the black ink can be adjusted by the type of pigment and the amount of solvent, and from the viewpoint of setting the pH of the water extract of the non-aqueous ink composition in the range of 3.0 to 7.0, it is preferable that the black ink does not contain an amino group-containing alcohol.
　アミノ基含有アルコールは、分子内にアミノ基と水酸基とを有する化合物であり、プリンタの吐出ヘッド部分でのノズルの詰まりの発生を抑える観点から使用される場合がある。アミノ基含有アルコールとしては、例えば、２－アミノ－１－ブタノール、２－アミノ－２－メチル－１－プロパノール、２－アミノ－２－メチル－１，３－プロパンジオール、２－アミノ－２－エチル－１，３－プロパンジオール、トリス（ヒドロキシメチル）アミノメタン等が挙げられる。 Amino group-containing alcohols are compounds that have an amino group and a hydroxyl group in the molecule, and are sometimes used to prevent nozzle clogging in the ejection head of a printer. Examples of amino group-containing alcohols include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and tris(hydroxymethyl)aminomethane.
　本発明の非水系インク組成物がホワイトインクである場合、当該非水系インク組成物中に含まれる水の量は、１０，０００質量ｐｐｍ未満であることが好ましい。ホワイトインク中の水分の含有量を上記特定した範囲内とすることで、インクの安定性を向上させることができる。インク中の水分量を１０，０００質量ｐｐｍ未満とする方法としては、インク調製前の材料の水分量を予め減少させる方法や、調製後のインクの水分量を減少させる方法が挙げられ、インクの粘度上昇を抑える観点から、顔料に含まれる水分量を予め減少させた後にインクを調製することが好ましい。水分量を減少させる方法としては、脱水剤を用いる方法や加温等、従来公知の方法が使用できる。ホワイトインク中の水分量は９，０００質量ｐｐｍ未満であることが好ましく、８，０００質量ｐｐｍ未満であることがより好ましい。ホワイトインクに含まれる顔料量は１～２０質量％が好ましく、５～１８質量％が好ましい。ホワイトインクは透明基材に印刷した際の隠蔽率を高める等の目的から他の顔料インクよりも顔料量を多く配合する場合が多く、酸化チタン等の無機顔料は水を吸水しやすいことから、ホワイトインク中の水分量を１０，０００質量ｐｐｍ未満とすることは、インクの保存安定性を高める上で特に重要である。 When the non-aqueous ink composition of the present invention is a white ink, the amount of water contained in the non-aqueous ink composition is preferably less than 10,000 ppm by mass. By setting the moisture content in the white ink within the above-specified range, the stability of the ink can be improved. Methods for setting the moisture content in the ink to less than 10,000 ppm by mass include a method of reducing the moisture content of the materials before preparing the ink, and a method of reducing the moisture content of the ink after preparation. From the viewpoint of suppressing an increase in the viscosity of the ink, it is preferable to prepare the ink after reducing the moisture content in the pigment beforehand. As a method for reducing the moisture content, a conventionally known method such as a method using a dehydrating agent or heating can be used. The moisture content in the white ink is preferably less than 9,000 ppm by mass, and more preferably less than 8,000 ppm by mass. The amount of pigment contained in the white ink is preferably 1 to 20% by mass, and more preferably 5 to 18% by mass. White inks often contain a larger amount of pigment than other pigment inks in order to increase the hiding power when printed on transparent substrates, and inorganic pigments such as titanium oxide are prone to absorbing water, so keeping the moisture content in the white ink below 10,000 ppm by mass is particularly important in terms of improving the storage stability of the ink.
　本発明の非水系インク組成物は、必要に応じて適宜選択される各種成分を混合し、必要に応じて、使用するインクジェットプリントヘッドのノズル径の約１／１０以下のポアサイズを持つフィルターを用い、得られた混合物を濾過することによって、調製できる。 The non-aqueous ink composition of the present invention can be prepared by mixing various components appropriately selected as needed, and, if necessary, filtering the resulting mixture using a filter having a pore size of about 1/10 or less of the nozzle diameter of the inkjet printhead to be used.
　本発明の非水系インク組成物は、その２５℃における粘度が、２．５ｍＰａ・ｓ以上７．０ｍＰａ・ｓ未満であることが好ましく、２．８～６．５ｍＰａ・ｓであることがより好ましく、３．０～６．０ｍＰａ・ｓであることがさらに好ましい。２５℃におけるインク組成物の粘度が上記特定した範囲内にあれば、良好な吐出安定性が得られる。インクの粘度は、コーンプレート型粘度計を用いて測定できる。本明細書では、インクの粘度を「粘度（Ｒ）」とも称する。 The non-aqueous ink composition of the present invention preferably has a viscosity at 25°C of 2.5 mPa·s or more and less than 7.0 mPa·s, more preferably 2.8 to 6.5 mPa·s, and even more preferably 3.0 to 6.0 mPa·s. When the viscosity of the ink composition at 25°C is within the above specified range, good ejection stability is obtained. The ink viscosity can be measured using a cone-plate viscometer. In this specification, the ink viscosity is also referred to as "viscosity (R)".
　本発明の非水系インク組成物は、その２５℃における表面張力が、２０～３５ｍＮ／ｍであることが好ましく、２３～３３ｍＮ／ｍであることがより好ましく、２５～３０ｍＮ／ｍであることが更に好ましい。２５℃におけるインク表面張力が上記特定した範囲内にあれば、良好な吐出安定性が得られるとともに、被印刷面におけるインクの濡れ性が良好になり、インクの乾燥性の向上や印刷物の光沢性の向上につながる。インクの表面張力は、プレート法により測定できる。 The non-aqueous ink composition of the present invention preferably has a surface tension at 25°C of 20 to 35 mN/m, more preferably 23 to 33 mN/m, and even more preferably 25 to 30 mN/m. If the ink surface tension at 25°C is within the above specified range, good ejection stability is obtained and the ink has good wettability on the printed surface, leading to improved ink drying properties and gloss of the printed material. The surface tension of the ink can be measured by the plate method.
　次に、本発明の非水系インクセットについて説明する。 Next, we will explain the non-aqueous ink set of the present invention.
　本発明の非水系インクセットは、シアンインク、マゼンタインク、およびイエローインクを少なくとも備えるインクジェット印刷用の非水系インクセットであって、
　シアンインク、マゼンタインク、およびイエローインクが、（Ａ）有機溶媒、（Ｂ）樹脂、および（Ｃ）顔料を含み、
　（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物
を含む、非水系インクセットである。
　ここで、（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が４．０～３０質量％の範囲内である。 The non-aqueous ink set of the present invention is a non-aqueous ink set for ink-jet printing comprising at least a cyan ink, a magenta ink, and a yellow ink,
The cyan ink, the magenta ink, and the yellow ink each contain (A) an organic solvent, (B) a resin, and (C) a pigment;
(A) The organic solvent is
The non-aqueous ink set includes (A-1) a glycol ether solvent having a boiling point of less than 200°C, and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the (A-2) amide bond- or urea bond-containing compound has a pH of 7.0 or higher.
Here, the amount of (A-1) glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %, and the amount of (A-2) the amide bond- or urea bond-containing compound in the organic solvent (A) is within a range of 4.0 to 30 mass %.
　本発明の非水系インクセットにおいて「（Ａ）有機溶媒」、「（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤」、「（Ａ－２）アミド結合またはウレア結合含有化合物」、「（Ｂ）樹脂」および「（Ｃ）顔料」は、本発明の非水系インクセットの説明において記載したとおりである。 In the non-aqueous ink set of the present invention, "(A) organic solvent," "(A-1) glycol ether solvent with a boiling point of less than 200°C," "(A-2) amide bond or urea bond-containing compound," "(B) resin," and "(C) pigment" are as described in the description of the non-aqueous ink set of the present invention.
　本明細書において、インクジェット印刷用の非水系インクセットとは、インクジェットプリンタによる印刷に使用できる非水系インクセットを意味し、非水系インクセットとは、非水系インク組成物で構成されるインクセットを意味する。すなわち、本発明の非水系インクセットを構成するインクは、非水系インク組成物である。 In this specification, a non-aqueous ink set for inkjet printing means a non-aqueous ink set that can be used for printing with an inkjet printer, and a non-aqueous ink set means an ink set that is composed of a non-aqueous ink composition. In other words, the inks that constitute the non-aqueous ink set of the present invention are non-aqueous ink compositions.
　本発明の非水系インクセットを構成するインクは、少なくともシアンインク、マゼンタインクおよびイエローインクからなるが、これらとは異なる色を発するインク、例えばブラックインクを備えることも可能である。また、シアンインク、マゼンタインク、イエローインク、ブラックインクといった基本色インクの他、ライトシアンインク、ライトマゼンタインク、ライトイエローインク、ライトブラックインク、オレンジインク、ホワイトインク等が本発明の非水系インクセットを構成するインクの例として挙げられる。 The inks constituting the non-aqueous ink set of the present invention are at least cyan ink, magenta ink, and yellow ink, but it is also possible to include an ink that emits a different color, such as black ink. In addition to the basic color inks such as cyan ink, magenta ink, yellow ink, and black ink, examples of inks constituting the non-aqueous ink set of the present invention include light cyan ink, light magenta ink, light yellow ink, light black ink, orange ink, and white ink.
　本発明の非水系インクセットを構成するインクはいずれも上述した本発明の非水系インク組成物であることが好ましい。 It is preferable that all of the inks constituting the non-aqueous ink set of the present invention are the non-aqueous ink compositions of the present invention described above.
　本発明の非水系インクセットが、シアンインク、マゼンタインクおよびイエローインクに加えて、オレンジインクを備える場合、当該オレンジインクは、（Ａ）有機溶媒、（Ｂ）樹脂、および（Ｃ）顔料を含み、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が１．０～３０質量％の範囲内であることが好ましい。当該オレンジインクは、上述した本発明の非水系インク組成物であることが好ましい。 When the non-aqueous ink set of the present invention includes an orange ink in addition to a cyan ink, a magenta ink, and a yellow ink, the orange ink contains (A) an organic solvent, (B) a resin, and (C) a pigment,
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
(A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The amount of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is preferably within a range of 1.0 to 30 mass %. The orange ink is preferably the non-aqueous ink composition of the present invention described above.
　本発明の非水系インクセットが、シアンインク、マゼンタインクおよびイエローインクに加えて、さらなるインク（ただし、オレンジインクを除く。）を備える場合、当該さらなるインクは、（Ａ）有機溶媒、（Ｂ）樹脂、および（Ｃ）顔料を含み、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が４．０～３０質量％の範囲内であることが好ましい。当該さらなるインクは、上述した本発明の非水系インク組成物であることが好ましい。 When the non-aqueous ink set of the present invention includes an additional ink (excluding the orange ink) in addition to the cyan ink, the magenta ink, and the yellow ink, the additional ink contains (A) an organic solvent, (B) a resin, and (C) a pigment,
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
(A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The amount of the amide bond or urea bond-containing compound (A-2) in the organic solvent (A) is preferably within a range of 4.0 to 30 mass %. The further ink is preferably the non-aqueous ink composition of the present invention described above.
　尚、インクセットにおいては各色インクにおける（Ａ－１）沸点２００℃未満のグリコール系溶剤と（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物の割合が同程度であることが好ましい。（Ａ－１）と（Ａ－２）の配合比を同程度、特には１０％以下程度さらには５％以下程度に揃えることで印刷物の乾燥性や光沢を制御しやすくなることから、得られる印刷物の耐ブロッキング性と光沢がより向上する。さらには、各色インクの粘度を揃えることも好ましく、２５℃における粘度（Ｒ）の差は０．５ｍＰａ・ｓ以下であることが好ましく、２５℃における各インクの粘度（Ｒ）はともに３．０～６．０ｍＰａ・ｓの範囲内であることが好ましい。各色インクの粘度をこの範囲に調整することで、耐ブロッキング性と光沢に優れた印刷物を得やすくなる。 In the ink set, it is preferable that the ratio of the (A-2) amide bond or urea bond-containing compound in each color ink is approximately the same, and that the pH of a mixture of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the (A-2) amide bond or urea bond-containing compound is 7.0 or higher. By making the blending ratio of (A-1) and (A-2) approximately the same, particularly approximately 10% or less, and even 5% or less, it becomes easier to control the drying property and gloss of the printed matter, and the blocking resistance and gloss of the obtained printed matter are further improved. Furthermore, it is also preferable to make the viscosity of each color ink the same, and the difference in viscosity (R) at 25°C is preferably 0.5 mPa·s or less, and the viscosity (R) of each ink at 25°C is preferably within the range of 3.0 to 6.0 mPa·s. By adjusting the viscosity of each ink color within this range, it becomes easier to obtain printed matter with excellent blocking resistance and gloss.
　次に、本発明の印刷方法について説明する。 Next, we will explain the printing method of the present invention.
　本発明の印刷方法は、（Ａ）有機溶媒および（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物を用いて印刷層を形成する印刷方法であって、
（Ａ）有機溶媒は、
（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
（Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の割合が６０～９５質量％の範囲内であるとともに、
（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の割合が４．０～３０質量％の範囲内であることを特徴とする、印刷方法である。 The printing method of the present invention is a printing method for forming a printed layer using a non-aqueous ink composition for inkjet printing, which contains (A) an organic solvent and (B) a resin, comprising the steps of:
(A) The organic solvent is
The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
The ratio of (A-1) glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
The printing method is characterized in that the ratio of the amide bond- or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 4.0 to 30 mass %.
　また、本発明者は、本発明の印刷方法において、非水系インク組成物がオレンジインクである場合、（Ａ）有機溶剤中の（Ａ－２）成分の量が４．０質量％を下回る場合であっても、（Ａ－２）成分による効果を十分に発揮できることを見出した。すなわち、本発明の印刷方法において、非水系インク組成物がオレンジインクである場合、（Ａ）有機溶剤中の（Ａ－２）成分の量は、１．０～３０質量％の範囲内であることが好ましい。 The inventors have also found that in the printing method of the present invention, when the non-aqueous ink composition is an orange ink, the effect of the component (A-2) can be fully exhibited even when the amount of the component (A-2) in the organic solvent (A) is less than 4.0% by mass. In other words, in the printing method of the present invention, when the non-aqueous ink composition is an orange ink, the amount of the component (A-2) in the organic solvent (A) is preferably within the range of 1.0 to 30% by mass.
　本発明の印刷方法において「インクジェット印刷用の非水系インク組成物」、「（Ａ）有機溶媒」、「（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤」、「（Ａ－２）水溶液のｐＨが７．０以上であるアミド結合またはウレア結合含有化合物」および「（Ｂ）樹脂」は、本発明の非水系インク組成物の説明において記載したとおりである。 In the printing method of the present invention, the "non-aqueous ink composition for inkjet printing," "(A) organic solvent," "(A-1) glycol ether solvent with a boiling point of less than 200°C," "(A-2) amide bond or urea bond-containing compound with an aqueous solution having a pH of 7.0 or higher," and "(B) resin" are as described in the description of the non-aqueous ink composition of the present invention.
　本明細書において、印刷層とは、インクを用いた印刷により形成される層を意味する。 In this specification, the printed layer refers to a layer formed by printing with ink.
　本発明の印刷方法において、非水系インク組成物は、上述した本発明の非水系インク組成物であることが好ましい。また、複数の非水系インク組成物から印刷層を形成する場合は、上述した本発明の非水系インクセットを用いて印刷層を形成することが好ましい。 In the printing method of the present invention, the non-aqueous ink composition is preferably the non-aqueous ink composition of the present invention described above. Furthermore, when forming a printed layer from multiple non-aqueous ink compositions, it is preferable to form the printed layer using the non-aqueous ink set of the present invention described above.
　本発明の印刷方法において、印刷層が形成される基材は、特に限定されるものではないが、工業ラインで用いられる基材が好適に挙げられる。基材の形状としては、例えば、フィルム状、シート状、板状等がある。基材の材質としては、例えば、エポキシ樹脂、ＡＢＳ樹脂、ポリカーボネート、ポリ塩化ビニル、ポリスチレン、アクリル樹脂、特にはポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンテレフタラート（ＰＥＴ）、ポリプロピレン（ＰＰ）等のプラスチック、鉄、ステンレス、アルミニウム等の金属、木材、セメント、コンクリート、石膏、ケイ酸カルシウム、炭酸カルシウム、ガラス等が挙げられる。基材の具体例としては、塩ビシート、ターポリン、プラダン（プラスチック製ダンボール）、アクリル板、フレキシブルボード、ケイ酸カルシウム板、石膏スラグバーライト板、炭酸カルシウム板、木片セメント板、プレキャストコンクリート板、軽量発泡コンクリート（ＡＬＣ）板、石膏ボード、タイル、及びガラス板等が挙げられる。これらの中でも、ポリ塩化ビニル基材やターポリン基材であることが好ましい。（Ａ－２）成分は、ポリ塩化ビニル基材やターポリン基材への浸透力が高く、より滲みにくく、耐ブロッキング性に優れた印刷層が得られる。 In the printing method of the present invention, the substrate on which the printing layer is formed is not particularly limited, but substrates used in industrial lines are suitable. The substrate may be in the form of a film, sheet, plate, etc. Examples of the substrate material include epoxy resin, ABS resin, polycarbonate, polyvinyl chloride, polystyrene, acrylic resin, particularly plastics such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), and polypropylene (PP), metals such as iron, stainless steel, and aluminum, wood, cement, concrete, gypsum, calcium silicate, calcium carbonate, and glass. Specific examples of substrates include PVC sheets, tarpaulin, plastic cardboard, acrylic boards, flexible boards, calcium silicate boards, gypsum slag bar light boards, calcium carbonate boards, wood chip cement boards, precast concrete boards, lightweight foamed concrete (ALC) boards, gypsum boards, tiles, and glass boards. Among these, polyvinyl chloride substrates and tarpaulin substrates are preferred. Component (A-2) has high penetration into polyvinyl chloride and tarpaulin substrates, and produces a printed layer that is less prone to bleeding and has excellent blocking resistance.
　本発明の印刷方法において、印刷は、インクジェット印刷方式にて行われる。インクジェット印刷には、種々のインクジェットプリンタに使用することができる。インクジェットプリンタとしては、例えば、荷電制御方式又はピエゾ方式によりインク組成物を噴出させるインクジェットプリンタが挙げられる。また、大型インクジェットプリンタ、具体例としては工業ラインで生産される物品への印刷を目的としたインクジェットプリンタも好適に使用できる。 In the printing method of the present invention, printing is performed by an inkjet printing method. Various inkjet printers can be used for inkjet printing. Examples of inkjet printers include inkjet printers that eject ink compositions using a charge control method or a piezoelectric method. Large inkjet printers, specifically inkjet printers designed for printing on items produced on industrial lines, can also be suitably used.
　以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.
＜＜実施例１～１９および比較例１～７＞＞
　表１～１３に示す量（質量部）で各成分を含有する混合物をそれぞれビーズミルで３時間練合してインク１～１０４を調製した。 <<Examples 1 to 19 and Comparative Examples 1 to 7>>
Mixtures containing the components in the amounts (parts by mass) shown in Tables 1 to 13 were kneaded in a bead mill for 3 hours to prepare inks 1 to 104.
　用いた顔料は、イエロー顔料：コマリックスイエロー１５０（Ｚｅｙａ　Ｃｈｅｍｉｃａｌｓ社製）、シアン顔料：クロモファイブルーＡ－２２０ＪＣ（大日精化工業社製）、ブラック顔料：モナーク１０００（キャボット社製）、マゼンタ顔料：Ｆａｓｔｏｇｅｎ　Ｓｕｐｅｒ　Ｍａｇｅｎｔａ　ＲＧ（ＤＩＣ社製）であり、用いた分散剤は、ＤＩＳＰＥＲＢＹＫ－２１５０（ＢＹＫ社製）又はＳＯＬＳＰＥＲＳＥ３２０００（Ｌｕｂｒｉｚｏｌ社製）であり、用いた樹脂はＶＩＮＮＯＬ　Ｈ１５／４２（塩化ビニル－酢酸ビニル共重合樹脂、ワッカーケミー社製）又はダイヤナールＢＲ－８７（アクリル系樹脂、三菱ケミカル社製）である。 The pigments used were yellow pigment: Comalix Yellow 150 (Zeyah Chemicals), cyan pigment: Chromophie Blue A-220JC (Dainichiseika Color & Chemicals), black pigment: Monarch 1000 (Cabot), magenta pigment: Fastogen Super Magenta RG (DIC), the dispersant used was DISPERBYK-2150 (BYK) or SOLSPERSE32000 (Lubrizol), and the resin used was VINNOL H15/42 (vinyl chloride-vinyl acetate copolymer resin, Wacker Chemie) or Dianall BR-87 (acrylic resin, Mitsubishi Chemical).
＜ヘッドの耐腐食性＞
　プリンタヘッドにインク１～１０４を充填し、室温で１００時間浸漬した後ノズル周辺の錆の有無をデジタルマイクロスコープで観察し、以下の基準に従い評価した。結果を表１４に示す。
（基準）
○：マゼンタインク、イエローインク、シアンインク、ブラックインクのいずれの場合も錆が発生していない。
×：マゼンタインク、イエローインク、シアンインク、ブラックインクのうち１つ以上のインクの場合で錆が発生している。 <Head corrosion resistance>
The printer head was filled with inks 1 to 104 and immersed at room temperature for 100 hours, after which the presence or absence of rust around the nozzles was observed with a digital microscope and evaluated according to the following criteria. The results are shown in Table 14.
(standard)
◯: No rust was observed in any of the cases of magenta ink, yellow ink, cyan ink, and black ink.
x: Rust occurred in the case of one or more of magenta ink, yellow ink, cyan ink, and black ink.
＜吐出安定性＞
　表１４に記載のブラックインクについて、ラージフォーマット用インクジェットプリンタにインクを充填した。テストパターン画像を印刷後、１００％ベタ画像を１０００時間印刷した。印刷後再度テストパターンを印刷し、以下の基準に従い評価した。結果を表１４に示す。
（基準）
◎：テストパターンの欠損、テストパターンの乱れが１％未満。
○：テストパターンの欠損、テストパターンの乱れが５％未満。
△：テストパターンの欠損、テストパターンの乱れが５％～１０％。
×：テストパターンの欠損、テストパターンの乱れが１０％を超える。 <Discharge stability>
A large format inkjet printer was filled with the black inks shown in Table 14. After printing a test pattern image, a 100% solid image was printed for 1000 hours. After printing, the test pattern was printed again and evaluated according to the following criteria. The results are shown in Table 14.
(standard)
⊚: Test pattern loss and test pattern disorder are less than 1%.
◯: Test pattern loss and test pattern disorder are less than 5%.
△: Test pattern loss and test pattern disorder of 5% to 10%.
x: The test pattern is missing or distorted by more than 10%.
＜耐ブロッキング性＞
　表１４に記載のブラックインクをバーコーター＃７で、４５℃に加温した光沢塩ビシート上に塗布した。塗布後、インク膜に２００ｇの分銅を１０秒ごとに置き、分銅の跡がつくか評価した。以下の基準に従う評価結果を表１４に示す。評価が◎又は〇であるインクは、ロールメディアに印刷して巻き取る際にもブロッキングを起こしにくい印刷物を形成できるインクである。
（基準）
　◎：２分以内に塗膜上に分銅の跡がつかなくなる。
　〇：３分以内に塗膜上に分銅の跡がつかなくなる。
　×：３分経過しても塗膜に分銅の跡がつく。 <Blocking resistance>
The black inks shown in Table 14 were applied to a glossy PVC sheet heated to 45° C. using bar coater #7. After application, a 200 g weight was placed on the ink film every 10 seconds to evaluate whether the weight left a mark. The evaluation results according to the following criteria are shown in Table 14. Inks rated as ⊚ or ◯ are inks that can form printed matter that is less likely to cause blocking even when printed on roll media and then wound up.
(standard)
⊚: No trace of the weight remains on the coating within 2 minutes.
◯: No trace of the weight remains on the coating within 3 minutes.
×: Traces of the weight remain on the coating even after 3 minutes.
＜耐色間滲み性＞
　表１４の各種インクセットを用いて、ＣＭＹ色の３００％混色のベタ画像とＭＹ色の２００％混色のベタ画像が隣接するように印刷した。以下の基準に従う評価結果を表１４に示す。評価が〇であるインクを用いた画像は滲みにくい。
（基準）
　〇：隣接部の色間で滲みが見られなかった。
　×：隣接部の色間で滲みが見られた。 <Resistance to inter-color bleeding>
A solid image of a 300% mixture of CMY colors and a solid image of a 200% mixture of MY colors were printed adjacent to each other using the various ink sets in Table 14. The evaluation results according to the following criteria are shown in Table 14. Images using inks rated as ◯ are less likely to bleed.
(standard)
◯: No bleeding was observed between adjacent colors.
×: Bleeding was observed between adjacent colors.
＜ドット径＞
　表１４に記載のブラックインクを用いてラージフォーマット用インクジェットプリンタでテストパターンを印刷し、ドット径をデジタルマイクロスコープで観察した。以下の基準に従う評価結果を表１４に示す。ドット径が８０μｍ以上の印刷画像は光沢が高い。
（基準）
　〇：ドット径が８０μｍ以上
　×：ドット径が８０μｍ未満 <Dot diameter>
A test pattern was printed by a large format inkjet printer using the black ink shown in Table 14, and the dot diameter was observed by a digital microscope. The evaluation results according to the following criteria are shown in Table 14. Printed images with dot diameters of 80 μm or more have high gloss.
(standard)
◯: Dot diameter is 80 μm or more ×: Dot diameter is less than 80 μm
＜印刷物の光沢＞
　表１４に記載のブラックインクを用いてラージフォーマット用インクジェットプリンタで１００％ベタ画像を印刷した。得られた印刷物を６０℃、１時間乾燥後、ＢＹＫ社製光沢計で２０°光沢を測定した。以下の基準に従う評価結果を表１４に示す。
（基準）
　◎：光沢値が４０以上
　〇：光沢値が３０以上
　×：光沢値が３０未満 <Gloss of printed matter>
A 100% solid image was printed by a large format inkjet printer using the black ink shown in Table 14. The resulting print was dried at 60° C. for 1 hour, and then the 20° gloss was measured using a gloss meter manufactured by BYK Corporation. The evaluation results according to the following criteria are shown in Table 14.
(standard)
◎: Gloss value is 40 or more. ◯: Gloss value is 30 or more. ×: Gloss value is less than 30.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　表中、「（Ａ－１）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量（質量％）を示し、「（Ａ－２）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量（質量％）を示し、「（Ａ－３）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－３）沸点が２２０℃以上３００℃未満であるグリコールまたはグリコールエーテル系溶剤の量（質量％）を示し、「（Ａ－１）／（Ａ－２）」は、（Ａ）有機溶剤中の（Ａ－１）成分の量の（Ａ）有機溶剤中の（Ａ－２）成分の量に対する質量比を示す。 In the table, "(A-1)/organic solvent" indicates the amount (mass %) of (A-1) glycol ether-based solvent with a boiling point of less than 200°C in (A) organic solvent, "(A-2)/organic solvent" indicates the amount (mass %) of (A-2) amide bond- or urea bond-containing compound in (A) organic solvent, "(A-3)/organic solvent" indicates the amount (mass %) of (A-3) glycol or glycol ether-based solvent with a boiling point of 220°C or more and less than 300°C in (A) organic solvent, and "(A-1)/(A-2)" indicates the mass ratio of the amount of (A-1) component in (A) organic solvent to the amount of (A-2) component in (A) organic solvent.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　加えて、ブラックインク５、４５、４９、５３、５７および７７について、水抽出物のｐＨを測定し、また、ヘッドの耐腐食性および連続吐出安定性の評価を行った。結果を表１５に示す。 In addition, the pH of the water extract was measured for black inks 5, 45, 49, 53, 57 and 77, and the head corrosion resistance and continuous ejection stability were evaluated. The results are shown in Table 15.
＜水抽出物のｐＨ＞
　分液ロートを用いてブラックインク１ｇを蒸留水１００ｇへ滴下し、滴下完了後によく混合・撹拌し、２０℃にて３０分間静置させた。その後、分液ロート内の下側に位置する水相（すなわち水抽出物）を取り出して、ｐＨメーターにて２０℃で水抽出物のｐＨを測定した。 <pH of water extract>
Using a separatory funnel, 1 g of black ink was dropped into 100 g of distilled water, and after completion of the dropwise addition, the mixture was thoroughly mixed and stirred, and allowed to stand for 30 minutes at 20° C. Thereafter, the aqueous phase (i.e., the aqueous extract) located at the bottom of the separatory funnel was removed, and the pH of the aqueous extract was measured at 20° C. using a pH meter.
＜ヘッドの耐腐食性＞
　プリンタヘッドにブラックインクを充填し、室温で１００時間浸漬した後ノズル周辺の錆の有無をデジタルマイクロスコープで観察し、以下の基準に従い評価した。
（基準）
○：錆が発生していない。
×：錆が発生している。 <Head corrosion resistance>
The printer head was filled with black ink and immersed at room temperature for 100 hours, after which the presence or absence of rust around the nozzles was observed with a digital microscope and evaluated according to the following criteria.
(standard)
○: No rust is formed.
×: Rust is observed.
＜連続吐出安定性評価＞
　１００％ベタ画像を５ｍ印刷した際の連続吐出安定性を以下の基準に基づいて評価した。
〇：５ｍ印刷した後も吐出インク滴の飛翔状態について液滴形状の変化や飛行曲がりがなく吐出されている。
△：５ｍ印刷した後の吐出インク滴の飛翔状態について、わずかな液滴形状の変化や飛行曲がりが確認されるが、実用上問題ないレベルである。
×：５ｍ印刷した後の吐出インク滴の飛翔状態について、いちじるしい液滴形状の変化や飛行曲がりが確認され、実用上問題がある。 <Continuous ejection stability evaluation>
The continuous ejection stability when a 100% solid image was printed for 5 m was evaluated based on the following criteria.
◯: Even after printing for 5 m, the ejected ink droplets were ejected without any change in droplet shape or deflection in flight.
Δ: After printing for 5 m, slight changes in droplet shape and flight deviation were observed in the flight state of the ejected ink droplets, but these were at a level that did not cause any practical problems.
x: After printing for 5 m, significant changes in droplet shape and flight deviation were observed in the flight state of the ejected ink droplets, which is problematic for practical use.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
＜＜実施例２０～２４および比較例８～１１＞＞
　表１６に示す量（質量部）で各成分を含有する混合物をそれぞれビーズミルで３時間練合してオレンジインクＯ１～Ｏ９を調製した。 <<Examples 20 to 24 and Comparative Examples 8 to 11>>
Mixtures containing the components in the amounts (parts by mass) shown in Table 16 were kneaded in a bead mill for 3 hours to prepare orange inks O1 to O9.
＜ヘッドの耐腐食性＞
　プリンタヘッドにインクＯ１～Ｏ９を充填し、室温で１００時間浸漬した後ノズル周辺の錆の有無をデジタルマイクロスコープで観察し、以下の基準に従い評価した。結果を表１６に示す。
（基準）
○：錆が発生していない。
×：錆が発生している。 <Head corrosion resistance>
The printer head was filled with inks O1 to O9 and immersed at room temperature for 100 hours, after which the presence or absence of rust around the nozzles was observed with a digital microscope and evaluated according to the following criteria. The results are shown in Table 16.
(standard)
○: No rust is formed.
×: Rust is observed.
＜吐出安定性＞
　表１６に記載のオレンジインクについて、ラージフォーマット用インクジェットプリンタにインクを充填した。テストパターン画像を印刷後、１００％ベタ画像を１０００時間印刷した。印刷後再度テストパターンを印刷し、以下の基準に従い評価した。結果を表１６に示す。
（基準）
◎：テストパターンの欠損、テストパターンの乱れが１％未満。
○：テストパターンの欠損、テストパターンの乱れが５％未満。
△：テストパターンの欠損、テストパターンの乱れが５％～１０％。
×：テストパターンの欠損、テストパターンの乱れが１０％を超える。 <Discharge stability>
The orange inks shown in Table 16 were filled into a large format inkjet printer. After printing a test pattern image, a 100% solid image was printed for 1000 hours. After printing, the test pattern was printed again and evaluated according to the following criteria. The results are shown in Table 16.
(standard)
⊚: Test pattern loss and test pattern disorder are less than 1%.
◯: Test pattern loss and test pattern disorder are less than 5%.
△: Test pattern loss and test pattern disorder of 5% to 10%.
x: The test pattern is missing or distorted by more than 10%.
＜耐ブロッキング性＞
　表１６に記載のオレンジインクをバーコーター＃７で、４５℃に加温した光沢塩ビシート上に塗布した。塗布後、インク膜に２００ｇの分銅を１０秒ごとに置き、分銅の跡がつくか評価した。以下の基準に従う評価結果を表１６に示す。評価が◎又は〇であるインクは、ロールメディアに印刷して巻き取る際にもブロッキングを起こしにくい印刷物を形成できるインクである。
（基準）
　◎：２分以内に塗膜上に分銅の跡がつかなくなる。
　〇：３分以内に塗膜上に分銅の跡がつかなくなる。
　×：３分経過しても塗膜に分銅の跡がつく。 <Blocking resistance>
The orange inks shown in Table 16 were applied to a glossy PVC sheet heated to 45° C. using bar coater #7. After application, a 200 g weight was placed on the ink film every 10 seconds to evaluate whether the weight left a mark. The evaluation results according to the following criteria are shown in Table 16. Inks rated as ⊚ or ◯ are inks that can form printed matter that is less likely to cause blocking even when printed on roll media and then wound up.
(standard)
⊚: No trace of the weight remains on the coating within 2 minutes.
◯: No trace of the weight remains on the coating within 3 minutes.
×: Traces of the weight remain on the coating even after 3 minutes.
＜耐色間滲み性＞
　表１６の各種オレンジインクと上記にて調製されたインク６、７、８よりなるインクセットを用いて、ＣＭＹ色の３００％混色のベタ画像と、オレンジ色の１００％混色のベタ画像が隣接するように印刷した。以下の基準に従う評価結果を表１６に示す。評価が〇であるインクを用いた画像は滲みにくい。
（基準）
　〇：隣接部の色間で滲みが見られなかった。
　×：隣接部の色間で滲みが見られた。 <Resistance to inter-color bleeding>
Using an ink set consisting of the various orange inks in Table 16 and inks 6, 7, and 8 prepared above, a solid image of 300% CMY color mixture and a solid image of 100% orange color mixture were printed adjacent to each other. The evaluation results according to the following criteria are shown in Table 16. Images using inks rated ◯ are less likely to bleed.
(standard)
◯: No bleeding was observed between adjacent colors.
×: Bleeding was observed between adjacent colors.
＜印刷物の光沢＞
　表１６に記載のオレンジインクを用いてラージフォーマット用インクジェットプリンタで１００％ベタ画像を印刷した。得られた印刷物を６０℃、１時間乾燥後、ＢＹＫ社製光沢計で２０°光沢を測定した。以下の基準に従う評価結果を表１６に示す。
（基準）
　◎：光沢値が４０以上
　〇：光沢値が３０以上
　×：光沢値が３０未満 <Gloss of printed matter>
A 100% solid image was printed by a large format inkjet printer using the orange ink shown in Table 16. The resulting print was dried at 60° C. for 1 hour, and then the 20° gloss was measured using a gloss meter manufactured by BYK Corporation. The evaluation results according to the following criteria are shown in Table 16.
(standard)
◎: Gloss value is 40 or more. ◯: Gloss value is 30 or more. ×: Gloss value is less than 30.
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
　表中、「（Ａ－１）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量（質量％）を示し、「（Ａ－２）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量（質量％）を示し、「（Ａ－３）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－３）沸点が２２０℃以上３００℃未満であるグリコールまたはグリコールエーテル系溶剤の量（質量％）を示し、「（Ａ－１）／（Ａ－２）」は、（Ａ）有機溶剤中の（Ａ－１）成分の量の（Ａ）有機溶剤中の（Ａ－２）成分の量に対する質量比を示す。 In the table, "(A-1)/organic solvent" indicates the amount (mass %) of (A-1) glycol ether-based solvent with a boiling point of less than 200°C in (A) organic solvent, "(A-2)/organic solvent" indicates the amount (mass %) of (A-2) amide bond- or urea bond-containing compound in (A) organic solvent, "(A-3)/organic solvent" indicates the amount (mass %) of (A-3) glycol or glycol ether-based solvent with a boiling point of 220°C or more and less than 300°C in (A) organic solvent, and "(A-1)/(A-2)" indicates the mass ratio of the amount of (A-1) component in (A) organic solvent to the amount of (A-2) component in (A) organic solvent.
＜＜実施例２５～３０＞＞
＜ホワイトインクＷ１～Ｗ６の調製＞
　予め脱水剤を用いて脱水処理した酸化チタン顔料を用いて、表１７に示す量（質量部）で各成分を含有する混合物をそれぞれビーズミルで３時間練合してホワイトインクＷ１～Ｗ６を調製した。得られたインクの２５℃における粘度をコーンプレート型粘度計で測定し、これを初期粘度とした。また、インクＷ１～Ｗ６の水分量を、水分計（カールフィッシャー法）により測定した。 <<Examples 25 to 30>>
<Preparation of White Inks W1 to W6>
Using titanium oxide pigment that had been dehydrated in advance using a dehydrating agent, mixtures containing each component in the amounts (parts by mass) shown in Table 17 were kneaded in a bead mill for 3 hours to prepare white inks W1 to W6. The viscosity of the resulting inks at 25°C was measured using a cone-plate viscometer, and this was taken as the initial viscosity. The moisture content of inks W1 to W6 was also measured using a moisture meter (Karl Fischer method).
＜ヘッドの耐腐食性＞
　プリンタヘッドにホワイトインクＷ１～Ｗ６を充填し、室温で１００時間浸漬した後ノズル周辺の錆の有無をデジタルマイクロスコープで観察し、以下の基準に従い評価した。結果を表１７に示す。
（基準）
○：錆が発生していない。
×：錆が発生している。 <Head corrosion resistance>
The printer head was filled with white ink W1 to W6, and after immersion at room temperature for 100 hours, the presence or absence of rust around the nozzles was observed with a digital microscope and evaluated according to the following criteria. The results are shown in Table 17.
(standard)
○: No rust is formed.
×: Rust is observed.
＜吐出安定性＞
　ホワイトインクＷ１～Ｗ６について、ラージフォーマット用インクジェットプリンタにインクを充填した。テストパターン画像を印刷後、１００％ベタ画像を１０００時間印刷した。印刷後再度テストパターンを印刷し、以下の基準に従い評価した。結果を表１７に示す。
（基準）
◎：テストパターンの欠損、テストパターンの乱れが１％未満。
○：テストパターンの欠損、テストパターンの乱れが５％未満。
△：テストパターンの欠損、テストパターンの乱れが５％～１０％。
×：テストパターンの欠損、テストパターンの乱れが１０％を超える。 <Discharge stability>
For the white inks W1 to W6, the ink was filled into a large format inkjet printer. After printing a test pattern image, a 100% solid image was printed for 1000 hours. After printing, the test pattern was printed again and evaluated according to the following criteria. The results are shown in Table 17.
(standard)
⊚: Test pattern loss and test pattern disorder are less than 1%.
◯: Test pattern loss and test pattern disorder are less than 5%.
△: Test pattern loss and test pattern disorder of 5% to 10%.
x: The test pattern is missing or distorted by more than 10%.
＜耐ブロッキング性＞
　表１７に記載のホワイトインクＷ１～Ｗ６をバーコーター＃７で、４５℃に加温した光沢塩ビシート上に塗布した。塗布後、インク膜に２００ｇの分銅を１０秒ごとに置き、分銅の跡がつくか評価した。以下の基準に従う評価結果を表１７に示す。評価が◎又は〇であるインクは、ロールメディアに印刷して巻き取る際にもブロッキングを起こしにくい印刷物を形成できるインクである。
（基準）
　◎：２分以内に塗膜上に分銅の跡がつかなくなる。
　〇：３分以内に塗膜上に分銅の跡がつかなくなる。
　×：３分経過しても塗膜に分銅の跡がつく。 <Blocking resistance>
White inks W1 to W6 shown in Table 17 were applied to a glossy PVC sheet heated to 45°C using bar coater #7. After application, a 200g weight was placed on the ink film every 10 seconds to evaluate whether the weight left a mark. The evaluation results according to the following criteria are shown in Table 17. Inks rated as ⊚ or ◯ are inks that can form printed matter that is less likely to cause blocking when printed on roll media and then wound up.
(standard)
⊚: No trace of the weight remains on the coating within 2 minutes.
◯: No trace of the weight remains on the coating within 3 minutes.
×: Traces of the weight remain on the coating even after 3 minutes.
＜耐色間滲み性＞
　表１７の各種ホワイトインクと上記にて調製されたインク６、７、８よりなるインクセットを用いて、ＣＭＹ色の３００％混色のベタ画像とホワイト色の１００％混色のベタ画像が隣接するように印刷した。以下の基準に従う評価結果を表１７に示す。評価が〇であるインクを用いた画像は滲みにくい。
（基準）
　〇：隣接部の色間で滲みが見られなかった。
　×：隣接部の色間で滲みが見られた。 <Resistance to inter-color bleeding>
Using an ink set consisting of the various white inks in Table 17 and inks 6, 7, and 8 prepared above, a solid image of 300% CMY color mixture and a solid image of 100% white color mixture were printed adjacent to each other. The evaluation results according to the following criteria are shown in Table 17. Images using inks rated ◯ are less likely to bleed.
(standard)
◯: No bleeding was observed between adjacent colors.
×: Bleeding was observed between adjacent colors.
＜印刷物の光沢＞
　表１７に記載のホワイトインクを用いてラージフォーマット用インクジェットプリンタで１００％ベタ画像を印刷した。得られた印刷物を６０℃、１時間で乾燥後、ＢＹＫ社製光沢計で２０°光沢を測定した。以下の基準に従う評価結果を表１７に示す。
（基準）
　◎：光沢値が４０以上
　〇：光沢値が３０以上
　×：光沢値が３０未満 <Gloss of printed matter>
A 100% solid image was printed by a large format inkjet printer using the white ink shown in Table 17. The resulting print was dried at 60° C. for 1 hour, and then the 20° gloss was measured using a gloss meter manufactured by BYK Corporation. The evaluation results according to the following criteria are shown in Table 17.
(standard)
◎: Gloss value is 40 or more. ◯: Gloss value is 30 or more. ×: Gloss value is less than 30.
＜貯蔵安定性＞
　ホワイトインクＷ１～Ｗ６を５０℃で２８日間静置保管し、保管前後のインクの粘度を測定して、初期粘度からの粘度変化率を求め、下記の基準に従い貯蔵安定性を評価した。結果を表１７に示す。
（基準）
◎：粘度変化率が０～０．９％
○：粘度変化率が１．０％～２．９％
△：粘度変化率が３．０％～１４．９％
×：粘度変化率が１５．０％以上 <Storage stability>
The white inks W1 to W6 were stored at 50° C. for 28 days, and the viscosity of the inks was measured before and after storage to determine the rate of change in viscosity from the initial viscosity, and the storage stability was evaluated according to the following criteria. The results are shown in Table 17.
(standard)
◎: Viscosity change rate is 0 to 0.9%
○: Viscosity change rate is 1.0% to 2.9%
△: Viscosity change rate is 3.0% to 14.9%
×: Viscosity change rate is 15.0% or more
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
　表中、「（Ａ－１）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量（質量％）を示し、「（Ａ－２）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量（質量％）を示し、「（Ａ－３）／有機溶剤」は、（Ａ）有機溶媒中の（Ａ－３）沸点が２２０℃以上３００℃未満であるグリコールまたはグリコールエーテル系溶剤の量（質量％）を示し、「（Ａ－１）／（Ａ－２）」は、（Ａ）有機溶剤中の（Ａ－１）成分の量の（Ａ）有機溶剤中の（Ａ－２）成分の量に対する質量比を示す。 In the table, "(A-1)/organic solvent" indicates the amount (mass %) of (A-1) glycol ether-based solvent with a boiling point of less than 200°C in (A) organic solvent, "(A-2)/organic solvent" indicates the amount (mass %) of (A-2) amide bond- or urea bond-containing compound in (A) organic solvent, "(A-3)/organic solvent" indicates the amount (mass %) of (A-3) glycol or glycol ether-based solvent with a boiling point of 220°C or more and less than 300°C in (A) organic solvent, and "(A-1)/(A-2)" indicates the mass ratio of the amount of (A-1) component in (A) organic solvent to the amount of (A-2) component in (A) organic solvent.

Claims (10)

  1. （Ａ）有機溶媒と（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物であって、
    （Ａ）有機溶媒は、
    （Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
    （Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
    （Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
    （Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が４．０～３０質量％の範囲内であることを特徴とする、非水系インク組成物。     A non-aqueous ink composition for inkjet printing comprising (A) an organic solvent and (B) a resin,
    (A) The organic solvent is
    The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
    (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
    A non-aqueous ink composition, comprising (A-2) an amide bond- or urea bond-containing compound in an organic solvent (A) in an amount within the range of 4.0 to 30% by mass.
  2. （Ａ）有機溶媒と（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物であって、
    前記非水系インク組成物が、オレンジインクであり、
    （Ａ）有機溶媒は、
    （Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
    （Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
    （Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
    （Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が１．０～３０質量％の範囲内であることを特徴とする、非水系インク組成物。     A non-aqueous ink composition for inkjet printing comprising (A) an organic solvent and (B) a resin,
    the non-aqueous ink composition is an orange ink,
    (A) The organic solvent is
    The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
    (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
    A non-aqueous ink composition, comprising (A-2) an amide bond- or urea bond-containing compound in an organic solvent (A) in an amount within the range of 1.0 to 30% by mass.
  3. （Ａ）有機溶媒が、さらに
    （Ａ－３）沸点が２２０℃以上３００℃未満であるグリコールまたはグリコールエーテル系溶剤を含むことを特徴とする、請求項１または２に記載のインク組成物。     3. The ink composition according to claim 1, wherein the organic solvent (A) further comprises (A-3) a glycol or glycol ether solvent having a boiling point of 220° C. or higher and lower than 300° C.
  4. （Ａ－２）アミド結合またはウレア結合含有化合物が、アルキルアミド系溶剤、環状アミド系溶剤、芳香族アミド系溶剤、アルキルウレア系溶剤、および環状ウレア系溶剤より選ばれる少なくとも１種を含むことを特徴とする、請求項１または２に記載のインク組成物。 The ink composition according to claim 1 or 2, characterized in that (A-2) the amide bond or urea bond-containing compound contains at least one solvent selected from the group consisting of alkylamide solvents, cyclic amide solvents, aromatic amide solvents, alkylurea solvents, and cyclic urea solvents.
  5. 前記非水系インク組成物が、ブラックインクであり、
    前記非水系インク組成物の水抽出物のｐＨが３．０～７．０の範囲内である、請求項１に記載のインク組成物。     the non-aqueous ink composition is a black ink,
    The ink composition according to claim 1, wherein the pH of the aqueous extract of the non-aqueous ink composition is within the range of 3.0 to 7.0.
  6. 前記非水系インク組成物が、ホワイトインクであり、
    前記非水系インク組成物中に含まれる水の量が１０，０００質量ｐｐｍ未満である、請求項１に記載のインク組成物。     the non-aqueous ink composition is a white ink,
    The ink composition according to claim 1 , wherein the amount of water contained in the non-aqueous ink composition is less than 10,000 ppm by mass.
  7. シアンインク、マゼンタインク、およびイエローインクを少なくとも備えるインクジェット印刷用の非水系インクセットであって、
    シアンインク、マゼンタインク、およびイエローインクが、（Ａ）有機溶媒、（Ｂ）樹脂、および（Ｃ）顔料を含み、
    （Ａ）有機溶媒は、
    （Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
    （Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
    （Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
    （Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が４．０～３０質量％の範囲内であることを特徴とする、非水系インクセット。     A non-aqueous ink set for inkjet printing comprising at least a cyan ink, a magenta ink, and a yellow ink,
    The cyan ink, the magenta ink, and the yellow ink each contain (A) an organic solvent, (B) a resin, and (C) a pigment;
    (A) The organic solvent is
    The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
    (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
    A non-aqueous ink set, characterized in that the amount of (A-2) an amide bond or urea bond-containing compound in (A) an organic solvent is within the range of 4.0 to 30 mass %.
  8. 前記非水系インクセットが、オレンジインクを備え、
    オレンジインクが、（Ａ）有機溶媒、（Ｂ）樹脂、および（Ｃ）顔料を含み、
    （Ａ）有機溶媒は、
    （Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
    （Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
    （Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
    （Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が１．０～３０質量％の範囲内であることを特徴とする、請求項７に記載の非水系インクセット。     the non-aqueous ink set comprises an orange ink,
    the orange ink comprises (A) an organic solvent, (B) a resin, and (C) a pigment;
    (A) The organic solvent is
    The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
    (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
    8. The non-aqueous ink set according to claim 7, wherein the amount of the amide bond or urea bond-containing compound (A-2) in the organic solvent (A) is within the range of 1.0 to 30 mass %.
  9. （Ａ）有機溶媒および（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物を用いて印刷層を形成する印刷方法であって、
    （Ａ）有機溶媒は、
    （Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
    （Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
    （Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
    （Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が４．０～３０質量％の範囲内であることを特徴とする、印刷方法。     A printing method for forming a printed layer using a non-aqueous ink composition for inkjet printing, the non-aqueous ink composition comprising (A) an organic solvent and (B) a resin, the method comprising the steps of:
    (A) The organic solvent is
    The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
    (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
    A printing method, characterized in that the amount of (A-2) the amide bond- or urea bond-containing compound in (A) the organic solvent is within the range of 4.0 to 30 mass %.
  10. （Ａ）有機溶媒および（Ｂ）樹脂を含むインクジェット印刷用の非水系インク組成物を用いて印刷層を形成する印刷方法であって、
    前記非水系インク組成物が、オレンジインクであり、
    （Ａ）有機溶媒は、
    （Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤、および
    （Ａ－２）アミド結合またはウレア結合含有化合物であって、５０質量部の水と、４７．５質量部のジエチレングリコールエチルメチルエーテルと、１２．５質量部の（Ａ－２）アミド結合またはウレア結合含有化合物とからなる混合液のｐＨが７．０以上である、（Ａ－２）アミド結合またはウレア結合含有化合物を含み、
    （Ａ）有機溶媒中の（Ａ－１）沸点２００℃未満のグリコールエーテル系溶剤の量が６０～９５質量％の範囲内であるとともに、
    （Ａ）有機溶媒中の（Ａ－２）アミド結合またはウレア結合含有化合物の量が１．０～３０質量％の範囲内であることを特徴とする、印刷方法。     A printing method for forming a printed layer using a non-aqueous ink composition for inkjet printing, the non-aqueous ink composition comprising (A) an organic solvent and (B) a resin, the method comprising the steps of:
    the non-aqueous ink composition is an orange ink,
    (A) The organic solvent is
    The present invention comprises (A-1) a glycol ether solvent having a boiling point of less than 200° C., and (A-2) an amide bond- or urea bond-containing compound, wherein a mixed solution consisting of 50 parts by mass of water, 47.5 parts by mass of diethylene glycol ethyl methyl ether, and 12.5 parts by mass of the amide bond- or urea bond-containing compound (A-2) has a pH of 7.0 or higher,
    (A-1) The amount of the glycol ether solvent having a boiling point of less than 200° C. in the organic solvent (A) is within a range of 60 to 95 mass %,
    A printing method, characterized in that the amount of (A-2) the amide bond- or urea bond-containing compound in (A) the organic solvent is within the range of 1.0 to 30 mass %.
PCT/JP2024/013138 2023-03-31 2024-03-29 Non-aqueous ink composition, non-aqueous ink set, and printing method WO2024204751A1 (en)

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JP2008037984A (en) * 2006-08-04 2008-02-21 Konica Minolta Ij Technologies Inc Method for ink-jet recording
JP2008208171A (en) * 2007-02-23 2008-09-11 General Technology Kk Oil-based inkjet ink
JP2013177597A (en) * 2013-04-05 2013-09-09 Dnp Fine Chemicals Co Ltd Oily ink set
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