WO2014084161A1 - インク組成物及び捺染方法 - Google Patents
インク組成物及び捺染方法 Download PDFInfo
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- WO2014084161A1 WO2014084161A1 PCT/JP2013/081622 JP2013081622W WO2014084161A1 WO 2014084161 A1 WO2014084161 A1 WO 2014084161A1 JP 2013081622 W JP2013081622 W JP 2013081622W WO 2014084161 A1 WO2014084161 A1 WO 2014084161A1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920006304 triacetate fiber Polymers 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
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- 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
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
- C08K5/235—Diazo and polyazo compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5221—Polymers of unsaturated hydrocarbons, e.g. polystyrene polyalkylene
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
-
- 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
Definitions
- the present invention relates to an ink composition used for ink jet printing containing a pigment, water, a specific polymer, a styrene butadiene resin, a water-soluble organic solvent, a nonionic surfactant, and an alkyl ether solvent, and further uses the ink composition.
- the present invention relates to an inkjet printing method and a dyeing method.
- Inkjet recording has become widespread as a printing method for offices and homes as information is digitized. In recent years, many applications have been developed for commercial printing and textile printing. As the use of ink jet recording expands, the colorant used in the ink jet ink is changed from a conventional water-soluble dye such as an acid dye or a direct dye to a water-insoluble colorant, that is, a disperse dye or a dye. Various colorants such as pigments have been used.
- a recorded image using a water-soluble dye as a colorant has low durability against light, ozone, water and the like.
- a recorded image using a pigment as a colorant is known to be excellent in various fastness properties against light, ozone, water and the like.
- an ink containing a colorant that is insoluble in water, such as a pigment has a drawback that the dispersed state of the pigment is broken and the pigment is agglomerated when it loses the moisture contained therein for some reason and becomes dry. Since the pigment in the ink once agglomerated in this way cannot be returned again to the dispersed state even if a liquid medium such as water is added (redispersibility is poor), improvement of the pigment is strongly demanded.
- an ink containing a pigment is required to be stable over a long period of time. It is known that a pigment existing in a dispersed state as particles in an ink undergoes a sedimentation phenomenon over time due to aggregation of pigment particles. For this reason, there are problems such as a density gradient in the ink, and the initial printing characteristics cannot be obtained, and the aggregated particles are clogged in the nozzles and cannot be ejected. .
- Patent Document 1 As an ink-jet ink using a pigment, the ink of Patent Document 1 can be mentioned. This is a dispersed ink composition using a polymer dispersant. Patent Document 2 discloses an ink composition using a self-dispersing pigment.
- An object of the present invention is to provide a pigment ink composition used for inkjet printing excellent in redispersibility and storage stability, and an inkjet printing method and a dyeing method using the same.
- the present inventors have found that the above ink composition containing a pigment, water, a specific polymer, a styrene-butadiene resin, a water-soluble organic solvent, and a nonionic surfactant is used.
- the present inventors have found that the above problems can be solved and have completed the present invention. That is, the present invention relates to the following [1] to [9].
- Pigment, water, polymer D consisting of at least two monomers selected from the group consisting of monomer A, monomer B and monomer C represented by the following formula (1), styrene-butadiene resin, water-soluble organic solvent, and An ink composition for inkjet printing, which contains a nonionic surfactant.
- Monomer A A monomer in which R is a hydrogen atom in the following formula (1).
- Monomer B A monomer in which R is a C1-C4 alkyl group in the following formula (1).
- Monomer C A monomer in which R is an aryl group or an aryl C1-C4 alkyl group in the following formula (1).
- the content of each component relative to the total mass of the ink composition is The above pigment: 1 to 15% by mass, Polymer D: 0.1 to 15% by mass, Styrene-butadiene resin: 1 to 20% by mass, Water-soluble organic solvent: 10 to 45% by mass, Nonionic surfactant: 0.01 to 5% by mass,
- [6] The above-mentioned [6], wherein the recording material is a fiber selected from the group consisting of polyester, cellulose, polyamide, and natural fibers, a mixed fiber containing these fibers, or a fabric containing these fibers.
- Inkjet printing method [8] The pigment contained in the ink composition adhered to the recording material using the ink jet textile printing method according to the above [6] or [7] is dyed on the recording material by a steaming or baking treatment, and dyeing is performed. Inkjet dyeing method to be performed. [9] The inkjet dyeing method according to [8], wherein the steaming or baking treatment temperature is 80 to 250 ° C., and the treatment time is in the range of 10 seconds to 30 minutes. [10] A dyed product dyed by the inkjet dyeing method according to [8] or [9].
- the present invention it is possible to provide a pigment ink composition used for inkjet printing excellent in storage stability and redispersibility, and an inkjet printing method and a dyeing method using the same.
- ink composition means the “(pigment) ink composition used for inkjet printing”.
- % and “parts” including examples and the like are both described on a mass basis.
- the pigment is not particularly limited, and a known pigment can be used.
- a known pigment can be used.
- inorganic pigments, organic pigments, extender pigments and the like are known.
- the inorganic pigment examples include carbon black, metal oxide, hydroxide, sulfide, ferrocyanide, and metal chloride.
- carbon black is preferable as the black pigment.
- carbon black there are various types of carbon black, such as thermal black and acetylene black obtained by pyrolysis method; oil furnace black, gas furnace black, lamp black, gas black, and channel black obtained by incomplete combustion method. It is done.
- acetylene black, oil furnace black, gas furnace black, lamp black, channel black and the like are preferable as carbon black.
- the carbon black for example, Raven760ULTRA, Raven780ULTRA, Raven790ULTRA, Raven1060ULTRA, Raven1080ULTRA, Raven1170, Raven1190ULTRA II, Raven1200, Raven1250, Raven1255, Raven1500, Raven2000, Raven2500ULTRA, Raven3500, Raven5000ULTRA II, Raven5250, Raven5750, Raven7000 (or, (Manufactured by Columbia Carbon Co.); Monarch700, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monar h1300, Monarch 1400, Regal 1330R, Regal 1400R, Regal 1660R, Mogu L (above, manufactured by Cabot Corporation); Color Black FW1, Color Black FW2, 160 Black, FW200C, Color Black FW2C, Color Black FW2C, Color Black FW2C , Printex U, Print
- a metal oxide as a white pigment.
- the metal oxide include zinc oxide, titanium oxide, and zirconia oxide, and titanium oxide is preferable.
- the type of titanium oxide include rutile type and anatase type. Titanium oxide may be used as a powder as it is, or may be silicon dioxide, aluminum oxide, zirconia oxide, zinc oxide, or an organic substance having a hydroxyl group, etc. whose surface is treated. Of these, surface-treated titanium oxide is preferred.
- titanium oxide examples include, for example, DUAWHITE TCR-52, TITON R-32, TITONE R-7E, TITONE R-21, TITONE R-62N, TITONE R-42 (above, manufactured by Sakai Chemical Industry Co., Ltd.); TIPAQUE CR-50, TIPAQUE CR-50-2, TIPAQUE CR-58, TIPAQUE CR-60, TIPAQUE CR-80, TIPAQUE CR-90 (manufactured by Ishihara Sangyo Co., Ltd.); TITANIX JA-600A, TITANIX JR-605 (Above, manufactured by Teica Corporation); ST-455, ST-455WB, ST-457SA, ST-457EC (above, manufactured by Titanium Industry Co., Ltd.);
- organic pigment examples include, for example, an azo pigment having at least one azo group in the molecule, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, a dioxazine pigment, a perylene pigment, a perinone pigment, a thioindigo pigment, an anthraquinone pigment, and a quinophthalone. Pigments. Specific examples of the organic pigment include C.I. I.
- extender pigment examples include silica, calcium carbonate, talc, clay, barium sulfate, and white carbon. These extender pigments may be used alone, but are usually used in combination with an inorganic pigment or an organic pigment.
- a single pigment is usually used.
- two or more kinds of pigments may be used in combination.
- extender pigments can also be used in combination for improving fluidity.
- two or more pigments selected from inorganic pigments and organic pigments can be used in combination for adjusting the hue of the dyed product.
- the hue adjustment here is carried out for the purpose of obtaining a dyed product with shades; expanding the color gamut of dyeing; For this purpose, several kinds of organic pigments can be used together to adjust the desired hue.
- Polymer D As a method for stabilizing a pigment dispersion in an aqueous medium (meaning a mixed solvent of water and a water-soluble organic solvent other than an alkyl ether solvent and an alkyl ether solvent described later), a dispersant such as a resin is generally used. A method of stabilizing the pigment dispersion by entropy, ion repulsive force, steric repulsive force, or the like is used.
- the dispersant has a hydrophilic part and a hydrophobic part, and the hydrophobic part is adsorbed on the pigment surface and dispersed in an aqueous medium at the hydrophilic part.
- the above polymer D can be used as a dispersant having such properties.
- the polymer D is a polymer obtained by polymerizing at least two types of monomers selected from the group consisting of the monomer A, the monomer B, and the monomer C represented by the above formula (1). Preferably, at least one type is selected from monomer A, monomer B, and monomer C.
- the polymer D may be any of random copolymers, alternating copolymers, block copolymers, and graft copolymers of these monomers.
- the mass average molecular weight of the polymer D is usually 10,000 to 60,000, preferably 10,000 to 40,000, more preferably 10,000 to 30,000. When the mass average molecular weight is within these ranges, the stability of the pigment dispersion becomes good.
- the acid value of the polymer D is usually 50 to 300, preferably 90 to 200, more preferably 100 to 150, in units of mgKOH / g. If the acid value is too small, the solubility of the polymer D in water or an aqueous medium may decrease, and if it is too large, the color developability may decrease.
- Examples of the polymer D include Hiros X VS- 1202 (Random polymer having an acid value of 140 mgKOH / g and a mass average molecular weight of 11,000, which is made of methyl methacrylate, butyl methacrylate, and methacrylic acid) manufactured by Seiko PMC.
- the polymer D may be used after neutralizing the acid value as necessary.
- the degree of neutralization is 100%.
- the degree of neutralization of polymer D is usually about 50 to 200%, preferably 80 to 150%, more preferably about 100 to 120% in the ink composition.
- Examples of the neutralizing agent used for neutralizing the polymer D include, for example, alkali metal hydroxides, alkaline earth metal hydroxides, inorganic bases such as ammonia, and organic bases such as aliphatic amine compounds and alkanolamine compounds. Etc.
- alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
- alkaline earth metal hydroxide examples include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide.
- alkali metal hydroxides and ammonia are preferable, and lithium hydroxide, sodium hydroxide, and ammonia are particularly preferable.
- alkanolamine compounds examples include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine, N-methyldiethanolamine and other mono, di, or tri C1. -C3 alkanolamine compounds. Among these, tertiary amines are preferable, and triethanolamine is particularly preferable.
- Examples of the aliphatic amine compound include mono-, di-, or tri-C1-C3 amine compounds such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine, and trimethylamine. Of these, triethylamine is preferred.
- neutralizers may be used alone or in combination of two or more.
- the monomer A is a monomer in which R is a hydrogen atom in the above formula (1), that is, methacrylic acid.
- the monomer B is a monomer in which R is a C1-C4 alkyl group in the above formula (1).
- Examples of the monomer B include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate.
- the monomer C is a monomer in which R is an aryl group or an aryl C1-C4 alkyl group in the above formula (1).
- R is an aryl group or an aryl C1-C4 alkyl group in the above formula (1).
- aryl a C6-C10 aryl group is preferable, and a phenyl group or a naphthyl group is particularly preferable.
- an alkyl moiety such as phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl and the like is linear or branched, preferably linear phenyl C1-C4 alkyl group; naphthylmethyl, naphthylethyl, And alkyl groups such as naphthylpropyl and naphthylbutyl are linear or branched, preferably a linear naphthyl C1-C4 alkyl group. Of these, a phenyl C1-C4 alkyl group is preferred.
- the monomer C include, for example, phenyl methacrylate, benzyl methacrylate, and phenethyl methacrylate.
- the styrene-butadiene resin is often sold in the form of latex (emulsion) and can be easily purchased. Specific examples thereof include, for example, Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, Nipol 2507H, Nipol LX303A (manufactured by Nippon Zeon Co., Ltd.), grades 0695, 0696, 0561, 0589, 0602, 2108, 05 , 0545, 0548, 0568, 0569, 0573, 0597C, 0850Z latex (above, manufactured by JSR Corporation), etc., most of which are liquids obtained by emulsifying resin with a solid content of 30 to 60%.
- any of the above-described latexes can be used, and among them, a carboxy-modified styrene-butadiene resin is preferably used.
- resins include Nipol LX415M, Nipol LX432M, Nipol LX433C, Nipol LX421, 0695, 0696, 0533, 0545, 0548, 0568, 0568, 0573, 0597C, 0850Z, and 0695, 0533, 0568. , 0597C, 0850Z.
- a single styrene-butadiene resin may be used, or two to three types may be used in combination.
- water-soluble organic solvent examples include C1-C4 monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; ethylene glycol, 1, 2- or C2- such as 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, 1,3-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, etc.
- C1-C4 monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol
- ethylene glycol 1, 2- or C2- such as 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, 1,
- C6-diol glycerin, hexane-1,2,6-triol, C3-C6 triol such as trimethylolpropane; carboxylic acid amide such as N, N-dimethylformamide, N, N-dimethylacetamide; 2-pyrrolidone, N- Methyl-2-pyrrolidone, 1,3-dimethylimidazolidine-2- , Heterocyclic ureas such as 1,3-dimethylhexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; 1,2- Linear or cyclic ethers such as dimethoxyethane, tetrahydrofuran, dioxane; di- or tri-C2-C3 alkylene glycols or thioglycols such as diethylene glycol, triethylene glycol, dipropylene glycol,
- C2-C6 diol in which 1,2-propylene glycol
- C3-C6 triol in which glycerin
- polyglyceryl ether in which diglycerin
- C1-C4 alkyl ethers of polyhydric alcohols butyl carbitol is preferred.
- These water-soluble organic solvents may be used alone or in combination.
- polyglyceryl ether preferably glycerin and / or diglycerin
- C2-C6 diol preferably ethylene glycol, 1,2- or 1,3-propylene glycol, more preferably ethylene glycol, 1,2 -Propylene glycol.
- Nonionic surfactant examples include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether.
- Ether type polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc.
- Ester series 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, , 5-dimethyl-1-hexyne-3-acetylene glycol (alcohol) -based ol; Nissin Chemical Industry Co. trade name Surfynol RTM 104,105PG50,82,420,440,465,485, DF-110D, Olfine RTM STG; polyglycol ether type (for example, TergIt RTM 15-S-7 manufactured by SIGMA-ALDRICH) and the like.
- the nonionic surfactants can be used alone or in combination, and are preferably Surfinol-based, more preferably Surfinol RTM 420, Surfinol RTM 440, Surfinol RTM 465.
- Surfinol-based more preferably Surfinol RTM 420, Surfinol RTM 440, Surfinol RTM 465.
- the superscript “RTM” means a registered trademark.
- Examples of the content of each component with respect to the total mass of the ink composition used for the ink jet textile printing include the following ranges.
- Pigment Usually 1 to 15%, preferably 1 to 10%, more preferably 1 to 7%.
- Polymer D Usually 0.1 to 15%, preferably 0.1 to 9%, more preferably 0.2 to 6%.
- Styrene-butadiene resin usually 1 to 20%, preferably 3 to 15%, more preferably 3 to 12%.
- Water-soluble organic solvent usually 10 to 45%, preferably 15 to 38%, more preferably 20 to 35%.
- Nonionic surfactant Usually 0.01 to 5%, preferably 0.05 to 3%, more preferably 0.1 to 2.5%. The balance is water.
- the method for preparing the ink composition is not particularly limited. Usually, after preparing an aqueous pigment dispersion containing the pigment and the polymer D, a styrene-butadiene resin, a water-soluble organic solvent, a nonionic surfactant, and The ink composition is prepared by adding other components as necessary.
- the pigment, polymer D, and styrene-butadiene resin are mixed with water or an aqueous solvent, a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, and the like.
- a method of dispersing using a sand mill (bead mill) is preferable.
- the pigment dispersion using a sand mill (bead mill) is prepared by using beads with a small system (approximately 0.01 to 1 mm in diameter) and increasing the dispersion efficiency by increasing the filling rate of the beads. It is desirable.
- the pigment particle size can be reduced, and a dispersion having good dispersibility can be obtained.
- an antifoaming agent such as silicone or acetylene glycol may be added for the purpose of suppressing this.
- some antifoaming agents inhibit pigment dispersion and micronization, it is preferable to select and use one that does not have such an adverse effect.
- the polymer D can be used as a pigment dispersant.
- the polymer D may be in a state of being adsorbed on a part of the pigment surface, or in a state of covering the entire pigment surface (referred to as a microencapsulated pigment or the like). The latter is preferred.
- any of the known microencapsulation methods can be used. There are roughly two methods, a physical / mechanical method and a chemical method. As the latter chemical method, a surface precipitation method, a kneading method, an interfacial polymerization method (also referred to as a surface polymerization method) and the like have been proposed. Among these, the surface precipitation method includes an acid precipitation method and a phase inversion emulsification method.
- any method may be used and is not particularly limited, but among these, the surface precipitation method is preferable, and the phase inversion emulsification method is particularly preferable.
- phase inversion emulsification method for example, a solution of a hydrophobic organic solvent in which a dispersant is dissolved and a liquid containing a neutralizing agent and water are mixed to obtain an emulsified (emulsion or microemulsion) liquid, and a pigment is further added. Then, after mixing and dispersing, the solvent is removed to obtain an aqueous pigment dispersion.
- the average particle diameter of the pigment in the pigment dispersion prepared as described above is usually 200 nm or less, preferably 50 to 150 nm, more preferably 60 to 120 nm. By setting the average particle size within this range, the dispersion stability and ejection stability are excellent, and the dyeing density is increased.
- the average particle diameter can be measured using a laser light scattering method.
- the pH of the ink composition is preferably pH 5 to 11 and more preferably pH 7 to 10 for the purpose of improving storage stability.
- the surface tension of the ink composition at 25 ° C. is preferably 10 to 50 mN / m, more preferably 20 to 40 mN / m. Further, the viscosity at 25 ° C. of the ink composition is preferably 30 mPa ⁇ s or less, more preferably 20 mPa ⁇ s or less, and particularly preferably 2 to 10 mPa ⁇ s.
- the pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent and a surfactant as described later.
- the content of the polymer D can be expressed by a numerical value called a fractional ratio, and this fractional ratio can be obtained by the following formula.
- Ratio of parts number of parts of polymer D / number of parts of pigment
- the intensity ratio is usually 0.1 to 1.0, preferably 0.1 to 0.6, more preferably 0.2 to 0.4. When the ratio is within this range, a pigment dispersion excellent in stability and a good dyed product can be obtained.
- ink preparation agents other than those described above can be used as appropriate.
- examples thereof include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, antioxidants, and surfactants.
- antiseptic / antifungal agents include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, antioxidants, and surfactants.
- antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. .
- preservatives include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole. , Isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, Examples include benzyl bromacetate and inorganic salt compounds. Specific examples of the organic halogen compound include, for example, sodium pentachlorophenol.
- pyridine oxide compound examples include sodium 2-pyridinethiol-1-oxide.
- isothiazoline-based compound examples include, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazoline-3- ON, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium Examples include chloride.
- antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, manufactured by Arch Chemical Co., Ltd., trade names Proxel RTM GXL (S), Proxel RTM XL-2 (S), and the like. .
- any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the prepared ink.
- the same materials as those listed above in “Neutralizing agent used for neutralizing polymer D” can be used.
- Other specific examples include, for example, alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium bicarbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; disodium phosphate and the like And the like.
- the chelating reagent include, for example, disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.
- rust preventive examples include, for example, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
- water-soluble ultraviolet absorber examples include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.
- water-soluble polymer compound examples include polyvinyl alcohol, cellulose derivatives, polyamine or polyimine.
- organic and metal complex anti-fading agents can be used.
- organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic rings. It is done.
- the inkjet printing method is a method of performing printing by discharging droplets of the ink composition in accordance with a recording signal and attaching them to a recording material.
- the above-mentioned textile printing method is a known method, for example, a charge control method for ejecting ink using electrostatic attraction force; a drop-on-demand method (pressure pulse method) using vibration pressure of a piezoelectric element; Either an acoustic ink jet method that irradiates ink using a radiation pressure instead of a beam; an ink jet method that discharges ink using the radiation pressure; a thermal ink jet method that heats ink to form bubbles and uses the generated pressure; Can be used.
- Examples of the recording material in the inkjet printing method include fibers selected from the group consisting of polyester, cellulose, polyamide, and natural fibers.
- Examples of the polyester fiber include a fiber mainly composed of polyethylene terephthalate.
- Examples of the cellulose fiber include cotton, cotton, rayon, triacetate fiber, and diacetate fiber.
- Examples of polyamide fibers include nylon fibers.
- Examples of natural fibers include silk and wool.
- the above fiber may be a single material fiber or a blended fiber thereof.
- These fibers may be provided with an ink receiving layer (bleeding prevention layer).
- This method of forming the ink receiving layer on the fiber is a publicly known and publicly available technique, and the fiber having the ink receiving layer is commercially available.
- the ink receiving layer is not particularly limited as long as it has the function.
- the inkjet dyeing method is a method in which the pigment contained in the ink composition attached to the recording material using the inkjet printing method is dyed on the recording material by a steaming or baking treatment to perform dyeing.
- a steaming or baking treatment for example, in a high-temperature steamer, it is usually 80 to 250 ° C., preferably 170 to 180 ° C., usually 10 seconds to 30 minutes, preferably about 10 minutes (wet heat fixation).
- baking (thermosol) treatment it can be dyed by treatment usually at 80 to 250 ° C., preferably 190 to 210 ° C., usually 10 seconds to 30 minutes, preferably 60 to 180 seconds (dry heat fixing). ).
- the dyed product means a recording material dyed by the ink jet dyeing method.
- a container containing the ink composition is set at a predetermined position of an inkjet printer for printing capable of transporting a fabric, and a recording material is printed by the inkjet printing method.
- You can print on In the inkjet printing method full color printing can be performed by selecting the type of pigment contained in the ink composition and using it as an ink set. For example, it may be used as an ink set of the above four colors of yellow, red, blue, and black, and if necessary, it is appropriately selected from pigments of each color such as green, violet, orange to brown, etc. It can also be used as an ink set.
- the ink composition described above has good ink filling into the ink jet head, and can perform stable discharge without bending or rubbing during printing. Further, in both cases of continuous printing and intermittent printing, it is possible to perform good discharge without clogging the nozzles. Further, the storage stability during storage is good, and the redispersibility is very good even when the ink composition has been dried by losing moisture or the like in the ink composition. Also, in dyeing fibers, there is no bleeding and high color development, and in full color printing, adjacent colors are not mixed and high quality. Moreover, it is excellent also in various fastness after dyeing
- Hyros X VS-1220 (9 parts) manufactured by Seiko PMC was dissolved in 2-butanone (30 parts). A solution prepared by dissolving 0.9 part of sodium hydroxide in ion-exchanged water (76 parts) was added to this solution, and the mixture was stirred for 1 hour to obtain an emulsion. To the resulting liquid, C.I. I. Pigment Red 122 (manufactured by High Performance Colors Ltd., HPC Red 1220, 30 parts) was added, and dispersion treatment was performed for 15 hours using a sand grinder at 1500 rpm. After ion-exchanged water (150 parts) was dropped into the obtained liquid, the dispersing beads were separated by filtration.
- C.I. I. Pigment Red 122 manufactured by High Performance Colors Ltd., HPC Red 1220, 30 parts
- Dispersion 1 A portion of 2-butanone and water in the mother liquor obtained was distilled off under reduced pressure using an evaporator and concentrated to obtain a dispersion having a solid content of 12.2%. This is designated as “Dispersion 1”.
- the solid content in the aqueous solution was determined by a dry weight method using MS-70 manufactured by A & D Corporation.
- the average particle diameter of the pigment contained in the dispersion 1 was 181 nm, and the viscosity of the dispersion 1 at 25 ° C. was 6.7 mPa ⁇ s.
- Preparation Example 2 C. used in Preparation Example 1 above I. In place of Pigment Red 122, C.I. I. A dispersion was obtained in the same manner as in Preparation Example 1, except that Pigment Black 7 was used. This is designated as “Dispersion 2”. The solid content of Dispersion 2 was 11.9%, the average particle size of the pigment contained in Dispersion 2 was 88 nm, and the viscosity of Dispersion 2 at 25 ° C. was 4.6 mPa ⁇ s.
- Preparation Example 3 C. used in Preparation Example 1 above I. In place of Pigment Red 122, C.I. I. A dispersion was obtained in the same manner as in Preparation Example 1 except that Pigment Blue 15: 3 was used. This is designated as “Dispersion 3”. The solid content of Dispersion 3 was 12.1%, the average particle size of the pigment contained in Dispersion 3 was 102 nm, and the viscosity of Dispersion 3 at 25 ° C. was 6.2 mPa ⁇ s.
- Preparation Example 4 C. used in Preparation Example 1 above I. In place of Pigment Red 122, C.I. I. A dispersion was obtained in the same manner as in Preparation Example 1, except that Pigment Yellow 155 was used. This is designated as “Dispersion 4”. The solid content of the dispersion 4 was 12.2%, the average particle size of the pigment contained in the dispersion 4 was 82 nm, and the viscosity of the dispersion 4 at 25 ° C. was 2.4 mPa ⁇ s.
- Example 5 to 16 Inks of Examples 5 to 16 used in the evaluation test were obtained by mixing the above dispersions 1 to 4 and the respective components shown in Table 1 below and filtering out impurities with a 5 ⁇ m membrane filter. All inks were adjusted so that the pigment content was 6%.
- DG Diglycerin 1,2-PG: 1,2-Propylene glycol 0533: Grade 0533 latex manufactured by JSR Corporation 0568: Grade 0568 latex manufactured by JSR Corporation 0597C: Grade 0597C manufactured by JSR Corporation Latex SF420: Surfynol 420 DF-110D: Surfynol DF-110D TEA: Triethanolamine BC: Butyl carbitol UA-150: Permarin UA-150
- Preparation Example 5 A polymer dispersant (block copolymer B) obtained by following the synthesis example 4 of International Publication No. 2013/115071 was dissolved in 6 parts and 30 parts of 2-butanone to obtain a uniform solution. A solution obtained by dissolving 0.44 parts of sodium hydroxide in 41 parts of ion-exchanged water was added to this, and the mixture was stirred for 1 hour to prepare an emulsified solution in which the polymer dispersant was dissolved. At this time, there was no precipitation of crystals. In addition, C.I. I. 20 parts of Pigment Red 122 (manufactured by High Performance Colors Ltd., HPC Red 1220) was added, and dispersion was performed with a sand grinder.
- C.I. I. 20 parts of Pigment Red 122 manufactured by High Performance Colors Ltd., HPC Red 1220
- Dispersion was performed at 1500 rpm for 15 hours to obtain a liquid. 100 parts of ion-exchanged water was added dropwise to the resulting liquid, and the liquid was filtered to remove the beads for dispersion. Then, 2-butanone and water were distilled off under reduced pressure using an evaporator to obtain a solid content of 15.1%. A dispersion was obtained. This is designated as “Dispersion 5”. The average particle diameter of the pigment contained in the dispersion 5 was 96 nm, and the viscosity of the dispersion 5 at 25 ° C. was 6.0 mPa ⁇ s.
- Preparation Example 6 A polymer dispersant (block copolymer A) obtained by following the synthesis example 3 of International Publication No. 2013/115071 was dissolved in 6 parts and 30 parts of 2-butanone to obtain a uniform solution. A solution obtained by dissolving 0.45 parts of sodium hydroxide in 42 parts of ion-exchanged water was added thereto, and the mixture was stirred for 1 hour to prepare an emulsified solution in which the polymer dispersant was dissolved. At this time, there was no precipitation of crystals. In addition, C.I. I. 20 parts of Pigment Red 122 (manufactured by High Performance Colors Ltd., HPC Red 1220) was added, and dispersion was performed with a sand grinder.
- Pigment Red 122 manufactured by High Performance Colors Ltd., HPC Red 1220
- Dispersion was performed at 1500 rpm for 15 hours to obtain a liquid. 100 parts of ion-exchanged water was added dropwise to the resulting liquid, and the liquid was filtered to remove the dispersing beads. Then, 2-butanone and water were distilled off under reduced pressure using an evaporator to obtain a solid content of 13.7%. A dispersion was obtained. This is designated as “Dispersion 6”. The average particle diameter of the pigment contained in the dispersion 6 was 80 nm, and the viscosity of the dispersion 6 at 25 ° C. was 6.7 mPa ⁇ s.
- Preparation Example 7 A polymer dispersant (block copolymer C) obtained by following the synthesis example 5 of International Publication No. 2013/115071 was dissolved in 6 parts and 30 parts of 2-butanone to obtain a uniform solution. A solution obtained by dissolving 0.43 parts of sodium hydroxide in 42 parts of ion-exchanged water was added thereto, and the mixture was stirred for 1 hour to prepare an emulsified solution in which the polymer dispersant was dissolved. At this time, there was no precipitation of crystals. In addition, C.I. I. 20 parts of Pigment Red 122 (manufactured by High Performance Colors Ltd., HPC Red 1220) was added, and dispersion was performed with a sand grinder.
- Pigment Red 122 manufactured by High Performance Colors Ltd., HPC Red 1220
- Dispersion was performed at 1500 rpm for 15 hours to obtain a liquid. 100 parts of ion-exchanged water was added dropwise to the obtained liquid, and this liquid was filtered to remove the beads for dispersion. Then, 2-butanone and water were distilled off under reduced pressure using an evaporator to obtain a solid content of 13.9%. A dispersion was obtained. This is designated as “Dispersion 7”. The average particle diameter of the pigment contained in the dispersion 7 was 102 nm, and the viscosity of the dispersion 7 at 25 ° C. was 7.4 mPa ⁇ s.
- Preparation Example 8 A polymer dispersant (block copolymer D) obtained by following the synthesis example 6 of International Publication No. 2013/115071 was dissolved in 6 parts and 30 parts of 2-butanone to obtain a uniform solution. A solution obtained by dissolving 0.44 parts of sodium hydroxide in 41 parts of ion-exchanged water was added to this, and the mixture was stirred for 1 hour to prepare an emulsified solution in which the polymer dispersant was dissolved. At this time, there was no precipitation of crystals. In addition, C.I. I. 20 parts of Pigment Red 122 (manufactured by High Performance Colors Ltd., HPC Red 1220) was added, and dispersion was performed with a sand grinder.
- Pigment Red 122 manufactured by High Performance Colors Ltd., HPC Red 1220
- Dispersion was performed at 1500 rpm for 15 hours to obtain a liquid. 100 parts of ion-exchanged water was added dropwise to the resulting liquid, and the liquid was filtered to remove the beads for dispersion. Then, 2-butanone and water were distilled off under reduced pressure using an evaporator to obtain a solid content of 12.7%. A dispersion was obtained. This is designated as “Dispersion 8”. The average particle diameter of the pigment contained in the dispersion 8 was 102 nm, and the viscosity of the dispersion 8 at 25 ° C. was 20.2 mPa ⁇ s.
- Preparation Example 9 A polymer dispersant (block copolymer E) obtained by following the synthesis example 7 of International Publication No. 2013/115071 was dissolved in 6 parts and 30 parts of 2-butanone to obtain a uniform solution. A solution prepared by dissolving 0.38 parts of sodium hydroxide in 88 parts of ion-exchanged water was added to this, and the mixture was stirred for 1 hour to prepare an emulsified solution in which the polymer dispersant was dissolved. At this time, there was no precipitation of crystals. In addition, C.I. I. 20 parts of Pigment Red 122 (manufactured by High Performance Colors Ltd., HPC Red 1220) was added, and dispersion was performed with a sand grinder.
- Pigment Red 122 manufactured by High Performance Colors Ltd., HPC Red 1220
- Dispersion was performed at 1500 rpm for 15 hours to obtain a liquid. 100 parts of ion-exchanged water was added dropwise to the resulting liquid, and the liquid was filtered to remove the beads for dispersion. Then, 2-butanone and water were distilled off under reduced pressure using an evaporator to obtain a solid content of 11.7%. A dispersion was obtained. This is designated as “Dispersion 9”. The average particle diameter of the pigment contained in the dispersion 9 was 104 nm, and the viscosity of the dispersion 9 at 25 ° C. was 3.0 mPa ⁇ s.
- Preparation Example 10 A polymer dispersant (block copolymer F) obtained by following the synthesis example 8 of International Publication No. 2013/115071 was dissolved in 6 parts and 30 parts of 2-butanone to obtain a uniform solution. A solution prepared by dissolving 0.51 part of sodium hydroxide in 41 parts of ion-exchanged water was added thereto, and the mixture was stirred for 1 hour to prepare an emulsified solution in which the polymer dispersant was dissolved. At this time, there was no precipitation of crystals. In addition, C.I. I. 20 parts of Pigment Red 122 (manufactured by High Performance Colors Ltd., HPC Red 1220) was added, and dispersion was performed with a sand grinder.
- Pigment Red 122 manufactured by High Performance Colors Ltd., HPC Red 1220
- Dispersion was performed at 1500 rpm for 15 hours to obtain a liquid. 100 parts of ion-exchanged water was added dropwise to the obtained liquid, and this liquid was filtered to remove the dispersing beads, and then 2-butanone and water were distilled off under reduced pressure using an evaporator to obtain a solid content of 12.68%. A dispersion was obtained. This is designated as “dispersion 10”. The average particle diameter of the pigment contained in the dispersion 10 was 110 nm, and the viscosity of the dispersion 10 at 25 ° C. was 10.4 mPa ⁇ s.
- Preparation Example 14 The polymer dispersant (block copolymer A) obtained by following the synthesis example 3 of International Publication No. 2013/115071 was dissolved in 4 parts and 25 parts of 2-butanone to obtain a uniform solution. A solution obtained by dissolving 0.45 parts of sodium hydroxide in 42 parts of ion-exchanged water was added thereto, and the mixture was stirred for 1 hour to prepare an emulsified solution in which the polymer dispersant was dissolved. At this time, there was no precipitation of crystals. To this was added 40 parts of Taipei CR-50-2 (manufactured by Ishihara Sangyo Co., Ltd.) and dispersed with a sand grinder.
- Taipei CR-50-2 manufactured by Ishihara Sangyo Co., Ltd.
- Dispersion was performed at 1500 rpm for 15 hours to obtain a liquid. 100 parts of ion-exchanged water was added dropwise to the resulting liquid, and this liquid was filtered to remove the beads for dispersion. Then, 2-butanone and water were distilled off under reduced pressure using an evaporator to obtain a solid content of 30.0%. A dispersion was obtained. This is designated as “Dispersion 14”. The average particle diameter of the pigment contained in the dispersion 14 was 266 nm, and the viscosity of the dispersion 14 at 25 ° C. was 4.0 mPa ⁇ s.
- Example 17 to 21 The ink compositions of Examples 17 to 21 used in the evaluation test were prepared by mixing the dispersion 6 and the dispersions 11 to 13 and the components shown in Table 3 below and filtering out impurities with a 5 ⁇ m membrane filter. I got a thing. All ink compositions were adjusted so that the pigment content was 6%. Abbreviations and blanks in Table 3 below have the same meanings as in Tables 1 and 2 above. “0850Z” means a latex of grade 0850Z manufactured by JSR Corporation.
- the pigment ink of the present invention is extremely useful as an ink for inkjet textile printing.
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Abstract
Description
一方、顔料を着色剤として用いた記録画像は、光、オゾン、水等に対する各種堅牢性には優れることが知られている。
しかし、顔料のように水に不溶な着色剤を含有するインクは、何らかの要因により含有する水分を失って乾燥状態になると顔料の分散状態が壊れ、顔料の凝集が生じるという欠点があった。このように一度凝集したインク中の顔料は、水等の液媒体を加えても再び分散状態に戻すことができない(再分散性が悪い)ため、その改善が強く求められている。
顔料、水、下記式(1)で表されるモノマーA、モノマーB、及びモノマーCよりなる群から選択される少なくとも2種類のモノマーからなるポリマーD、スチレン-ブタジエン樹脂、水溶性有機溶剤、及びノニオン界面活性剤を含有する、インクジェット捺染に用いるインク組成物。
モノマーA:下記式(1)中、Rが水素原子であるモノマー。
モノマーB:下記式(1)中、RがC1-C4アルキル基であるモノマー。
モノマーC:下記式(1)中、Rがアリール基又はアリールC1-C4アルキル基であるモノマー。
インク組成物の総質量に対する各成分の含有量が、
上記顔料:1~15質量%、
上記ポリマーD:0.1~15質量%、
上記スチレン-ブタジエン樹脂:1~20質量%、
上記水溶性有機溶剤:10~45質量%、
上記ノニオン界面活性剤:0.01~5質量%であり、
残部が水である、上記[1]に記載のインク組成物。
[3]
上記スチレン-ブタジエン樹脂がカルボキシ変性スチレン-ブタジエン樹脂である、上記[1]又は[2]に記載のインク組成物。
[4]
上記水溶性有機溶剤がポリグリセリルエーテル及びC2-C6ジオールを含む、上記[1]~[3]のいずれか一項に記載のインク組成物。
[5]
25℃において、表面張力が20~40mN/m、粘度が2~10mPa・sである、上記[1]~[4]のいずれか一項に記載のインク組成物。
[6]
上記[1]~[5]のいずれか一項に記載のインク組成物の液滴を、記録信号に応じて吐出させ、被記録材に付着させることにより捺染を行うインクジェット捺染方法。
[7]
上記被記録材が、ポリエステル、セルロース、ポリアミド、及び天然繊維よりなる群から選択される繊維、これらの繊維を含有する混紡繊維、又はこれらの繊維を含有する布帛である、上記[6]に記載のインクジェット捺染方法。
[8]
上記[6]又は[7]に記載のインクジェット捺染方法を用いて被記録材に付着させたインク組成物が含有する顔料を、スチーミング又はベーキング処理により上記被記録材に染着させ、染色を行うインクジェット染色方法。
[9]
上記スチーミング又はベーキング処理の処理温度が80~250℃であり、処理時間が10秒から30分の範囲である、上記[8]に記載のインクジェット染色方法。
[10]
前記[8]又は[9]に記載のインクジェット染色方法により染色された染色物。
上記の顔料としては、特に限定されるものではなく、公知の顔料が使用できる。顔料としては、無機顔料、有機顔料、体質顔料等が知られている。
カーボンブラックには種類があり、例えば、熱分解法により得られるサーマルブラック、アセチレンブラック;不完全燃焼法により得られるオイルファーネスブラック、ガスファーネスブラック、ランプブラック、ガスブラック、及びチャンネルブラック;等が挙げられる。
カーボンブラックの具体例としては、例えば、Raven760ULTRA、Raven780ULTRA、Raven790ULTRA、Raven1060ULTRA、Raven1080ULTRA、Raven1170、Raven1190ULTRA II、Raven1200、Raven1250、Raven1255、Raven1500、Raven2000、Raven2500ULTRA、Raven3500、Raven5000ULTRA II、Raven5250、Raven5750、Raven7000(以上、コロンビア・カーボン社製);Monarch700、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Regal1330R、Regal1400R、Regal1660R、Mogul L(以上、キャボット社製);Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW200、Color Black S150、Color Black S160、Color Black S170、Printex 35、Printex U、Printex V、 Printex 140U、 Printex 140V、 SpecIal Black 4、SpecIal Black 4A、SpecIal Black 5、Special Black 6(以上、デグサ社製);MA7、MA8、MA100、MA600、MCF-88、No.25、No.33、No.40、No.47、No.52、No.900、No.2300(以上、三菱化学社製);等が挙げられる。
酸化チタンの具体例としては、例えば、DUAWHITE TCR-52、TITONE R-32、TITONE R-7E、TITONE R-21、TITONE R-62N、TITONE R-42(以上、堺化学工業株式会社製);TIPAQUE CR-50、TIPAQUE CR-50-2、TIPAQUE CR-58、TIPAQUE CR-60、TIPAQUE CR-80、TIPAQUE CR-90(以上、石原産業株式会社製);TITANIX JA-600A、TITANIX JR-605(以上、テイカ株式会社製);ST-455、ST-455WB、ST-457SA、ST-457EC(以上、チタン工業株式会社製);等が挙げられる。
有機顔料の具体例としては、例えば、C.I.Pigment Yellow 1、2、3、12、13、14、16、17、24、55、73、74、75、83、93、94、95、97、98、108、114、128、129、138、139、150、151、154、155、180、185、193、199、202等のイエロー色の顔料;C.I.Pigment Red 5、7、12、48、48:1、57、88、112、122、123、146、149、166、168、177、178、179、184、185、202、206、207、254、255、257、260、264、272等のレッド色の顔料;C.I.Pigment Blue 1、2、3、15、15:1、15:2、15:3、15:4、15:6、16、22、25、60、66、80等のブルー色の顔料;C.I.Pigment Violet 19、23、29、37、38、50等のバイオレット色の顔料;C.I.Pigment Orange13、16、36、34、43、68、69、71、73等のオレンジ~ブラウン色の顔料;C.I.Pigment Green7、36、54等のグリーン色の顔料;C.I.Pigment Black 1等のブラック色の顔料;等が挙げられる。
さらに、染色物の色相調整のため、無機顔料及び有機顔料から選択される2種以上の顔料を併用することもできる。ここでいう色相調整は、濃淡をつけた染色物を得ること;染色の色域を広げること;等を目的として行われる。このような目的のためには、数種類の有機顔料を併用し、望みの色相に調整することができる。
水性媒体(水と、後記するアルキルエーテル溶剤以外の水溶性有機溶剤及びアルキルエーテル溶剤の混合溶媒を意味する)中で顔料分散物を安定化させる方法としては、一般に樹脂等の分散剤を用いてエントロピー的、イオン反発力、立体反発力等によって顔料分散物を安定化する方法が用いられる。ここで、分散剤は親水性部分と疎水性部分とを有し、疎水性部分が顔料表面に吸着し、親水性部分で水性媒体に分散する性質を有すると考えられる。さらに、顔料表面への吸着状態によっては、顔料を水性媒体に溶解させることも可能である。上記のポリマーDは、このような性質を有する分散剤として使用できる。
ポリマーDは、上記式(1)で表されるモノマーA、モノマーB、及びモノマーCよりなる群から選択される少なくとも2種類のモノマーを重合してなるポリマーである。好ましくは、モノマーA、モノマーB、及びモノマーCから少なくとも1種類ずつが選択される。
また、ポリマーDは、これらのモノマーのランダム共重合体、交互共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよい。
また、アルカリ土類金属の水酸化物として、例えば、水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム等が挙げられる。
無機塩基の中ではアルカリ金属の水酸化物及びアンモニアが好ましく、中でも水酸化リチウム、水酸化ナトリウム、及びアンモニアが好ましい。
モノマーAは、上記式(1)中、Rが水素原子であるモノマー、すなわちメタクリル酸である。
モノマーBは、上記式(1)中、RがC1-C4アルキル基であるモノマーである。
モノマーBとしては、メチルメタクリレート、エチルメタクリレート、n-プロピルメタクリレート、イソプロピルメタクリレート、n-ブチルメタクリレート、イソブチルメタクリレート等が挙げられる。
モノマーCは、上記式(1)中、Rがアリール基又はアリールC1-C4アルキル基であるモノマーである。
上記アリールとしては、C6-C10アリール基が好ましく、中でもフェニル基又はナフチル基が好ましい。
上記アリールC1-C4アルキル基としては、フェニルメチル、フェニルエチル、フェニルプロピル、フェニルブチル等のアルキル部分が直鎖又は分岐鎖、好ましくは直鎖のフェニルC1-C4アルキル基;ナフチルメチル、ナフチルエチル、ナフチルプロピル、ナフチルブチル等のアルキル部分が直鎖又は分岐鎖、好ましくは直鎖のナフチルC1-C4アルキル基;等が挙げられる。これらの中ではフェニルC1-C4アルキル基が好ましい。
モノマーCの具体例としては、例えば、フェニルメタクリレート、ベンジルメタクリレート、フェネチルメタクリレートが挙げられる。
上記スチレン-ブタジエン樹脂は、ラテックス(エマルション)の形で販売されていることも多く、容易に購入することができる。その具体例としては、例えば、Nipol LX415M、NipolLX432M,Nipol LX433C、Nipol LX421、Nipol 2507H、Nipol LX303A(以上、日本ゼオン(株)製)、グレードとして0695、0696、0561、0589、0602、2108、0533、0545、0548、0568、0569、0573、0597C、0850Zのラテックス(以上、JSR(株)製)等が挙げられ、その多くは固形分が30~60%で樹脂を乳化した液体である。
スチレン-ブタジエン樹脂としては、上記したいずれのラテックスも使用することができるが、中でもカルボキシ変性スチレン-ブタジエン樹脂を使用するのが好ましい。そのような樹脂の例としては、例えば、Nipol LX415M、NipolLX432M,Nipol LX433C、Nipol LX421、0695、0696、0533、0545、0548、0568、0569、0573、0597C、0850Zが挙げられ、0695、0533、0568、0597C、0850Zが好ましい。
スチレン-ブタジエン樹脂は単一のものを使用してもよいし、2~3種類を併用してもよい。
上記水溶性有機溶剤としては、例えば、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、第二ブタノール、第三ブタノール等のC1-C4モノオール;エチレングリコール、1,2-又は1,3-プロピレングリコール、1,2-又は1,4-ブチレングリコール、1,3-ペンタンジオール、1,5-ペンタンジオール、1,2-ヘキサンジオール、1,6-ヘキサンジオール等のC2-C6ジオール;グリセリン、ヘキサン-1,2,6-トリオール、トリメチロールプロパン等のC3-C6トリオール;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のカルボン酸アミド;2-ピロリドン、N-メチル-2-ピロリドン、1,3-ジメチルイミダゾリジン-2-オン、1,3-ジメチルヘキサヒドロピリミド-2-オン等の複素環式尿素類;アセトン、メチルエチルケトン、2-メチル-2-ヒドロキシペンタン-4-オン等のケトン又はケトアルコール;1,2-ジメトキシエタン、テトラヒドロフラン、ジオキサン等の直鎖又は環状エーテル;ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、チオジグリコール等のジ若しくはトリC2-C3アルキレングリコール又はチオグリコール;テトラエチレングリコール、ポリエチレングリコール(好ましくは分子量400、800、1540等の分子量が2000以下のもの)、ポリプロピレングリコール等の、繰り返し単位が4以上で、分子量が約20000以下程度のポリC2-C3アルキレングリコール(好ましくは液状のもの);ジグリセリン、トリグリセリン、ポリグリセリン等のポリグリセリルエーテル;ポリオキシエチレンポリグリセリルエーテル、ポリオキシプロピレンポリグリセリルエーテル等のポリオキシC2-C3アルキレンポリグリセリルエーテル;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジ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モノエチルエーテル、ジエチレングリコールモノブチルエーテル(ブチルカルビトール)、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル等の多価アルコールのC1-C4アルキルエーテル;γ-ブチロラクトン、エチレンカーボネート等の環状エステル又はカーボネート;ジメチルスルホキシド;酢酸;等が挙げられる。
これらの中では、C2-C6ジオール(中では1,2-プロピレングリコール);C3-C6トリオール(中ではグリセリン);ポリグリセリルエーテル(中ではジグリセリン);及び、多価アルコールのC1-C4アルキルエーテル(中ではブチルカルビトール);が好ましい。
これらの水溶性有機溶剤は1種類を使用してもよく、また複数を併用してもよい。これらの中では、ポリグリセリルエーテル(好ましくはグリセリン及び/又はジグリセリン)と、C2-C6ジオール(好ましくはエチレングリコール、1,2-又は1,3-プロピレングリコール、より好ましくはエチレングリコール、1,2-プロピレングリコール)とを含有するのが好ましい。
上記ノニオン界面活性剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル等のエーテル系;ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等のエステル系;2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、3,6-ジメチル-4-オクチン-3,6-ジオール、3,5-ジメチル-1-ヘキシン-3-オール等のアセチレングリコール(アルコール)系;日信化学社製 商品名サーフィノールRTM104、105PG50、82、420、440、465、485、DF-110D、オルフィンRTMSTG;ポリグリコールエーテル系(例えばSIGMA-ALDRICH社製のTergItolRTM15-S-7等);等が挙げられる。上記ノニオン界面活性剤は、単独又は混合して用いることができ、好ましくはサーフィノール系、より好ましくはサーフィノールRTM420、サーフィノールRTM440、サーフィノールRTM465である。
なお、本明細書において、上付きの「RTM」は登録商標を意味する。
顔料:通常1~15%、好ましくは1~10%、より好ましくは1~7%。
ポリマーD:通常0.1~15%、好ましくは0.1~9%、より好ましくは0.2~6%。
スチレン-ブタジエン樹脂:通常1~20%、好ましくは3~15%、より好ましくは3~12%。
水溶性有機溶剤:通常10~45%、好ましくは15~38%、より好ましくは20~35%。
ノニオン界面活性剤:通常0.01~5%、好ましくは0.05~3%、より好ましくは0.1~2.5%。
なお、残部は水である。
このような条件で分散を行うことにより、顔料の粒子サイズを小さくすることができ、分散性が良好な分散液を得ることができる。
また、該分散液の調製後に、濾過及び/又は遠心分離等により、粒子サイズの大きい成分を除去することも好ましく行われる。
また、該分散液の調製時に激しく泡立ち等が生じるときは、これを抑える目的で、シリコーン系、アセチレングリコール系等の消泡剤を極微量添加してもよい。ただし、消泡剤には、顔料の分散や微粒子化を阻害するものがあるため、そのような悪影響を及ぼさないものを適宜選択して使用するのが好ましい。
ポリマーDにより顔料をマイクロカプセル化するときは、いずれの手法を用いてもよく、特に限定されないが、これらの中では表面析出法が好ましく、中でも転相乳化法が好ましい。
上記のようにして調製される顔料分散液中における顔料の平均粒径は、通常200nm以下、好ましくは50~150nm、より好ましくは60~120nmである。平均粒径をこの範囲とすることによって、分散安定性及び吐出安定性が優れるとともに、染色濃度が高くなる。なお、平均粒径は、レーザ光散乱法を用いて測定できる。
また、インク組成物の25℃における表面張力としては、10~50mN/mが好ましく、20~40mN/mがより好ましい。
さらに、インク組成物の25℃における粘度としては、30mPa・s以下が好ましく、20mPa・s以下がより好ましく、2~10mPa・sが特に好ましい。
本発明のインク組成物のpH、表面張力は、後記するようなpH調整剤、界面活性剤で適宜調整することが可能である。
分原比=ポリマーDの部数/顔料の部数
有機ハロゲン系化合物の具体例としては、例えばペンタクロロフェノールナトリウムが挙げられる。ピリジンオキシド系化合物の具体例としては、例えば2-ピリジンチオール-1-オキサイドナトリウムが挙げられる。イソチアゾリン系化合物の具体例としては、例えば、1,2-ベンズイソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オンマグネシウムクロライド、5-クロロ-2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド、2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド等が挙げられる。その他の防腐防黴剤の具体例としては、無水酢酸ナトリウム、ソルビン酸ナトリウム、安息香酸ナトリウム、アーチケミカル社製、商品名プロクセルRTMGXL(S)やプロクセルRTMXL-2(S)等が挙げられる。
他の具体例としては、例えば、炭酸リチウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩;ケイ酸ナトリウム、酢酸カリウム等の有機酸のアルカリ金属塩;リン酸二ナトリウム等のリン酸塩;等が挙げられる。
ポリエステル繊維としては、ポリエチレンテレフタレートを主成分とする繊維が挙げられる。
セルロース繊維としては、綿、木綿、レーヨン、トリアセテート繊維、ジアセテート繊維等が挙げられる。
ポリアミド繊維としては、ナイロン繊維等が挙げられる。
天然繊維としては、絹、羊毛等が挙げられる。
上記の繊維は単一素材の繊維であっても、これらの混紡繊維であってもよい。また、これらの繊維にインク受容層(滲み防止層)を設けたものでもよい。この繊維へのインク受容層の形成方法は公知公用の技術であり、インク受容層を有する繊維は市場から入手できる。また、公知公用の技術から適宜構成成分、形成方法等を選定し、該繊維にインク受容層を設けることもできる。該インク受容層はその機能を有するものであれば、特に限定されるものではない
スチーミング処理としては、例えば、高温スチーマーでは通常80~250℃、好ましくは170~180℃、通常10秒~30分、好ましくは10分程度の処理で染着させることができる(湿熱固着)。
また、ベーキング(サーモゾル)処理としては、通常80~250℃、好ましくは190~210℃、通常10秒~30分、好ましくは60~180秒程度の処理で染着させることができる(乾熱固着)。
このようにして、上記インクジェット染色方法により染色された染色物が得られる。なお、染色物とは、上記インクジェット染色方法により染色された被記録材を意味する。
上記インクジェット捺染方法は、上記インク組成物中に含有する顔料の種類を選択してインクセットとして使用し、フルカラー捺染を行うことができる。例えば、上記イエロー、レッド、ブルー、及びブラックの4色のインクセットとして使用してもよいし、必要に応じて、グリーン、バイオレット、オレンジ~ブラウン等の各色の顔料から適宜選択し、4色以上のインクセットとして使用することもできる。
また、貯蔵時の保存安定性が良好であり、仮にインク組成物中の水分等を失って、インク組成物を乾燥させてしまったときであっても、再分散性が極めて良好である。
また、繊維の染色において、滲みがなく高発色であり、フルカラー捺染において隣接した色が混ざらず高品質である。
また、染着後の各種の堅牢性、例えば耐光性、耐水性等にも優れる。
星光PMC社製ハイロスX VS-1202(9部)を、2-ブタノン(30部)に溶解した。この溶液に、0.9部の水酸化ナトリウムをイオン交換水(76部)に溶解させた液を加え、1時間撹拌することにより乳化液を得た。得られた液にC.I.Pigment Red 122(High Performance Colours Ltd社製、HPC Red 1220、30部)を加え、サンドグラインダーで1500rpmの条件下、15時間分散処理を行った。得られた液にイオン交換水(150部)を滴下した後、分散用ビーズを濾別した。得られた母液中の2-ブタノン及び水の一部を、エバポレータで減圧留去して濃縮することにより、固形分12.2%の分散液を得た。これを「分散液1」とする。なお、水溶液中の固形分は、株式会社エイ・アンド・デイ社製、MS-70を用いて乾燥重量法により求めた。分散液1に含まれる顔料の平均粒子径は181nm、分散液1の25℃における粘度は6.7mPa・sであった。
上記調製例1で使用したC.I.Pigment Red 122の代わりに、C.I.Pigment Black 7を用いる以外は調製例1と同様にして分散液を得た。これを「分散液2」とする。分散液2の固形分は11.9%、分散液2に含まれる顔料の平均粒子径は88nm、分散液2の25℃における粘度は4.6mPa・sであった。
上記調製例1で使用したC.I.Pigment Red 122の代わりに、C.I.Pigment Blue 15:3を用いる以外は調製例1と同様にして、分散液を得た。これを「分散液3」とする。分散液3の固形分は12.1%、分散液3に含まれる顔料の平均粒子径は102nm、分散液3の25℃における粘度は6.2mPa・sであった。
上記調製例1で使用したC.I.Pigment Red 122の代わりに、C.I.Pigment Yellow 155を用いる以外は調製例1と同様にして、分散液を得た。これを「分散液4」とする。分散液4の固形分は12.2%、分散液4に含まれる顔料の平均粒子径は82nm、分散液4の25℃における粘度は2.4mPa・sであった。
上記分散液1~4と、下記表1に記載の各成分とを混合し、5μmのメンブランフィルタで夾雑物を濾別することにより、評価試験に用いる実施例5~16のインクを得た。いずれのインクも、顔料の含有量が6%になるように調整した。
各実施例で用いたスチレン-ブタジエン樹脂の代わりに、ポリカーボネート系ウレタン樹脂ラテックスであるパーマリンUA-150[三洋化成工業(株)製]を使用し、下記表2の各成分を混合することにより、評価試験に用いる比較例1~4のインクをそれぞれ調製した。いずれのインクも、顔料の含有量が6%になるように調整した。
DG:ジグリセリン
1,2-PG:1,2-プロピレングリコール
0533:JSR(株)製のグレード0533のラテックス
0568:JSR(株)製のグレード0568のラテックス
0597C:JSR(株)製のグレード0597Cのラテックス
SF420:サーフィノール420
DF-110D:サーフィノールDF-110D
TEA:トリエタノールアミン
BC:ブチルカルビトール
UA-150:パーマリンUA-150
上記実施例5~16、及び比較例1~4のインク組成物をガラスシャーレの上に5mlのせ、シャーレ底に薄くまんべんなく回し広げた後、余剰の液体を捨てた。これを35℃の乾燥機で4時間乾燥させた後、室温で2mlのイオン交換水を滴下し、乾燥したインク組成物の再分散性を目視にて、下記の4段階で評価した。
乾燥後であっても再分散するものは、残渣を生じることなく全て液状に戻るため、目視にて判断することができる。結果を上記表1及び表2に示す。
A:残渣なく、全て再分散する。
B:残渣が少し残るが、ほとんどが再分散している。
C:残渣は多く残るが、多少再分散している。
D:まったく再分散しない。
各実施例及び比較例のインク組成物をそれぞれ蓋付ガラス製サンプル瓶に入れ、60℃の乾燥機で3日間静置した。各サンプル瓶を静かに逆さまにし、保存安定性として沈殿物の有無を目視にて、下記の2段階で評価した。結果を上記表1及び表2に示す。
A:沈殿物は確認されない。
D:明らかに沈殿物が確認される。
国際公開第2013/115071号の合成例4を追試することにより得た高分子分散剤(ブロック共重合体B)を6部、2-ブタノン30部に溶解させ、均一な溶液とした。これに、0.44部の水酸化ナトリウムを41部のイオン交換水に溶解させた液を加え、1時間撹拌することで高分子分散剤が溶解した乳化溶液を調製した。このとき、結晶の析出はなかった。これにC.I.Pigment Red 122(High Performance Colours Ltd社製、HPC Red 1220)を20部加え、サンドグラインダーで分散を行った。分散は1500rpmの条件下で15時間分散させて液を得た。得られた液にイオン交換水100部を滴下し、この液を濾過して分散用ビーズを取り除いた後、エバポレータで2-ブタノン及び水を減圧留去することにより、固形分15.1%の分散液を得た。これを「分散液5」とする。分散液5に含まれる顔料の平均粒子径は96nm、分散液5の25℃における粘度は6.0mPa・sであった。
国際公開第2013/115071号の合成例3を追試することにより得た高分子分散剤(ブロック共重合体A)を6部、2-ブタノン30部に溶解させ、均一な溶液とした。これに、0.45部の水酸化ナトリウムを42部のイオン交換水に溶解させた液を加え、1時間撹拌することで高分子分散剤が溶解した乳化溶液を調製した。このとき、結晶の析出はなかった。これにC.I.Pigment Red 122(High Performance Colours Ltd社製、HPC Red 1220)を20部加え、サンドグラインダーで分散を行った。分散は1500rpmの条件下で15時間分散させて液を得た。得られた液にイオン交換水100部を滴下し、この液を濾過して分散用ビーズを取り除いた後、エバポレータで2-ブタノン及び水を減圧留去することにより、固形分13.7%の分散液を得た。これを「分散液6」とする。分散液6に含まれる顔料の平均粒子径は80nm、分散液6の25℃における粘度は6.7mPa・sであった。
国際公開第2013/115071号の合成例5を追試することにより得た高分子分散剤(ブロック共重合体C)を6部、2-ブタノン30部に溶解させ、均一な溶液とした。これに、0.43部の水酸化ナトリウムを42部のイオン交換水に溶解させた液を加え、1時間撹拌することで高分子分散剤が溶解した乳化溶液を調製した。このとき、結晶の析出はなかった。これにC.I.Pigment Red 122(High Performance Colours Ltd社製、HPC Red 1220)を20部加え、サンドグラインダーで分散を行った。分散は1500rpmの条件下で15時間分散させて液を得た。得られた液にイオン交換水100部を滴下し、この液を濾過して分散用ビーズを取り除いた後、エバポレータで2-ブタノン及び水を減圧留去することにより、固形分13.9%の分散液を得た。これを「分散液7」とする。分散液7に含まれる顔料の平均粒子径は102nm、分散液7の25℃における粘度は7.4mPa・sであった。
国際公開第2013/115071号の合成例6を追試することにより得た高分子分散剤(ブロック共重合体D)を6部、2-ブタノン30部に溶解させ、均一な溶液とした。これに、0.44部の水酸化ナトリウムを41部のイオン交換水に溶解させた液を加え、1時間撹拌することで高分子分散剤が溶解した乳化溶液を調製した。このとき、結晶の析出はなかった。これにC.I.Pigment Red 122(High Performance Colours Ltd社製、HPC Red 1220)を20部加え、サンドグラインダーで分散を行った。分散は1500rpmの条件下で15時間分散させて液を得た。得られた液にイオン交換水100部を滴下し、この液を濾過して分散用ビーズを取り除いた後、エバポレータで2-ブタノン及び水を減圧留去することにより、固形分12.7%の分散液を得た。これを「分散液8」とする。分散液8に含まれる顔料の平均粒子径は102nm、分散液8の25℃における粘度は20.2mPa・sであった。
国際公開第2013/115071号の合成例7を追試することにより得た高分子分散剤(ブロック共重合体E)を6部、2-ブタノン30部に溶解させ、均一な溶液とした。これに、0.38部の水酸化ナトリウムを88部のイオン交換水に溶解させた液を加え、1時間撹拌することで高分子分散剤が溶解した乳化溶液を調製した。このとき、結晶の析出はなかった。これにC.I.Pigment Red 122(High Performance Colours Ltd社製、HPC Red 1220)を20部加え、サンドグラインダーで分散を行った。分散は1500rpmの条件下で15時間分散させて液を得た。得られた液にイオン交換水100部を滴下し、この液を濾過して分散用ビーズを取り除いた後、エバポレータで2-ブタノン及び水を減圧留去することにより、固形分11.7%の分散液を得た。これを「分散液9」とする。分散液9に含まれる顔料の平均粒子径は104nm、分散液9の25℃における粘度は3.0mPa・sであった。
国際公開第2013/115071号の合成例8を追試することにより得た高分子分散剤(ブロック共重合体F)を6部、2-ブタノン30部に溶解させ、均一な溶液とした。これに、0.51部の水酸化ナトリウムを41部のイオン交換水に溶解させた液を加え、1時間撹拌することで高分子分散剤が溶解した乳化溶液を調製した。このとき、結晶の析出はなかった。これにC.I.Pigment Red 122(High Performance Colours Ltd社製、HPC Red 1220)を20部加え、サンドグラインダーで分散を行った。分散は1500rpmの条件下で15時間分散させて液を得た。得られた液にイオン交換水100部を滴下し、この液を濾過して分散用ビーズを取り除いた後、エバポレータで2-ブタノン及び水を減圧留去することにより、固形分12.68%の分散液を得た。これを「分散液10」とする。分散液10に含まれる顔料の平均粒子径は110nm、分散液10の25℃における粘度は10.4mPa・sであった。
C.I.Pigment Red 122の代わりに、C.I.Pigment Black 7を用いる以外は上記調製例6と同様にして、固形分12.9%の分散液を得た。これを「分散液11」とする。分散液11に含まれる顔料の平均粒子径は88nm、分散液11の25℃における粘度は4.6mPa・sであった。
C.I.Pigment Red 122の代わりに、C.I.Pigment Blue 15:3を用いる以外は上記調製例6と同様にして、固形分12.4%の分散液を得た。これを「分散液12」とする。分散液12に含まれる顔料の平均粒子径は102nm、分散液12の25℃における粘度は6.2mPa・sであった。
C.I.Pigment Red 122の代わりに、C.I.Pigment Yellow 155を用いる以外は上記調製例6と同様にして、固形分14.1%の分散液を得た。これを「分散液13」とする。分散液13に含まれる顔料の平均粒子径は82nm、分散液13の25℃における粘度は2.4mPa・sであった。
国際公開第2013/115071号の合成例3を追試することにより得た高分子分散剤(ブロック共重合体A)を4部、2-ブタノン25部に溶解させ、均一な溶液とした。これに、0.45部の水酸化ナトリウムを42部のイオン交換水に溶解させた液を加え、1時間撹拌することで高分子分散剤が溶解した乳化溶液を調製した。このとき、結晶の析出はなかった。これにタイペークCR-50-2(石原産業株式会社製)を40部加え、サンドグラインダーで分散を行った。分散は1500rpmの条件下で15時間分散させて液を得た。得られた液にイオン交換水100部を滴下し、この液を濾過して分散用ビーズを取り除いた後、エバポレータで2-ブタノン及び水を減圧留去することにより、固形分30.0%の分散液を得た。これを「分散液14」とする。分散液14に含まれる顔料の平均粒子径は266nm、分散液14の25℃における粘度は4.0mPa・sであった。
上記分散液6及び分散液11~13と下記表3に記載の各成分とを混合し、5μmのメンブランフィルタで夾雑物を濾別することにより、評価試験に用いる実施例17~21のインク組成物を得た。いずれのインク組成物も、顔料の含有量が6%になるように調整した。
下記表3中の略号等及び空欄は、上記表1及び表2と同じ意味を有する。また、「0850Z」は、JSR株式会社製のグレード0850Zのラテックスを意味する。
Claims (10)
- インク組成物の総質量に対する各成分の含有量が、
前記顔料:1~15質量%、
前記ポリマーD:0.1~15質量%、
前記スチレン-ブタジエン樹脂:1~20質量%、
前記水溶性有機溶剤:10~45質量%、
前記ノニオン界面活性剤:0.01~5質量%であり、
残部が水である、請求項1に記載のインク組成物。 - 前記スチレン-ブタジエン樹脂がカルボキシ変性スチレン-ブタジエン樹脂である、請求項1又は2に記載のインク組成物。
- 前記水溶性有機溶剤がポリグリセリルエーテル及びC2-C6ジオールを含む、請求項1~3のいずれか一項に記載のインク組成物。
- 25℃において、表面張力が20~40mN/m、粘度が2~10mPa・sである、請求項1~4のいずれか一項に記載のインク組成物。
- 請求項1~5のいずれか一項に記載のインク組成物の液滴を、記録信号に応じて吐出させ、被記録材に付着させることにより捺染を行うインクジェット捺染方法。
- 前記被記録材が、ポリエステル、セルロース、ポリアミド、及び天然繊維よりなる群から選択される繊維、これらの繊維を含有する混紡繊維、又はこれらの繊維を含有する布帛である、請求項6に記載のインクジェット捺染方法。
- 請求項6又は7に記載のインクジェット捺染方法を用いて被記録材に付着させたインク組成物が含有する顔料を、スチーミング又はベーキング処理により前記被記録材に染着させ、染色を行うインクジェット染色方法。
- 前記スチーミング又はベーキング処理の処理温度が80~250℃であり、処理時間が10秒から30分の範囲である、請求項8に記載のインクジェット染色方法。
- 請求項8又は9に記載のインクジェット染色方法により染色された染色物。
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US14/443,842 US9181446B2 (en) | 2012-11-28 | 2013-11-25 | Ink composition and printing method |
CA2892657A CA2892657A1 (en) | 2012-11-28 | 2013-11-25 | Ink composition and printing method |
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JP2018165336A (ja) * | 2017-03-28 | 2018-10-25 | Jsr株式会社 | テキスタイル用インク、テキスタイル捺染方法及び捺染物 |
JP2019090015A (ja) * | 2017-11-10 | 2019-06-13 | 日本化薬株式会社 | 捺染用インク組成物 |
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US20190367753A1 (en) * | 2018-06-05 | 2019-12-05 | Xerox Corporation | Aqueous Ink Composition Comprising A Polymer Additive |
KR102116078B1 (ko) | 2018-09-18 | 2020-05-28 | 재단법인경북테크노파크 | 천연색소를 활용한 디지털 날염용 친환경잉크 제조방법 |
US20240010019A1 (en) * | 2020-03-12 | 2024-01-11 | Cryovac, Llc | Printing compositions and methods therefor |
KR102663901B1 (ko) | 2021-11-02 | 2024-05-08 | 주식회사 디티아이 | 디지털 날염용 천연잉크 제조방법 |
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CA2892657A1 (en) | 2014-06-05 |
JP2018080338A (ja) | 2018-05-24 |
JP2019214723A (ja) | 2019-12-19 |
BR112015012085A2 (pt) | 2017-07-11 |
KR20150090896A (ko) | 2015-08-06 |
CN104812850B (zh) | 2019-05-03 |
US20150284577A1 (en) | 2015-10-08 |
JPWO2014084161A1 (ja) | 2017-01-05 |
JP6761079B2 (ja) | 2020-09-23 |
US9181446B2 (en) | 2015-11-10 |
EP2927287A1 (en) | 2015-10-07 |
KR102132506B1 (ko) | 2020-07-09 |
EP2927287A4 (en) | 2015-11-18 |
CN104812850A (zh) | 2015-07-29 |
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