WO2020004228A1 - Encre, cartouche d'encre, ensemble d'encres, imprimante à jet d'encre et procédé d'impression de textile par jet d'encre - Google Patents

Encre, cartouche d'encre, ensemble d'encres, imprimante à jet d'encre et procédé d'impression de textile par jet d'encre Download PDF

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Publication number
WO2020004228A1
WO2020004228A1 PCT/JP2019/024546 JP2019024546W WO2020004228A1 WO 2020004228 A1 WO2020004228 A1 WO 2020004228A1 JP 2019024546 W JP2019024546 W JP 2019024546W WO 2020004228 A1 WO2020004228 A1 WO 2020004228A1
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WO
WIPO (PCT)
Prior art keywords
ink
resin
mass
dye
colored resin
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2019/024546
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English (en)
Japanese (ja)
Inventor
児玉　邦彦
小林　博美
藤江　賀彦
理俊 水村
誠 大元
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to JP2020527460A priority Critical patent/JPWO2020004228A1/ja
Publication of WO2020004228A1 publication Critical patent/WO2020004228A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by 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
    • C09D11/38—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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/12—Disazo dyes from other coupling components "C"
    • C09B31/14—Heterocyclic components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink

Definitions

  • the present invention relates to an ink, an ink cartridge, an ink set, an inkjet printer, and an inkjet printing method.
  • a colorant used for coloring a fabric is either a dye or a pigment, and as a method of industrially coloring a fabric using these colorants, a screen printing method, a roller printing method, a transfer method, Ink jet systems and the like have been used.
  • the ink jet method does not require the production of a plate compared to other methods, can quickly form an image with excellent gradation, and further uses only the required amount of ink as a formed image, so that waste liquid is reduced. It can be said that this is an excellent image forming method having environmental advantages such as a small amount.
  • Patent Literature 1 describes a printing ink including a coloring agent including a coloring material including a polymer compound, water, and a water-soluble organic solvent.
  • Patent Literature 2 describes an aqueous ink for inkjet containing a dispersion and a disperse dye.
  • Patent Document 3 discloses an inkjet printing liquid containing heat-reactive composite resin particles in an aqueous medium.
  • Patent Document 4 describes an inkjet ink including an aqueous medium and a capsule including a core containing one or more thermosetting compounds, a polymer shell surrounding the core.
  • An object of the present invention is to color various kinds of fabrics, and to obtain the color development, inkjet dischargeability, stability with time, and color fastness (washing resistance, rub resistance, and sweat resistance) of an obtained image.
  • An object of the present invention is to provide an ink excellent in the above, an ink cartridge filled with the ink, an ink set, an ink jet printer, and an ink jet printing method using the ink.
  • the object of the present invention has been achieved by the following means.
  • the colored resin particles contain a dye (A) and a resin (B) represented by the following formula (1), and the dye (A) and the resin (B) Wherein the mass ratio (dye (A)) / (resin (B)) is 1.2 or more.
  • R 101 to R 120 each independently represent a hydrogen atom or a substituent.
  • the aqueous organic solvent contains 17% by mass or more based on the ink of a solvent having a boiling point of 150 ° C. or more at 1 atm consisting of only carbon atoms, hydrogen atoms, and oxygen atoms, or contains only carbon atoms, hydrogen atoms, and oxygen atoms.
  • the ink according to any one of [1] to [4], comprising a solvent having a boiling point of 200 ° C. or more at 1 atm in an amount of 15% by mass or more based on the ink.
  • An ink-jet printing method comprising the step of printing the ink according to any one of [1] to [11] on a fabric by an ink-jet method.
  • the inkjet printing method according to [12] further comprising a heat treatment step.
  • the inkjet printing method according to [12] or [13] further comprising a pretreatment step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated fabric.
  • the coagulant is an ammonium cationic polymer.
  • Step (1) a step of emulsifying a mixture containing the dye (a), resin (b), water (c), and organic solvent (d) represented by the following formula (1) to obtain an emulsion.
  • the ratio (a) / (b) is 1.2 or more, and the mass ratio (a) / (d) of the dye (a) and the organic solvent (d) in the mixture in the step (1) is 1 /. 9 to 1/1.
  • R 101 to R 120 each independently represent a hydrogen atom or a substituent.
  • various types of cloths can be colored, and extremely high color developing property, inkjet dischargeability, and stability over time can be achieved. Furthermore, dyeing fastness (washing resistance, abrasion resistance, Ink, an ink cartridge filled with the ink, an ink set, an ink jet printer, and an ink jet printing method using the ink.
  • dyeing fastness washing resistance, abrasion resistance, Ink, an ink cartridge filled with the ink, an ink set, an ink jet printer, and an ink jet printing method using the ink.
  • a specific dye by containing it in the colored resin particles at a high concentration, while suppressing the solid content concentration in the ink, it is possible to increase the dye concentration in the ink, thereby extremely It is presumed that both high color developability, inkjet dischargeability, and stability over time can be achieved.
  • the content of the water-dispersible resin contained in the colored resin particles is small, good properties are exhibited even in a fastness test for contact with water such as washing, sweat, and wet
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • the “substituent group A” refers to a substituent described in [0117] of WO 2017/131107.
  • the substituent group A1 includes the following substituents.
  • Substituent group A1 Halogen atom, alkyl group (preferably having 1 to 30 carbon atoms), cycloalkyl group (preferably having 3 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), heterocyclic group (preferably having 3 to 30 carbon atoms) 30), an acyl group (preferably having 2 to 30 carbon atoms), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an alkoxy group (preferably having 1 to 30 carbon atoms), an aryloxy group (preferably having a carbon number of 30).
  • an acyloxy group (preferably having 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms), a carbamoyl group, a sulfamoyl group, An alkylsulfonyl group (preferably having 1 to 30 carbon atoms), an arylsulfonyl group (preferably having 6 to 30 carbon atoms), an amino group, Amino group (preferably having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably having 1 to 30 carbon atoms), arylsulfonylamino group (preferably having 6 to 30 carbon atoms), and substitution obtained by combining two or more of these. Base.
  • (meth) acrylate is used to mean “either or both of acrylate and methacrylate”.
  • the ink of the present invention contains (a) water, (b) an aqueous organic solvent, and (c) colored resin particles, wherein the colored resin particles are a dye (A) represented by the following formula (1), and a resin ( B), wherein the mass ratio (dye (A)) / (resin (B)) of the dye and the resin represented by the following formula (1) is 1.2 or more.
  • the colored resin particles are a dye (A) represented by the following formula (1), and a resin ( B), wherein the mass ratio (dye (A)) / (resin (B)) of the dye and the resin represented by the following formula (1) is 1.2 or more.
  • R 101 to R 120 each independently represent a hydrogen atom or a substituent.
  • the ink of the present invention contains water.
  • the water is not particularly limited, and ion-exchanged water, ultrafiltration water, reverse osmosis water, pure water such as distilled water, or ultrapure water can be used. More preferred.
  • the content of water in the ink of the present invention is preferably from 40 to 80% by mass, more preferably from 45 to 75% by mass, and particularly preferably from 50 to 75% by mass. When the content of water is within the above range, the stability of the ink is excellent (the sedimentation is unlikely to occur), and the ejection stability of the inkjet ink is also excellent.
  • the ink of the present invention contains an aqueous organic solvent.
  • the aqueous organic solvent preferably has a solubility in water at 25 ° C. of 10 g / 100 g-H 2 O or more, more preferably 20 g / 100 g-H 2 O or more, and is mixed with water at an arbitrary ratio.
  • the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents.
  • Examples include ethylene glycol monobutyl ether and acetonitrile.
  • the aqueous organic solvent preferably contains tetraethylene glycol.
  • the content of the aqueous organic solvent in the ink is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass.
  • the stability of the ink is excellent (sedimentation and the like are unlikely to occur), and the ejection stability as an inkjet ink is also excellent.
  • the water-soluble organic solvent preferably contains a solvent consisting of only carbon atoms, hydrogen atoms, and oxygen atoms. More preferably, the content is 30% by mass or more based on the organic solvent.
  • the water-soluble organic solvent contains only a carbon atom, a hydrogen atom, and an oxygen atom, and contains 17% by mass or more of a solvent having a boiling point of 150 ° C. or more at 1 atm with respect to the ink. It is preferable that a solvent containing only oxygen atoms and having a boiling point of 200 ° C. or more at 1 atm is contained in the ink in an amount of 15% by mass or more.
  • 1 atmospheric pressure is 101325 Pa.
  • Examples of the solvent containing only carbon atoms, hydrogen atoms, and oxygen atoms include propylene glycol (boiling point: 188.2 ° C.), ethylene glycol (boiling point: 197.3 ° C.), diethylene glycol (boiling point: 244.3 ° C.), and diethylene glycol (boiling point: 244.3 ° C.).
  • propylene glycol (boiling point: 188.2 ° C.), ethylene glycol (boiling point: 197.3 ° C.), diethylene glycol (boiling point: 244.3 ° C.), and diethylene glycol (boiling point: 244.3 ° C.).
  • ° C) triethylene glycol (boiling point 276 ° C), tetraethylene glycol (boiling point 314 ° C), and glycerin (boiling point 290 ° C) are preferred.
  • the ink of the present invention contains colored resin particles.
  • the average particle size of the colored resin particles is preferably 200 nm or less, more preferably 20 to 200 nm, and further preferably 40 to 150 nm.
  • the average particle diameter of the colored resin particles is 200 nm or less, it is easy to directly print on a fabric by an inkjet method.
  • a value of a volume average particle diameter (MV) measured using a particle size distribution analyzer (Nanotrack UPA EX150, manufactured by Nikkiso Co., Ltd.) was used.
  • the colored resin particles are present in a dispersed state.
  • the colored resin particles are easily mixed with water (easy to wet) as a property of the colored resin particles themselves or by using a dispersant in combination, and are regenerated by electrostatic repulsion (repulsive force) or steric repulsion. It has the function of preventing aggregation and suppressing sedimentation.
  • a method for dispersing the colored resin particles a known method can be used.
  • the colored resin particles in the ink of the present invention contain the dye (A) represented by the following formula (1) and the resin (B), and have a mass ratio of the dye represented by the following formula (1) to the resin (dye ( A)) / (Resin (B)) is 1.2 or more.
  • R 101 to R 120 each independently represent a hydrogen atom or a substituent.
  • R 101 to R 120 each independently represent a hydrogen atom or a substituent.
  • substituents include a substituent selected from the substituent group A (preferably, a substituent selected from the substituent group A1).
  • R 101 and R 102 each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group is more preferably an alkyl group having 1 to 30 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms, and most preferably represents a methyl group.
  • R 101 and R 102 preferably represent a hydrogen atom.
  • R 103 to R 118 is more preferably a halogen atom, an alkyl group, an alkoxy group, a nitro group, an aryl group, an acylamino group, or an alkoxycarbonyl group.
  • R 103 to R 118 preferably represent a hydrogen atom.
  • R 119 and R 120 each independently preferably represent an alkyl group, more preferably represent an alkyl group having 1 to 30 carbon atoms, still more preferably represent an alkyl group having 1 to 10 carbon atoms, Particularly preferably, it represents 1 to 6 alkyl groups, most preferably a methyl group.
  • each substituent may have a further substituent.
  • the further substituent is not particularly limited, and examples thereof include a substituent selected from the above-mentioned substituent group A1.
  • C.I. I. Solvent Black 3 is preferred.
  • C. I. Solvent Black 3 can be a commercially available product, for example, Oil Black HBB, Oil Black 860 (both manufactured by Orient Chemical Industry Co., Ltd.).
  • any resin may be used as long as it can disperse the dye (A) in water.
  • Preferred resins include urethane resins, resins having (meth) acrylate repeating units, and polyvinyl alcohol. And an acetal thereof, a formalin condensate of an aromatic sulfonate, and the like.
  • the resin (B) is at least selected from a urethane resin and a resin having a (meth) acrylic repeating unit. It is preferable to use one type.
  • the resin (B) is preferably a resin having at least one selected from a carboxyl group, a salt of a carboxyl group, and a polyalkyleneoxy structure. By having these functional groups, it has good ink stability, and also has good washing resistance and sweat resistance.
  • the urethane resin may be synthesized by a known method, or a commercially available product may be used.
  • a resin obtained by reacting a polyisocyanate and a polyol is preferable.
  • the polyisocyanate is not particularly limited as long as the polyisocyanate contains two or more isocyanate groups in one molecule.
  • polyisocyanates examples include tolylene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, and 2,6-diisocyanate methyl isocyanate.
  • HDI hexamethylene diisocyanate
  • Aromatic, aliphatic and alicyclic organic diisocyanates such as proate, isophorone diisocyanate (IPDI), methylcyclohexane-2,4- (or 2,6-) diisocyanate, and 4,4′-methylenebis (cyclohexyl isocyanate); Or a multimer containing a polyfunctional isocyanate group such as a burette or isocyanurate thereof, or a polymer of these isocyanates Alone or a mixture may be mentioned.
  • IPDI isophorone diisocyanate
  • methylcyclohexane-2,4- (or 2,6-) diisocyanate methylcyclohexane-2,4- (or 2,6-) diisocyanate
  • 4,4′-methylenebis cyclohexyl isocyanate
  • a multimer containing a polyfunctional isocyanate group such as a burette or isocyanurate thereof, or a polymer of these iso
  • an aliphatic and / or alicyclic organic diisocyanate compound is preferable, and specific examples thereof include aliphatic and alicyclic compounds such as HDI, IPDI, dodecane diisocyanate, cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate. Diisocyanates or mixtures of these isocyanates are more preferred.
  • the polyol is not particularly limited as long as it contains two or more hydroxyl groups in one molecule, and for example, a polymer polyol or a low molecular weight polyol can be used.
  • examples of the polymer polyol include a polyether polyol, a polyester polyol, and a polycarbonate polyol.
  • the polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a random copolymer of ethylene oxide and propylene oxide, a random copolymer of ethylene oxide and butylene oxide, and a block copolymer. Further, a polyether polyester polyol having an ether bond and an ester bond can be used.
  • the polyester polyol is not particularly limited, for example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate polyol, polyethylene seba Kate polyol, polybutylene sebacate polyol, poly- ⁇ -caprolactone polyol, poly (3-methyl-1,5-pentylene adipate) polyol and the like can be mentioned.
  • polycarbonate polyol examples include a linear aliphatic polycarbonate polyol, a branched aliphatic polycarbonate polyol, a polycarbonate polyol having an alicyclic structure in a main chain, and a polycarbonate polyol having an aromatic ring in a main chain.
  • the low molecular weight polyol is not particularly limited, but a low molecular weight diol can be used.
  • ethylene glycol 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl- 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 Aliphatic diols having 2 to 9 carbon atoms such as -hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol , 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis ( Diols having an alicyclic structure having 6 to 12 carbon atoms, such as (hydroxy
  • the polyol is a compound containing two or more hydroxyl groups, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol , 1,2-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol Linear aliphatic glycols such as polyethylene glycol, polypropylene glycol, 1,8-octanediol, 1,2-octanediol and 1,9-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, -Methyl-1,3-propan
  • the acidic group-containing polyol that can be used in the following method for producing a colored resin particle dispersion is a compound having two or more hydroxyl groups and one or more acidic groups in one molecule. It is used for introducing a carboxylate group or a sulfonate group for the purpose of emulsifying a colored resin in water and imparting dispersion stability of a colored resin particle dispersion.
  • the carboxyl group-containing polyol include, but are not limited to, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctane.
  • sulfone group-containing polyol examples include sulfonic acid diol ⁇ 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid ⁇ and sulfamic acid diol ⁇ N, N-bis (2-hydroxylalkyl) sulfamic acid And an alkylene oxide adduct thereof.
  • the salt of the polyol containing a carboxyl group and / or a sulfone group is not particularly limited, and examples thereof include ammonium salts, amine salts [primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propyl Amines and octylamine) salts, secondary monoamines (dimethylamine, diethylamine and dibutylamine) salts, tertiary monoamines (aliphatic tertiary such as trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine) Monoamines; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; tertiary monoamines containing aromatic rings such as benzyldimethylamine, ⁇ -methylbenzyldimethylamine; and N-dimethylaniline ) Salts, alkali
  • the polyol is not a salt but a carboxyl group and / or sulfone group-containing polyol
  • the amount of the neutralizing agent used is preferably such that 10 to 100 mol% of the carboxyl groups and / or sulfonic acid groups contained in the resin is neutralized, preferably 50 to 98 mol%, more preferably 70 to 95 mol%. It is.
  • the neutralizing agent is not particularly limited, and examples thereof include an alkaline compound capable of neutralizing the carboxyl group and / or the sulfone group.
  • an alkaline compound capable of neutralizing the carboxyl group and / or the sulfone group.
  • ammonia amines (primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propylamine and octylamine), secondary monoamines (dimethylamine, diethylamine and dibutylamine), tertiary monoamines ( Aliphatic tertiary monoamines such as trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; benzyldimethylamine, ⁇ -Methylbenzyldimethylamine; and terti
  • Chain extender examples include, but are not limited to, water, short-chain diols such as ethylene glycol, 1,3-propanediol, and 1,4-butanediol, hydrazine, ethylenediamine, diethyltriamine, triethylenetetramine, and tetraethylene.
  • chain extender examples include polyamines such as pentamine, pentaethylenehexamine, propylenediamine, hexamethylenediamine, and cyclohexylenediamine. These may be used alone or in combination of two or more.
  • the urethane resin may have a crosslinked structure.
  • the crosslinked structure refers to a structure obtained by using, as at least one monomer, a compound having a total of three or more hydroxyl groups and isocyanate groups in the molecule.
  • Examples of the compound having three or more hydroxyl groups and isocyanate groups in the molecule include trimethylolpropane, trimethylolethane, and pentaerythritol.
  • the urethane resin may further have a urea bond.
  • a resin having a urethane bond and a urea bond is also referred to as “urethane / urea resin”.
  • One type of preferred embodiment of the dye polymer in the present invention is a urethane / urea resin in which a first partial structure containing a urethane bond and a second partial structure containing a urethane bond are bound by a urea bond.
  • the colored resin particles are preferably used as a dispersion.
  • a method for producing a colored resin particle dispersion using, for example, a urethane resin as the resin (B) is not particularly limited, and examples thereof include the following methods.
  • a polymer having two or more isocyanate groups in one molecule in the presence or absence of an organic solvent containing no active hydrogen-containing group in the molecule eg, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, etc.
  • a isocyanate, a polyol having two or more hydroxyl groups in one molecule, an acidic group-containing polyol or a salt thereof is urethanized by a one-shot method or a multi-stage method to synthesize a urethane resin, and if necessary, the urethane resin Is neutralized with a neutralizing agent, a dye is added, water is dropped to a place where the reaction solution is vigorously stirred
  • the method for producing the colored resin particle dispersion includes, in advance, a polyisocyanate having two or more isocyanate groups in one molecule, a polyol having two or more hydroxyl groups in one molecule, an acidic group-containing polyol or a salt thereof. , A prepolymer is synthesized under the condition of an excess of isocyanate, a dye is added, and the mixture is dispersed in water. Then, a chain extender is added to obtain a colored resin particle dispersion.
  • polyisocyanate polyol, acidic group-containing polyol or salt thereof, neutralizing agent, and chain extender
  • the above-described polyisocyanate, acidic group-containing polyol or salt thereof, neutralizing agent, and chain extender may be used. it can.
  • any resin may be used as long as it has a (meth) acrylate repeating unit.
  • a resin composed of only a (meth) acrylate repeating unit and copolymerizable with (meth) acrylate examples of the resin include a resin made of a copolymer with a monomer.
  • a resin having a (meth) acrylate repeating unit a resin having a hydrophilic repeating unit and a hydrophobic repeating unit is preferable.
  • hydrophobic repeating unit examples include a linear alkyl (meth) acrylate (preferably a linear alkyl (meth) acrylate having 3 to 18 carbon atoms) and a branched alkyl (meth) acrylate (preferably a branched alkyl (meth) acrylate having 3 to 18 carbon atoms) (Meth) acrylate, more preferably isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate), aliphatic (meth) acrylate having a ring structure (preferably cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl ( (Meth) acrylate, adamantyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, etc.
  • a linear alkyl (meth) acrylate preferably a linear alkyl (meth) acryl
  • (meth) acrylate having an aromatic group preferably phenyl (meth) acrylate, benzyl (meth) acrylate Over DOO, phenethyl (meth) acrylate, phenoxyethyl (meth) acrylate, naphthyl (meth) acrylate), and (meth) acrylate and copolymerizable with styrene derivatives (preferably styrene).
  • hydrophilic repeating unit a repeating unit having a hydrophilic group selected from a hydroxyl group, an acid group (preferably a carboxyl group, a sulfonic acid group, a phosphoric acid group) or a salt thereof, and a polyoxyalkylene group is preferred.
  • a hydrophilic group selected from a hydroxyl group, an acid group (preferably a carboxyl group, a sulfonic acid group, a phosphoric acid group) or a salt thereof, and a polyoxyalkylene group.
  • a copolymer having at least a hydrophobic (meth) acrylate and a methacrylate having an acid group and a copolymer having at least styrene and a (meth) acrylate having an acid group are preferable.
  • a method for producing a colored resin particle dispersion using a resin having a (meth) acrylate repeating unit as the resin (B) is not particularly limited, and examples thereof include the following methods.
  • a monomer containing a (meth) acrylate monomer is polymerized in an organic solvent using a known method (for example, a radical polymerization method) to obtain a resin solution, and then a dye (A), water and, if necessary, a neutralizing agent
  • a method in which a surfactant is added and emulsification is performed, and then the solvent is removed.
  • the dye (A), a monomer, and an emulsifier are emulsified in water, and the monomer is dissolved in the presence of a polymerization initiator.
  • the content of the hydrophobic repeating unit in the resin having the (meth) acrylate repeating unit is preferably from 30 mol% to 95 mol%, more preferably 50 mol%, based on all repeating units of the resin having the (meth) acrylate repeating unit. % To 90 mol% is more preferred.
  • the content of the hydrophilic repeating unit in the resin having the (meth) acrylate repeating unit is preferably from 5 mol% to 70 mol%, more preferably 10 mol%, based on all repeating units of the resin having the (meth) acrylate repeating unit. % To 50 mol% is more preferred.
  • the weight average molecular weight (Mw) of the resin (B) is preferably from 1500 to 1,000,000, more preferably from 2,000 to 500,000, and still more preferably from 5,000 to 200,000.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin (B) can be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • HLC-8220GPC manufactured by Tosoh Corporation
  • columns were measured using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation) unless otherwise specified.
  • the average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated in terms of polystyrene.
  • the acid value of the resin is preferably from 5 to 200 mgKOH / g, more preferably from 10 to 150, still more preferably from 20 to 130 mgKOH / g, and particularly preferably from 30 to 120 mgKOH / g.
  • the acid value is 5 mgKOH / g or more
  • the acid value is 200 mgKOH / g or less
  • the hydrophilicity of the ink film of the dispersion of the colored resin particles after heat fixing does not increase, and the color fastness such as washing resistance and sweat resistance does not decrease. preferable.
  • the acid value of the resin is defined by the acid value of the resin before neutralization.
  • the acid value is calculated on the assumption that the resin contains a carboxylic acid or a sulfonic acid that is not neutralized.
  • the acid value can be measured according to the indicator titration method of JIS K 1557.
  • the mass ratio (dye (A)) / (resin (B)) of the dye (A) and the resin (B) represented by the above formula (1) in the colored resin particles is 1.2 or more.
  • the ratio of (dye (A)) / (resin (B)) is 1.5 or more, more preferably 2 or more, and still more preferably 2.5 or more.
  • the concentration of the dye can be increased without increasing the solid concentration in the ink, and a high dyeing concentration can be achieved. Agglomeration between the colored resin particles can be suppressed, and both inkjet dischargeability and temporal stability can be achieved.
  • the upper limit of (dye (A)) / (resin (B)) is preferably 19 or less, more preferably 9 or less, still more preferably 7 or less, and particularly preferably 5.5 or less.
  • the content of the colored resin particles in the ink of the present invention is preferably from 1 to 20% by mass, more preferably from 2 to 15% by mass, and more preferably from 3 to 12% by mass, based on the total amount of the ink, from the viewpoints of ensuring ejection stability and color development. Is more preferred.
  • the content of the dye (A) in the ink of the present invention is preferably 0.5 to 15% by mass, more preferably 1 to 12% by mass, and further preferably 2 to 10% by mass, based on the total amount of the ink.
  • the resin preferably has a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, or the like as a group capable of reacting with the crosslinkable group of the crosslinking agent. It is also preferable not to use a crosslinking agent in the inkjet ink for textile printing. It is also preferred that the colored fine particles of the inkjet ink for textile printing do not contain a crosslinking agent. Furthermore, it is also preferred that the resin does not have a group that can react with the crosslinkable group of the crosslinking agent.
  • the specific dye is preferably present in a form covered with the resin.
  • the polymer and the dye are not covalently linked. Since the polymer and the dye are not bound by a covalent bond, the mobility of the dye is enhanced, and a high color density can be exhibited.
  • the colored resin particles preferably have a form in which the dye is included in the polymer, that is, have a core-shell structure.
  • the core is made of the specific dye, and the shell is made of the resin.
  • the core-shell structure can be confirmed by a transmission electron microscope (TEM).
  • the ink of the present invention may further contain a crosslinking agent.
  • a crosslinking agent in order to further increase the adhesion between the fabric and the resin and improve the image fastness. It is preferable that the resin and the component constituting the fabric are bonded by the cross-linking agent.
  • the crosslinking agent is preferably a compound having at least two crosslinking groups.
  • As the crosslinkable group of the crosslinking agent a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group and the like are preferable.
  • the crosslinking agent examples include a blocked isocyanate compound, an oxazoline compound, and a carbodiimide compound.
  • a blocked isocyanate compound hexamethylene diisocyanate
  • H6XDI hydrogenated xylylene diisocyanate
  • IPDI isophorone diisocyanate
  • H12MDI A blocked isocyanate compound obtained by blocking a TMP (trimethylolpropane) adduct of dicyclohexylmethane diisocyanate) or an isocyanurate with a blocking agent is preferable, and the blocking agent may be DEM (diethyl malonate), DIPA (diisopropyl) based on its dissociation temperature.
  • the dissociation temperature of the crosslinking agent is preferably as low as possible from the viewpoint of crosslinking efficiency, and is preferably as high as possible from the viewpoint of storage stability. The dissociation temperature can be appropriately selected.
  • the dissociation temperature is preferably in the range of 90 ° C to 180 ° C, more preferably in the range of 90 ° C to 120 ° C, and particularly preferably in the range of 110 ° C to 120 ° C.
  • the crosslinking agent is preferably added to the ink as a water-soluble or self-emulsifying agent by imparting a hydrophilic group. In this state, the viscosity of the compounded ink can be reduced, and excellent redispersibility can be obtained.
  • crosslinking agent is preferably present in the ink of the present invention in the form of particles.
  • the crosslinker in the form of particles is referred to as “crosslinker particles”.
  • the cross-linking agent particles have a volume average particle diameter (MV) of 200 nm or less from the viewpoint of improving dischargeability in ink jet.
  • the volume average particle diameter can be measured by the same method as the above-described colored resin particles.
  • crosslinking agent particles examples include, but are not limited to, elastron BN-77 (block isocyanate, volume average particle diameter 19 nm, dissociation temperature of 120 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), elastron BN- 27 (block isocyanate, volume average particle diameter 108 nm, dissociation temperature of 180 ° C.
  • elastron BN-77 block isocyanate, volume average particle diameter 19 nm, dissociation temperature of 120 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • elastron BN- 27 block isocyanate, volume average particle diameter 108 nm, dissociation temperature of 180 ° C.
  • duranate WM44-70G block isocyanate, volume average particle diameter 42 nm, dissociation temperature of about 90 ° C., manufactured by Asahi Kasei Corporation
  • TRIXENE AQUA BI200 block isocyanate, volume average particle diameter 94 nm, dissociation temperature 110-120 ° C., manufactured by BAXENDEN
  • the content of the cross-linking agent in the ink is preferably 0.1 to 10% by mass, since it is necessary to incorporate a cross-linkable functional group sufficient to react the resin and the fabric. More preferably, it is 8 to 8% by mass, and still more preferably 1 to 5% by mass.
  • the ink of the present invention preferably further contains a pigment.
  • the pigment is preferably dispersed in the ink of the present invention.
  • the resin forms a film on the fabric, but depending on the color, the pigment is further dispersed in the film to adjust the hue or to increase the color density. It is preferable because it can be increased. Only one pigment may be used, or two or more pigments may be used.
  • the pigment that can be used in the present invention is not particularly limited, and examples thereof include carbon black and aniline black.
  • any of a water dispersion of a pigment obtained by dispersing a pigment in water using a dispersant or a self-dispersion pigment can be preferably used, and a self-dispersion pigment is preferable.
  • self-dispersible pigments that can be used include self-dispersible carbon blacks CAB-O-JET # 200, 300, and 400 (all manufactured by Cabot Corporation), BONJET CW-1 (500 ⁇ mol / g as a carboxy group), and CW-CW-1.
  • the content of the pigment in the inkjet ink for textile printing is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0.5 to 10% by mass. 5 mass% is more preferred.
  • the ink of the present invention preferably contains a wax.
  • the frictional resistance of the obtained ink film surface can be reduced, and the frictional property can be improved.
  • the wax is preferably present in the ink of the present invention in the form of particles.
  • the wax in the form of particles is called "wax particles".
  • the wax particles it is preferable to use a dispersion in which the wax is dispersed in water.
  • polyethylene also expressed as olefin
  • paraffin also expressed as carnauba
  • Carnauba is used from the viewpoint of improving the frictional property and the color density. These may be used alone or in combination of two or more, or two or more may be used as particles of a mixture thereof.
  • the dispersion form of the wax particles is preferably anionic or nonionic, and particularly preferably nonionic.
  • the nonionic property makes it easy for the wax component to be unevenly distributed on the surface of the ink film.
  • the interaction between the colorant and the pretreatment agent on the fabric is usually inhibited, and the color density may be deteriorated. It is presumed that the use can suppress the deterioration of the color density.
  • the melting point of the wax is preferably in the range of 60 ° C. to 120 ° C., and more preferably in the range of 60 ° C. to 100 ° C., from the viewpoint of improving stability and frictional properties.
  • the melting point of the wax can be measured with a general melting point measuring device.
  • the volume average particle diameter (MV) of the wax particles is preferably 0.3 ⁇ m or less, more preferably 0.2 ⁇ m or less, and particularly preferably 0.1 ⁇ m or less, from the viewpoint of dischargeability in ink jet.
  • the content of the wax in the ink is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 1 to 5% by mass.
  • wax particles commercially available products may be used, and without particular limitation, examples thereof include Polylon L-787 (manufactured by Chukyo Yushi Co., Ltd., polyethylene, nonion, melting point of 102 ° C., volume average particle diameter of 0.1 mm).
  • the ink of the present invention may contain components other than those described above.
  • Other components include, for example, colorants other than the above dyes and pigments, organic solvents, surfactants, pH adjusters, fluorescent brighteners, surface tension adjusters, defoamers, anti-drying agents, lubricants, Viscosity agents, ultraviolet absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, resistivity adjusters, rust inhibitors, inorganic pigments, reduction inhibitors, preservatives, fungicides, chelating agents, etc. No.
  • the ink of the present invention is preferably an ink-jet ink (ink-jet ink). Further, the ink of the present invention is preferably a printing ink, and particularly preferably an inkjet ink for printing.
  • the method for preparing the ink of the present invention is not particularly limited. For example, a method of first obtaining a dispersion of colored resin particles, and then mixing the dispersion of the colored resin particles with an aqueous organic solvent, water, and, if necessary, a surfactant, to prepare an ink. Is mentioned.
  • the ink of the present invention is useful from the viewpoint of workability because it can directly print on a fabric to which a pretreatment agent has not been applied, without bleeding.
  • the surface tension of the ink at 25 ° C. is preferably adjusted to 20 mN / m to 70 mN / m, and adjusted to 25 mN / m to 60 mN / m. Is more preferable.
  • the viscosity of the ink is preferably adjusted to 40 mPa ⁇ s or less, more preferably to 30 mPa ⁇ s or less, and particularly preferably to 20 mPa ⁇ s or less. preferable.
  • the viscosity is measured at 25 ° C. using an E-type rotational viscometer.
  • the surface tension and the viscosity are determined by various additives such as a viscosity modifier, a surface tension regulator, a specific resistance regulator, a film regulator, an ultraviolet absorber, an antioxidant, a discoloration inhibitor, a fungicide, and a rust inhibitor. It can be adjusted by adding a dispersant, a surfactant and the like.
  • the ink cartridge of the present invention is an ink cartridge filled with the above-described ink of the present invention (preferably an ink jet printing ink).
  • the ink jet printer of the present invention is an ink jet printer filled with the ink of the present invention (preferably an ink jet printing ink).
  • the ink set By using an ink set containing the ink of the present invention (preferably an inkjet ink for textile printing), a clearer image can be obtained when performing multicolor printing.
  • the ink set preferably contains at least one selected from a black ink, a cyan ink, a magenta ink, and a yellow ink, and contains all the black ink, cyan ink, magenta ink, and yellow ink. Is preferred.
  • the black ink is the ink of the present invention, so that the image clarity is particularly excellent.
  • magenta ink, yellow ink and other color inks used in the ink set of the present invention dye or pigment inks are preferable.
  • the dye is not particularly limited, but the following dyes are particularly preferable.
  • CI is an abbreviation for “color index”.
  • Disperse are disperse dyes, and those described as “Solvent” are oil-soluble dyes.
  • Solvent Blue 3 4, 5, 35, 36, 38, 44, 45, 59, 63, 67, 68, 70, 78, 83, 97, 101, 102, 104, 105, 111, 122, C. I.
  • the ink-jet printing method of the present invention is an ink-jet printing method including a step of printing the ink of the present invention (preferably an ink-jet ink for printing) directly on a fabric by an ink-jet method.
  • the cloth may be a cloth pretreated with an aqueous pretreatment liquid containing a flocculant. That is, the inkjet printing method of the present invention may include a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to the fabric to obtain a pretreated fabric.
  • directly printing the textile ink jet ink on the fabric by the inkjet method means that the transfer process is unnecessary, the process of applying the printing paste is unnecessary, and the textile ink jet ink is directly applied to the fabric. Refers to being stamped.
  • the inkjet printing method of the present invention does not generate waste materials such as wastewater and transfer paper, is a simple method, and is useful.
  • the pretreatment step in the second aspect is a step of applying an aqueous pretreatment liquid containing a flocculant to the fabric to obtain a pretreated fabric.
  • the method for applying the aqueous pretreatment liquid to the fabric is not particularly limited, and examples thereof include a coating method, a padding method, an inkjet method, a spray method, and a screen printing method.
  • the coagulant contained in the aqueous pretreatment liquid is not particularly limited as long as it has an action of coagulating an aqueous dispersion of a dye, a resin or a pigment, but is not particularly limited, and may be an organic acid, a polyvalent metal salt, and a cationic compound. It is preferable that at least one kind is selected.
  • the aggregating agent is a cationic compound or a polyvalent metal salt and the colored resin particles have an anionic group (preferably an acid group)
  • an anionic group preferably an acid group
  • a high-concentration colored cloth can be formed by printing with the above-described inkjet printing method.
  • the pre-treated cationic compound or polyvalent metal salt aggregates at the moment of contact with the ink containing the colored resin particles having an anionic group and stays on the fabric surface, resulting in a surface It is considered that the amount of the dye present in the dye increases and the concentration can be increased.
  • the flocculant is a cationic compound.
  • a polyvalent metal salt is a compound composed of a divalent or higher valent metal ion and an anion. Specifically, calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium hydroxide, calcium carbonate, magnesium chloride, magnesium acetate, magnesium sulfate, magnesium carbonate, barium sulfate, barium chloride, zinc sulfide, zinc carbonate, copper nitrate And the like.
  • the cationic compound is not particularly limited, and may be a low molecular compound or a high molecular compound.
  • the low molecular weight cationic compound include (2-hydroxyethyl) trimethylammonium chloride, benzoylcholine chloride, benzyltriethylammonium chloride, trimethylacetohydrazide ammonium chloride, 1-butyl-1-methylpyrrolidinium chloride, 3- Hydroxy-4- (trimethylammonio) butyrate hydrochloride, glycidyltrimethylammonium chloride, L-carnitine hydrochloride and the like can be mentioned.
  • high molecular weight cationic compound examples include, for example, polyallylamine or a derivative thereof, an amine-epihalohydrin copolymer, and other quaternary ammonium salt type cationic polymers.
  • Chargeable cationic polymers can be mentioned. In some cases, a water-dispersible cationic polymer may be used.
  • the coagulants may be used alone or in combination of two or more.
  • the aqueous pretreatment liquid may contain, for example, a surfactant and a resin in addition to water and an aqueous organic solvent.
  • the inkjet printing method of the present invention preferably further includes a heat treatment step.
  • a heat treatment step by performing a heat treatment step after printing on the fabric, the resin is likely to form a film.
  • the heat treatment step is preferably performed by heating the colored cloth.
  • the temperature of the heat treatment step is preferably from 100 to 220 ° C, more preferably from 130 to 200 ° C.
  • the heating time in the heat treatment step is preferably from 20 seconds to 300 seconds, more preferably from 30 to 240 seconds, and still more preferably from 40 to 180 seconds.
  • the fabric colored with the inkjet ink for textile printing of the present invention is further improved in texture flexibility and robustness (particularly rub resistance) by padding the entire surface of the colored fabric with a post-treatment agent, if necessary.
  • a colored cloth can be obtained.
  • post-treatment agents for softening include cationic surfactants, anionic surfactants, nonionic surfactants, dimethyl silicone oil, amino silicone oil, carboxy-modified silicone oil, hydroxy-modified silicone oil, and fatty acids. Amides, fatty acid amides, mineral oils, vegetable oils, animal oils, plasticizers and the like.
  • post-treatment agents for the purpose of improving the slipperiness of the colored cloth surface, metal soap, paraffin wax, carnauba wax, microstalin wax, dimethyl silicone oil, amino silicone oil, carboxy-modified silicone oil, hydroxy-modified silicone oil, etc. Is mentioned.
  • a colored cloth is immersed in a product obtained by emulsifying, thermally emulsifying, or dispersing these post-treatment agents in a water solvent by stirring with a mixer, squeezed and dried with a mangle or the like, and subjected to heat treatment. Further, by adding a small amount of a resin emulsion as a fixing agent in the post-treatment agent, the friction resistance of the colored cloth can be improved.
  • the blending amount with respect to the post-treatment agent is preferably less than 5%, which is preferable because the softness of the texture of the colored cloth is not easily impaired.
  • the resin emulsion to be added as a fixing agent to the post-treatment agent is not particularly limited, but is an acrylate resin emulsion, a urethane resin emulsion, an ethylene / vinyl acetate copolymer resin (EVA resin) emulsion, a silicone / acryl resin emulsion.
  • EVA resin ethylene / vinyl acetate copolymer resin
  • the glass transition point of these resin emulsions is preferably 0 ° C. or lower.
  • the inkjet printing method of the present invention can be applied to various types of fabrics.
  • fabrics include synthetic fibers such as nylon, polyester, and acrylonitrile; semi-synthetic fibers such as acetate and rayon; natural fibers such as cotton, silk, and wool; and mixed fibers, fabrics, and knits thereof.
  • Nonwoven fabrics and the like can be mentioned.
  • the effects of the present invention are remarkably exhibited when applied to a fabric containing at least one selected from cotton and polyester (specifically, cotton, polyester, and a blend of cotton / polyester).
  • Clothing includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses, and the like. It is also suitable for bedding and handkerchiefs.
  • urethane resin (U-1) having a residual isocyanate group at a terminal was synthesized. The presence of the residual isocyanate group was confirmed by potentiometric titration. Ethyl acetate was added thereto to adjust the solid content to 30% by mass.
  • the obtained urethane resin (U-1) had a weight average molecular weight in terms of polystyrene of 6,400 and an acid value of 39 mgKOH / g.
  • the dye / resin (mass ratio) and average particle diameter (MV) of the obtained colored resin particle dispersion were as shown in Table 1 below.
  • the resin or prepolymer used is also described.
  • Resins A-1 to A-6 each have a (meth) acrylate repeating unit.
  • Mw weight average molecular weight
  • dispersity dispersity
  • acid value mgKOH / g
  • the monomers (M-1) to (M-8) are as follows.
  • M-1 benzyl methacrylate
  • M-2 butyl acrylate
  • M-3 styrene
  • M-4 methacrylic acid
  • M-5 acrylic acid
  • M-6 2-methacryloyloxyethyl succinic acid (light ester HO- manufactured by Kyoeisha Chemical Co., Ltd.)
  • M-7 2-methacryloxyethyl acid phosphate (Light ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.)
  • M-8 polyethylene glycol monomethyl ether methacrylate (having an average of 9 ethyleneoxy repeating units) (Light ester 130MA manufactured by Kyoeisha Chemical Co., Ltd.)
  • TET tetraethylene glycol
  • GLY glycerin
  • DEG diethylene glycol
  • PG propylene glycol
  • Examples 1 to 7, 10 to 32, Comparative Examples 1 to 14 (inkjet printing) Katiomaster PD-7 (amine / epichlorohydrin condensation type ammonium cationic polymer flocculant; manufactured by Yokkaichi Gosei Co., Ltd., solid content 50% by mass) (50 parts by mass), BYK348 (manufactured by BYK Japan Japan Co., Ltd.) (5) Parts by mass), glycerin (100 parts by mass) and water (845 parts by mass) were mixed and stirred to prepare an aqueous pretreatment liquid.
  • Katiomaster PD-7 amine / epichlorohydrin condensation type ammonium cationic polymer flocculant; manufactured by Yokkaichi Gosei Co., Ltd., solid content 50% by mass) (50 parts by mass), BYK348 (manufactured by BYK Japan Japan Co., Ltd.) (5) Parts by mass), glycerin (100 parts by mass) and water (845 parts
  • the prepared aqueous pretreatment liquid was padded with a cotton cloth (with cotton broadsil, manufactured by Shisen, Co., Ltd., product code A02-01002) (referred to as "cotton” in the table below) and a polyester cloth (Shinosen, Inc.). (Product code A02-01019) (referred to as “polyester” in the table below) and a blend of 65% polyester and 35% cotton (blend polyester 65 / cotton 35 broad; product code A02-01030 manufactured by Shimosen Co., Ltd.) Each was squeezed at a squeezing ratio of 70% and dried for 24 hours to obtain a pretreated fabric. The squeezing ratio (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid with respect to the cloth after squeezing the cloth containing the aqueous treatment liquid.
  • the ink jet ink for textile printing obtained above is filled in an ink cartridge, and an image is recorded on the pretreated cloth shown in the table below using an ink jet printer (PX-045A, manufactured by Seiko Epson Corporation). A colored cloth was obtained.
  • ⁇ Color development> The color development was evaluated based on the following criteria based on OD (Optical Density) value.
  • SS OD value 1.6 or more S: OD value 1.4 or more and less than 1.6
  • A OD value 1.2 or more and less than 1.4
  • B OD value 1.0 or more and less than 1.2
  • C OD value 1. Less than 0
  • the obtained colored cloth was evaluated for washing resistance, sweat resistance, friction resistance, ejection stability, and stability over time as described below.
  • ⁇ Discharge stability> The number of sheets that can be printed on the entire surface of the A4 fabric without blurring the image and clogging the nozzles of the inkjet head was evaluated according to the following criteria.
  • the ink was heated at 50 ° C. for one month in a closed container, the ejection stability was similarly evaluated.
  • GLY glycerin PG: propylene glycol P1: self-dispersion type carbon black pigment CAB-O-JET 200 (manufactured by Cabot Corporation)
  • W1 Carnauba wax
  • CL1 Elastron BN-77 (block isocyanate, volume average particle diameter 19 nm, dissociation temperature of 120 ° C. or more, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
  • Examples 33 to 40 A colored cloth was obtained and evaluated in the same manner as in Example 1 except that the obtained ink jet printing inks (BI-27) to (BI-34) were used. Table 7 below shows the evaluation results of Examples 33 to 40.
  • Examples IS-1 to IS-3, Comparative Example IS-1C Preparation of inkjet ink (Qm)] (Preparation of pigment dispersion) 3 g of a styrene-acrylic acid copolymer (Joncryl 678, manufactured by BASF, trade name), 1.3 g of dimethylaminoethanol, and 80.7 g of ion-exchanged water were stirred and mixed at 70 ° C. Then, C.I. I. Pigment Red 112 (15 g) and zirconia beads having a particle diameter of 0.5 mm were filled at a volume ratio of 50% and dispersed using a sand grinder mill to obtain a pigment dispersion having a pigment content of 15% by mass.
  • a styrene-acrylic acid copolymer Joncryl 678, manufactured by BASF, trade name
  • inkjet ink (Qc) C. I. Pigment Red 112, and C.I. I.
  • An ink-jet ink (Qc) was prepared in the same manner as in the preparation of the ink-jet ink (Qm) except that Pigment Blue 15: 4 was used.
  • the inkjet ink (Qc) is a cyan ink.
  • inkjet ink (Qy) C. I. Pigment Red 112, and C.I. I.
  • An ink-jet ink (Qy) was prepared in the same manner as in the preparation of the ink-jet ink (Qm) except that Pigment Yellow 180 was used.
  • the inkjet ink (Qy) is a yellow ink.
  • inkjet ink (Qb) was prepared in the same manner as in the preparation of the ink-jet ink (Qm) except that carbon black was used instead of Pigment Red 112.
  • the inkjet ink (Qb) is a black ink.
  • Ink jet printing ink sets S1 to S3 and X1 were prepared using combinations of the ink jet inks shown in the table below.
  • the aqueous pretreatment liquid prepared above was applied to a polyester fabric (polyester tropical (manufactured by Teijin Limited), a product of Aizen Co., product code A02-01019) and a cotton fabric (with cotton broadsil, color Squeezed at a 70% squeezing rate for each of a blend of 65% polyester and 35% cotton (blend polyester 65 / cotton 35broad, product code of Aizen Co., Ltd., product code A02-01030). Dry for 24 hours.
  • the squeezing ratio (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid with respect to the cloth after squeezing the cloth containing the aqueous treatment liquid.
  • inkjet printing, heat treatment and evaluation The ink sets for ink jet textile printing S1 to S3 and X1 are loaded into an ink cartridge, and the polyester fabric (polyester tropical (polyester) after the pre-treatment step) is loaded using an ink jet printer (Carario PX-045A, manufactured by Seiko Epson Corporation).
  • various types of cloths can be colored, and the coloring property of an obtained image, inkjet dischargeability, aging stability, dyeing fastness (washing resistance, abrasion resistance, and sweat resistance) Ink), an ink cartridge filled with the above ink, an ink set, an ink jet printer, and an ink jet printing method using the above ink can be provided.

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

Abstract

La présente invention concerne : une encre qui comprend de l'eau, un solvant organique aqueux et des particules de résine colorée, les particules de résine comprenant une résine (B) et un colorant (A) représenté par une structure spécifique et le rapport de masse (colorant (A))/(résine (B)) entre le colorant (A) et la résine (B) est d'au moins 1,2 ; une cartouche d'encre étant chargée avec ladite encre ; un ensemble d'encres ; une imprimante à jet d'encre ; et un procédé d'impression de textile par jet d'encre comprenant une étape d'impression sur un tissu avec ladite encre par un procédé à jet d'encre.
PCT/JP2019/024546 2018-06-26 2019-06-20 Encre, cartouche d'encre, ensemble d'encres, imprimante à jet d'encre et procédé d'impression de textile par jet d'encre Ceased WO2020004228A1 (fr)

Priority Applications (1)

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JP2020527460A JPWO2020004228A1 (ja) 2018-06-26 2019-06-20 インク、インクカートリッジ、インクセット、インクジェットプリンタ及びインクジェット捺染方法

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JP2018121347 2018-06-26
JP2018-121347 2018-06-26

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WO2020004228A1 true WO2020004228A1 (fr) 2020-01-02

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JP2020132829A (ja) * 2019-02-26 2020-08-31 セイコーエプソン株式会社 インクジェットインク組成物及びインクジェット記録方法
JP2022014128A (ja) * 2020-07-06 2022-01-19 コニカミノルタ株式会社 インクジェット記録液セットおよび当該インクジェット記録液セットを用いる画像形成方法
CN116409074A (zh) * 2022-01-07 2023-07-11 精工爱普生株式会社 处理方法
CN117626687A (zh) * 2022-08-31 2024-03-01 精工爱普生株式会社 染料印染用处理液组合物、组合物组、印染方法及喷墨印染方法
CN117957289A (zh) * 2021-10-21 2024-04-30 Dnp精细化工股份有限公司 油墨组合物、油墨组、记录方法、记录物的制造方法和记录物
WO2025110169A1 (fr) * 2023-11-22 2025-05-30 三菱鉛筆株式会社 Dispersion de particules de résine et composition d'encre aqueuse contenant celle-ci

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JP2025165566A (ja) * 2024-04-23 2025-11-05 コニカミノルタ株式会社 インクジェット捺染方法、インクジェット捺染用インクセット、及びインクジェット捺染装置

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CN117957289A (zh) * 2021-10-21 2024-04-30 Dnp精细化工股份有限公司 油墨组合物、油墨组、记录方法、记录物的制造方法和记录物
CN116409074A (zh) * 2022-01-07 2023-07-11 精工爱普生株式会社 处理方法
CN117626687A (zh) * 2022-08-31 2024-03-01 精工爱普生株式会社 染料印染用处理液组合物、组合物组、印染方法及喷墨印染方法
WO2025110169A1 (fr) * 2023-11-22 2025-05-30 三菱鉛筆株式会社 Dispersion de particules de résine et composition d'encre aqueuse contenant celle-ci

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