Classifications

• • 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
• • 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
• • 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
  • B41M5/0023—Digital printing methods characterised by the inks used
• • 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
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
• • 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
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • 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
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

• the present invention relates to an aqueous ink for inkjet recording, an ink set for inkjet recording, and an inkjet recording method.
• UV ink an ultraviolet curable ink (UV ink) has been proposed.
• a general UV ink has a pigment dispersed in a monomer, and a polymer having a high image fastness can be obtained by polymerizing a monomer component with ultraviolet light after image formation.
• the UV ink has a problem in that the working environment is deteriorated due to the unique odor of the monomer used, and the safety is caused by migration of the monomer and the polymerization initiator from the printed matter. Therefore, in order to improve the image fastness of a printed material using a highly safe water-based pigment ink, an aqueous composition such as a water-based pigment ink containing carbodiimide and a coating liquid used in combination with the ink have been developed.
• Patent Document 1 discloses a vehicle and a carbodiimide dispersed and / or dissolved in the vehicle, with the object of enhancing the durability of an image printed on plain paper or cloth.
• An inkjet ink comprising a group-containing component and comprising an aqueous vehicle and a colorant dispersed in the aqueous vehicle with a polymeric dispersant is disclosed.
• a block copolymer of methacrylic acid / benzyl methacrylate / ethyltriethylene glycol methacrylate (13/15/4) and phenoxyethyl acrylate-g-ethoxy-triethylene acrylate were used as polymer dispersants.
• Glycol methacrylate-co-methacrylic acid (66/4/30) graft copolymers are disclosed.
• Patent Document 2 discloses pigments, organic solvents, polycarbonate-based urethane resins, water, and the like, with the object of obtaining an image having high gloss and excellent substrate adhesion and abrasion resistance. And an ink-jet ink containing a carbodiimide compound.
• the present invention relates to an aqueous ink jet recording ink containing a carbodiimide compound, a pigment, a vinyl polymer, and water, wherein the vinyl polymer is a polymer having a carboxy group having an acid value of 70 mgKOH / g or less, and the pigment contains a pigment.
• the present invention relates to a water-based ink for inkjet recording, which is in the form of polymer particles.
• Patent Document 2 is a technique relating to a coating film using a polycarbonate-based urethane resin, and the use of a vinyl polymer is not examined.
• the ink jet recording method is more suitable for prints of various kinds in a small amount than the analog printing method such as the gravure printing method, and it is desired that the application range of the recording medium by the ink jet recording method is expanded. With the expansion of such an application range, further improvement of the scratch resistance of printed matter is particularly required in printing on a recording medium for commercial printing or industrial printing using coated paper or a resin film.
• a heat-shrinkable resin film is widely used as a packaging base material for containers used in foods, medical fields, and the like, such as plastic bottles and plastic cases.
• a packaging base material for containers used in foods, medical fields, and the like, such as plastic bottles and plastic cases.
• important information such as product information such as a letter book, usage method, expiration date, lot number, etc. are printed. Also, improvement in scratch resistance is desired.
• the present invention relates to an aqueous ink for ink jet recording, an ink set for ink jet recording, and an ink jet recording method capable of obtaining a printed matter having excellent scratch resistance.
• an aqueous ink containing a carbodiimide compound and having a pigment dispersed with a vinyl polymer having a relatively low acid value can improve the scratch resistance of a printed matter obtained by inkjet recording. That is, the present invention relates to the following [1] to [3].
• An ink set for inkjet recording comprising an aqueous composition containing a carbodiimide compound and water, and an aqueous ink containing a pigment and a vinyl polymer, wherein the vinyl polymer has a carboxy group having an acid value of 70 mgKOH / g or less.
• An ink set for inkjet recording wherein the pigment is in the form of polymer particles containing the pigment.
• An inkjet recording method including the following steps 1 and 2.
• Step 1 A step of discharging a carbodiimide compound, a pigment, a vinyl polymer, and water onto the surface of a recording medium by an inkjet method to obtain a recorded image
• the vinyl polymer is a polymer having a carboxy group having an acid value of 70 mgKOH / g or less.
• pigments are in the form of pigment-containing polymer particles.
• Step 2 a step of heating the recorded image obtained in Step 1 at a temperature of 50 ° C. or more and 200 ° C. or less.
• the present invention it is possible to provide a water-based ink for ink-jet recording, an ink set for ink-jet recording, and an ink-jet recording method capable of obtaining a printed matter having excellent scratch resistance.
• a first embodiment of the aqueous ink for inkjet recording (hereinafter, also simply referred to as “aqueous ink” or “ink”) of the present invention is an aqueous ink for inkjet recording containing a carbodiimide compound, a pigment, a vinyl polymer, and water.
• the vinyl polymer is a polymer having a carboxy group having an acid value of 70 mgKOH / g or less, and the pigment is in the form of polymer particles containing the pigment.
• a second aspect is a combination comprising an aqueous composition containing a carbodiimide compound and water and an aqueous ink containing a pigment and a vinyl polymer, wherein the vinyl polymer has a carboxy group having an acid value of 70 mgKOH / g or less. And the pigment is in the form of polymer particles containing the pigment.
• the scratch resistance of the obtained printed matter can be improved.
• the abrasion resistance of the obtained printed matter can be improved by mixing the aqueous composition and the aqueous ink on the surface of the recording medium.
• “recording” is a concept including printing and printing for recording characters and images
• “printing” is a concept including printing and printing on which characters and images are recorded.
• “Aqueous” means that water occupies the largest proportion in the medium contained in the ink.
• the water-based ink of the present invention a printed matter having excellent scratch resistance can be obtained.
• the reason is not clear, but is considered as follows.
• the carbodiimide compound contained in the aqueous ink or the aqueous composition and a part of the carboxy groups of the vinyl polymer constituting the polymer particles containing the pigment undergo a crosslinking reaction on the surface of the recording medium, and the carbodiimide compound is strongly solidified on the recording medium.
• an ink film having an appropriate crosslinked structure can be formed. Further, when a vinyl polymer having a relatively low acid value such as an acid value of 70 mgKOH / g or less is used, electrostatic repulsion between the pigment-containing polymer particles is suppressed, and the polymer particles are dried when the ink is dried. Water is less likely to remain. Then, it is considered that the polymer particles easily adhere to each other, and a crosslinked structure may be generated between the polymer particles. It is considered that the pigment particles are fixed on the recording medium by the ink film, and as a result, the scratch resistance of the obtained printed matter is improved.
• a vinyl polymer having a relatively low acid value such as an acid value of 70 mgKOH / g or less
• ⁇ Carbodiimide compound> In the water-based ink of the present invention, by using a carbodiimide compound and a vinyl polymer having a carboxy group in combination, a strong film is formed on a recording medium while maintaining the storage stability of the water-based ink, and the scratch resistance of printed matter is improved. Performance can be improved.
• a carbodiimide compound a polycarbodiimide compound having two or more carbodiimide groups in one molecule is preferable.
• a polycarbodiimide compound a polymer containing a carbodiimide group (hereinafter, also referred to as a “carbodiimide group-containing polymer”) is preferable.
• the carbodiimide group equivalent of the carbodiimide group-containing polymer is preferably 200 or more, more preferably 250 or more, still more preferably 300 or more, from the viewpoint of improving the scratch resistance of the printed matter, and the storage stability of the aqueous composition. From the viewpoint, it is preferably 650 or less, more preferably 500 or less, further preferably 400 or less, and still more preferably 360 or less.
• carbodiimide group equivalent means the mass of the carbodiimide group containing polymer per 1 mol of carbodiimide groups.
• the polycarbodiimide compound is preferably an aqueous polycarbodiimide compound from the viewpoint of reactivity, stability, handleability, and the like.
• the aqueous polycarbodiimide compound has water solubility or water dispersibility, and examples thereof include a compound having a hydrophilic group at a terminal.
• Such an aqueous polycarbodiimide compound after forming an isocyanate-terminated polycarbodiimide by a condensation reaction involving decarbonation of an organic diisocyanate compound, further adding a known hydrophilic segment having a functional group having reactivity with an isocyanate group. Can be manufactured.
• carbodiimide group-containing polymers include carbodilite E-02, carbodilite E-03A, carbodilite E-05, carbodilite V-02, carbodilite V-02-L2, carbodilite V-04, (all manufactured by Nisshinbo Chemical Co., Ltd.). , Trade names).
• the pigment used in the present invention may be any of an inorganic pigment and an organic pigment, and may be a lake pigment or a fluorescent pigment. If necessary, they can be used in combination with extenders.
• the inorganic pigment include metal oxides such as carbon black, titanium oxide, iron oxide, red iron oxide, and chromium oxide, and pearlescent pigments. Particularly in a black ink, carbon black is preferable. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.
• organic pigments include azo pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments, chelate azo pigments; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindigos
• azo pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments, chelate azo pigments
• phthalocyanine pigments perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindigos
• polycyclic pigments such as linone pigment, quinophthalone pigment, diketopyrrolopyrrole pigment, benzimidazolone pigment, and sullen pigment.
• the hue is not particularly limited, and any of achromatic pigments such as white, black, and gray; and chromatic pigments such as yellow, magenta, cyan, blue, red, orange, and green can be used.
• achromatic pigments such as white, black, and gray
• chromatic pigments such as yellow, magenta, cyan, blue, red, orange, and green
• Specific examples of preferred organic pigments include C.I. I. Pigment Yellow 13, 17, 74, 83, 93, 97, 109, 110, 120, 128, 138, 139, 151, 154, 155, 174, 180; I. Pigment Red 48, 57: 1, 122, 146, 150, 176, 184, 185, 188, 202, 254; I. Pigment orange; C.I. I. Pigment Violet 19, 23; I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 60; I. Pigment Green 7, 36 or the like.
• the extender include silica
• the pigment and the vinyl polymer exist in the form of polymer particles containing a pigment (hereinafter also referred to as “pigment-containing polymer particles”) in an aqueous ink from the viewpoint of improving the recording density.
• containing a pigment refers to a form in which the pigment is included in the polymer particles, a form in which a part of the pigment is included in the polymer particles, and a part of the pigment is exposed from the polymer particles, Or, a form in which the polymer particles adhere to the surface of the pigment is included, and a mixture thereof is also included.
• a form in which the pigment is included in the polymer particles is preferable.
• the “pigment-containing polymer particles” is used as a concept including “pigment-containing crosslinked polymer particles” (pigment-containing crosslinked polymer particles) described below.
• the water-based ink of the present invention contains a vinyl polymer having a carboxy group having an acid value of 70 mgKOH / g or less as a resin having a reactive group that undergoes a cross-linking reaction with a carbodiimide compound, from the viewpoint of improving the scratch resistance of printed matter.
• the vinyl polymer is preferably a water-insoluble polymer from the viewpoint of improving the scratch resistance of the printed matter.
• the “water-insoluble polymer” refers to a polymer that has been dried at 105 ° C.
• the polymer preferably has a dissolution amount of 5 g or less, more preferably 1 g or less. The amount dissolved is the amount dissolved when 100% of the carboxy groups of the polymer are neutralized with sodium hydroxide.
• This vinyl polymer has a constituent unit derived from the component (a) and a constituent unit derived from the component (b).
• the vinyl polymer preferably has a structural unit derived from a hydrophilic nonionic monomer (c) in addition to the structural unit derived from the component (a) and the structural unit derived from the component (b).
• the ionic monomer (a) is preferably used as a monomer component of the vinyl polymer from the viewpoint of stably dispersing the pigment-containing polymer particles in the aqueous ink.
• the ionic monomer (a) include an anionic monomer and a cationic monomer, and an anionic monomer is preferable.
• the anionic monomer include a carboxylic acid monomer since the vinyl polymer has a carboxy group. In addition to the carboxylic acid monomer, a sulfonic acid monomer, a phosphoric acid monomer and the like may be used in combination.
• Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, 2-methacryloyloxymethylsuccinic acid, and the like.
• Examples of the sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 3-sulfopropyl (meth) acrylate.
• (meth) acrylate indicates acrylate and / or methacrylate. The same applies to the following.
• Examples of the phosphoric acid monomer include vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and the like.
• anionic monomers from the viewpoint of the dispersion stability of the anionic polymer particles in the aqueous ink, a carboxylic acid monomer is preferable, acrylic acid and methacrylic acid are more preferable, and methacrylic acid is further preferable.
• the hydrophobic monomer (b) is used as a monomer component of a vinyl polymer from the viewpoint of dispersion stability of the pigment-containing polymer particles.
• the hydrophobic monomer (b) include at least one selected from an alkyl (meth) acrylate, an aromatic group-containing monomer, and a macromonomer. It is preferable that the hydrophobic monomer (b) contains a macromonomer.
• the alkyl (meth) acrylate those having an alkyl group having 1 to 22 carbon atoms, preferably 6 to 18 carbon atoms are preferable.
• "(iso or tertiary)" and “(iso)” mean both the case where these groups exist and the case where these groups do not exist, and show the normal when these groups do not exist.
• aromatic group-containing monomer a vinyl monomer having an aromatic group having 6 to 22 carbon atoms which may have a substituent containing a hetero atom is preferable, and a styrene monomer and an aromatic group-containing (meth) acrylate Are more preferable, and it is also preferable to use them in combination.
• styrene monomer styrene, 2-methylstyrene, and divinylbenzene are preferable, and styrene is more preferable.
• aromatic group-containing (meth) acrylate benzyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like are preferable, and benzyl (meth) acrylate is more preferable.
• the macromonomer is a compound having a polymerizable functional group at one end and having a number average molecular weight of 500 to 100,000, preferably 1,000 to 10,000. From the viewpoint of dispersion stability of the pigment-containing polymer particles, It is used as a monomer component.
• As the polymerizable functional group present at one terminal an acryloyloxy group or a methacryloyloxy group is preferable, and a methacryloyloxy group is more preferable.
• the number average molecular weight of the macromonomer is measured by gel chromatography using chloroform containing 1 mmol / L dodecyldimethylamine as a solvent, and using polystyrene as a standard substance.
• an aromatic group-containing monomer-based macromonomer and a silicone-based macromonomer are preferable, and an aromatic group-containing monomer-based macromonomer is more preferable.
• aromatic group-containing monomer constituting the aromatic group-containing monomer-based macromonomer examples include the above-mentioned aromatic group-containing monomers, and styrene and benzyl (meth) acrylate are preferable, and styrene is more preferable.
• Specific examples of the styrene-based macromonomer include AS-6 (S), AN-6 (S), HS-6 (S) (trade name of Toagosei Co., Ltd.) and the like.
• silicone-based macromonomer examples include an organopolysiloxane having a polymerizable functional group at one end.
• the monomer component of the vinyl polymer preferably further contains a hydrophilic nonionic monomer (c) from the viewpoint of dispersion stability of the pigment-containing polymer particles.
• polypropylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acyl Rate, phenoxy (ethylene glycol-propylene glycol copolymer) (meth) acrylate are preferable, it is also preferred to use them.
• the commercially available component (c) include NK Esters TM-20G, 40G, 90G, and 230G of Shin-Nakamura Chemical Co., Ltd., and Blemmer PE-90 and 200 of Nippon Oil Co., Ltd. , 350, PME-100, 200, 400, etc., PP-500, 800, etc., AP-150, 400, 550, etc., 50 PEP-300, 50 POEP-800B, 43 PAPE-600B (all above are hydroxyl groups) Yes) and the like.
• the components (a) to (c) can be used alone or in combination of two or more.
• the content of the above components (a) to (c) in the monomer mixture (content as an unneutralized amount; the same applies hereinafter) or the components (a) to (c) in the vinyl polymer is as follows from the viewpoint of the dispersion stability of the pigment-containing polymer particles in the aqueous ink.
• the content of the component (a) is preferably at least 2% by mass, more preferably at least 4% by mass, still more preferably at least 5% by mass, and preferably at most 40% by mass, more preferably at most 30% by mass. , More preferably 25% by mass or less.
• the content of the component (b) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and preferably 98% by mass or less, more preferably 90% by mass or less. , More preferably 80% by mass or less.
• the content of the component (c) is 0% by mass or more, and when the component (c) is used, the content is preferably 2% by mass or more, more preferably 4% by mass or more, and still more preferably 6% by mass or more. And it is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.
• the content of the macromonomer is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and preferably 50% by mass or more. %, More preferably 40% by mass or less, further preferably 30% by mass or less.
• the mass ratio of [(a) component / (b) component] in the monomer mixture that is, the structural unit derived from the hydrophobic monomer (b) (when the structural unit derived from the hydrophobic monomer (b) is two or more types) Is the total amount) and the mass ratio of the structural unit derived from the ionic monomer (a) (the total amount when there are two or more structural units derived from the ionic monomer (a)) [(a) / (b)] Is preferably at least 0.01, more preferably at least 0.02, even more preferably at least 0.03, and preferably at most 1.0, more preferably at most 0.7, even more preferably at most 0.5. It is as follows.
• the vinyl polymer is produced by copolymerizing a monomer mixture by a known polymerization method.
• a solution polymerization method is preferable.
• the solvent used in the solution polymerization method is not particularly limited, and includes one or more polar organic solvents selected from aliphatic alcohols having 1 to 8 carbon atoms, ketones, ethers, esters, and the like.
• aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol, acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ketones having 3 to 6 carbon atoms are preferable, and methyl ethyl ketone is more preferable.
• a polymerization initiator or a polymerization chain transfer agent can be used.
• the polymerization initiator is preferably an azo compound, more preferably 2,2'-azobis (2,4-dimethylvaleronitrile), and the polymerization chain transfer agent is preferably a mercaptan, more preferably 2 -Mercaptoethanol and 2-mercaptopropionic acid.
• Preferred polymerization conditions vary depending on the type of polymerization initiator, etc., but the polymerization temperature is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and preferably 90 ° C. or lower, more preferably 85 ° C. or lower. .
• the polymerization time is preferably at least 1 hour, more preferably at least 1.5 hours, and preferably at most 20 hours, more preferably at most 10 hours.
• the polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon. From the viewpoint of improving the productivity of the aqueous dispersion of the pigment-containing polymer particles, the vinyl polymer is preferably used as a polymer solution without removing the solvent used for the polymerization reaction.
• the solid content concentration of the obtained vinyl polymer solution is preferably 30% by mass or more, more preferably 35% by mass or more, and preferably 60% from the viewpoint of improving the productivity of the aqueous dispersion of the pigment-containing polymer particles. % By mass, more preferably 50% by mass or less.
• the acid value of the vinyl polymer used in the present invention is preferably 70 mgKOH / g or less, preferably 68 mgKOH / g or less, more preferably 65 mgKOH / g or less, from the viewpoint of improving the scratch resistance of the printed matter. From the viewpoint of dispersing the pigment, it is preferably at least 20 mgKOH / g, more preferably at least 30 mgKOH / g, even more preferably at least 35 mgKOH / g.
• the weight average molecular weight of the vinyl polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and still more preferably 3 or more, from the viewpoint of improving the scratch resistance of the printed matter.
• the acid value and the weight average molecular weight can be measured by the methods described in Examples.
• Pigment-containing polymer particles (pigment-containing polymer particles) can be efficiently produced as a water dispersion by a method having the following steps (1) and (2) and, if necessary, further a step (3). Can be.
• Step (1) Step of dispersing a mixture containing a vinyl polymer, an organic solvent, a pigment, and water to obtain a dispersion of pigment-containing polymer particles
• Step (2) Dispersion obtained in Step (1)
• Step (3) mixing the aqueous dispersion of the pigment-containing polymer particles obtained in Step (2) with a crosslinking agent to remove the organic solvent from To obtain an aqueous dispersion of pigment-containing crosslinked polymer particles (hereinafter also referred to as “pigment-containing crosslinked polymer particles”)
• Step (1) is a step of subjecting a mixture containing a vinyl polymer, an organic solvent, a pigment, and water to a dispersion treatment to obtain a dispersion of pigment-containing polymer particles.
• step (1) first, the vinyl polymer is dissolved in an organic solvent, and then the pigment, water, and if necessary, a neutralizing agent, a surfactant, and the like are added to the obtained organic solvent solution and mixed.
• a method for obtaining an oil-in-water dispersion is preferred.
• the order of adding the vinyl polymer to the organic solvent solution is not limited, but it is preferable to add water, a neutralizing agent, and a pigment in this order.
• the organic solvent in which the vinyl polymer is dissolved is not particularly limited, and examples thereof include aliphatic alcohols having 2 to 6 carbon atoms, ketones having 3 to 8 carbon atoms, ethers such as dibutyl ether, tetrahydrofuran, and dioxane, and esters. Among these, organic solvents having 3 to 6 carbon atoms are preferable, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are preferable.
• the organic solvent used in the polymerization may be used as it is.
• the carboxy groups of the vinyl polymer is neutralized using a neutralizing agent.
• the pH of the resulting dispersion is preferably 5.5 or more, more preferably 6 or more from the viewpoint of handling properties such as reducing skin irritation, and preferably 13 or less from the viewpoint of suppressing corrosion of members. , More preferably 12 or less, still more preferably 11 or less.
• the neutralizing agent include bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and various amines.
• the vinyl polymer may be neutralized in advance.
• the degree of neutralization of the carboxy group of the vinyl polymer is preferably at least 10 mol%, more preferably at least 20 mol%, further preferably at least 30 mol%, and preferably at least 300 mol%, from the viewpoint of dispersion stability. Or less, more preferably 200 mol% or less, further preferably 150 mol% or less.
• the degree of neutralization can be determined by the following formula as the equivalent of the neutralizing agent to the carboxy group of the vinyl polymer. When the use equivalent of the neutralizing agent is 100 mol% or less, it is synonymous with the degree of neutralization.
• Use equivalent (mol%) of neutralizer [ ⁇ addition mass of neutralizer (g) / equivalent of neutralizer] / [ ⁇ weighted average acid value of vinyl polymer (mgKOH / g) ⁇ weight of vinyl polymer ( g) ⁇ / (56 ⁇ 1000)]] ⁇ 100
• the content of the pigment is preferably 5% by mass or more, more preferably 10% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less.
• the content of the vinyl polymer is preferably 2% by mass or more, more preferably 3% by mass or more, and preferably 40% by mass or less, more preferably 20% by mass or less.
• the content of the organic solvent is preferably 10% by mass or more, and is preferably 70% by mass or less, more preferably 50% by mass or less.
• the water content is preferably at least 10% by mass, more preferably at least 20% by mass, and preferably at most 70% by mass.
• the mass ratio of the pigment content to the vinyl polymer content [pigment / vinyl polymer] is preferably from 50/50 to 90/10, and more preferably from 60/40 to 80/20, from the viewpoint of dispersion stability. .
• the method for dispersing the mixture in step (1) is not particularly limited. Although the average particle size of the pigment-containing polymer particles can be reduced to a desired particle size only by the main dispersion, preferably, after the preliminary dispersion, the main dispersion is further performed by applying a shearing stress to the pigment-containing polymer. It is preferable to control the average particle size of the particles to a desired particle size.
• the temperature in the dispersion in step (1) is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, even more preferably 5 ° C. or higher, and is preferably 40 ° C. or lower, more preferably 30 ° C. or lower.
• the dispersion time is preferably at least 1 hour, more preferably at least 2 hours, and preferably at most 30 hours, more preferably at most 20 hours.
• Examples of a device for pre-dispersing the mixture include known mixing and stirring devices such as an anchor blade and a disper blade, among which a high-speed stirring and mixing device is preferable.
• Examples of the apparatus for applying the shear stress of the dispersion include kneaders such as a roll mill and a kneader, high-pressure homogenizers such as a microfluidizer (trade name, manufactured by Microfluidics), and media dispersers such as a paint shaker and a bead mill. These devices can also be used in combination.
• high-pressure homogenizer is preferable from the viewpoint of reducing the particle size of the pigment-containing polymer particles. More preferably, there is a method of performing high pressure dispersion treatment after preliminary dispersion using a disper or the like.
• “high-pressure dispersion” means dispersion at a dispersion pressure of 20 MPa or more.
• the dispersion pressure is preferably 50 MPa or more, more preferably 100 MPa or more, still more preferably 120 MPa or more, preferably 250 MPa or less, more preferably 200 MPa or less, from the viewpoint of reducing the particle diameter and the dispersion treatment efficiency.
• Step (2) is a step of removing the organic solvent from the dispersion obtained in step (1) to obtain an aqueous dispersion of pigment-containing polymer particles.
• the removal of the organic solvent can be performed by a known method.
• the organic solvent in the aqueous dispersion containing the pigment-containing polymer particles is preferably substantially removed, but may remain as long as the object of the present invention is not impaired.
• the amount of the residual organic solvent is preferably 0.1% by mass or less, more preferably 0.01% by mass or less. If necessary, the dispersion can be heated and stirred before the organic solvent is distilled off.
• the temperature of the dispersion when removing the organic solvent can be appropriately selected depending on the type of the organic solvent used, but under reduced pressure, is preferably 20 ° C.
• the temperature is more preferably 70 ° C or lower.
• the removal of the organic solvent is preferably performed until the concentration of the nonvolatile component (solid content) of the dispersion from which the organic solvent has been removed becomes preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 50% by mass or more. It is preferable to carry out the reaction until the amount becomes not more than 40% by mass, more preferably not more than 40% by mass, further preferably not more than 35% by mass.
• the solid concentration of the aqueous dispersion is measured by the method described in Examples.
• the obtained aqueous dispersion of the pigment-containing polymer particles is one in which the solid content of the pigment-containing polymer particles having the above-mentioned particle form is dispersed in water as a main medium.
• the average particle diameter of the pigment-containing polymer particles is preferably 40 nm or more, more preferably 50 nm or more, further preferably 60 nm or more, and preferably 400 nm or less, more preferably 400 nm or more, from the viewpoint of improving the scratch resistance of the printed matter. It is 250 nm or less, more preferably 200 nm or less, even more preferably 170 nm or less.
• the average particle size of the pigment-containing polymer particles is measured by the method described in Examples.
• Step (3) is a step of mixing the aqueous dispersion containing the pigment-containing polymer particles obtained in the step (2) with a crosslinking agent, and performing a crosslinking treatment to obtain an aqueous dispersion containing the pigment-containing crosslinked polymer particles.
• Step (3) is an optional step.
• the vinyl polymer constituting the pigment-containing polymer particles becomes a crosslinked polymer.
• the swelling of the vinyl polymer in the organic solvent is suppressed, so that the scratch resistance of the obtained printed matter can be improved.
• a method of the crosslinking treatment a method of reacting a mixture of the aqueous dispersion and the crosslinking agent at 60 ° C. or higher, preferably 65 ° C. or higher while stirring is mentioned.
• the crosslinking agent a water-insoluble polyfunctional epoxy compound having two or more epoxy groups in a molecule is preferable.
• a part of the carboxy group of the vinyl polymer is crosslinked by a water-insoluble polyfunctional epoxy compound.
• the crosslinking agent is more preferably a compound having two or more glycidyl ether groups in the molecule, and still more preferably a polyglycidyl ether compound of a polyhydric alcohol having three to eight hydrocarbon groups in the molecule.
• water-insoluble of the crosslinking agent means that when the crosslinking agent is dissolved in 25O ⁇ 0> C ion-exchanged water to 100 g until it is saturated, the dissolved amount is preferably less than 50 g.
• the amount of the dissolution is preferably 40 g or less, more preferably 35 g or less.
• the water content of the crosslinking agent is preferably less than 50% by mass, more preferably 40% by mass or less, and still more preferably 35% by mass or less, from the viewpoint of efficiently causing a crosslinking reaction in the aqueous medium.
• the water solubility refers to a dissolution rate (% by mass) when 10 parts by mass of a crosslinking agent is dissolved in 90 parts by mass of water at room temperature of 25 ° C.
• the molecular weight of the crosslinking agent is preferably 120 or more, more preferably 150 or more, still more preferably 200 or more, and preferably 2,000 or less, more preferably 1500 or less, and still more preferably 1,000 or less. It is as follows.
• the epoxy equivalent (g / eq) of the crosslinking agent is preferably 90 or more, more preferably 100 or more, further preferably 110 or more, and preferably 300 or less, more preferably 200 or less, and still more preferably 150 or less. is there.
• the measurement of the water content and the epoxy equivalent of the epoxy compound can be performed by the methods described in Examples.
• crosslinking agent examples include polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, And polyglycidyl ethers such as neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and hydrogenated bisphenol A type diglycidyl ether.
• polypropylene glycol diglycidyl ether water content 31% by mass
• trimethylolpropane polyglycidyl ether water content 27% by mass
• pentaerythritol polyglycidyl ether water content 0% by mass
• water-insoluble polyfunctional epoxy compound include Denacol EX series manufactured by Nagase ChemteX Corporation, Epiol BE manufactured by NOF Corporation, and B series manufactured by NOF Corporation.
• the amount of the crosslinking agent, especially the water-insoluble polyfunctional epoxy compound is preferably 0.1 mmol of the ionic group of the vinyl polymer in terms of the amount of the ionic group per 1 g of the vinyl polymer from the viewpoint of improving the scratch resistance of the printed matter. Above, more preferably 0.3 mmol or more, more preferably an amount that reacts with 0.5 mmol or more, and preferably 20 mmol or less of ionic groups of the polymer, more preferably 15 mmol or less, even more preferably 10 mmol or less, more preferably The amount is more preferably 5 mmol or less, and still more preferably 1.0 mmol or less.
• the pigment-containing crosslinked polymer particles obtained by the cross-linking treatment preferably contain at least 0.3 mmol, more preferably at least 0.5 mmol, of the ionic group neutralized with a base per 1 g of the polymer, and , 1.5 mmol or less.
• the crosslinking ratio of the pigment-containing polymer particles A is preferably at least 10 mol%, more preferably at least 20 mol%, further preferably at least 30 mol%, and preferably at most 80 mol%, more preferably at least 60 mol%. Or less, more preferably 50 mol% or less.
• the crosslinking ratio is a value obtained by dividing the number of moles of the reactive group of the crosslinking agent by the number of moles of the reactive group (carboxy group) capable of reacting with the crosslinking agent of the pigment-containing polymer particles.
• the water-based ink of the present invention preferably further contains a water-soluble organic solvent from the viewpoint of improving storage stability and inkjet dischargeability, and from the viewpoint of improving the scratch resistance of printed matter by forming a smooth ink film.
• the “water-soluble organic solvent” refers to an organic solvent in which the amount of the organic solvent dissolved in 100 ml of water at 25 ° C. is 10 ml or more.
• the boiling point of the water-soluble organic solvent is preferably 150 ° C. or higher, more preferably 160 ° C. or higher, even more preferably 170 ° C. or higher, even more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C.
• the boiling point of the water-soluble organic solvent is a weighted average value weighted by the content (% by mass) of each water-soluble organic solvent.
• water-soluble organic solvent examples include polyhydric alcohols, polyhydric alcohol alkyl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
• polyhydric alcohols are preferred from the viewpoint of improving the dischargeability, storage stability, and scratch resistance of the printed matter of the aqueous ink.
• the polyhydric alcohol can be used by mixing a plurality of polyhydric alcohols included in the concept of the polyhydric alcohol, and a part of the polyhydric alcohol can be substituted with the polyhydric alcohol alkyl ether.
• a polyhydric alcohol alkyl ether When a polyhydric alcohol alkyl ether is used, a mixture of a plurality of polyhydric alcohols included in the concept of polyhydric alcohol alkyl ether can be used as in the case of the polyhydric alcohol.
• polyhydric alcohol examples include ethylene glycol (boiling point: 197 ° C.), propylene glycol (boiling point: 188 ° C.), dipropylene glycol (boiling point: 232 ° C.), polypropylene glycol, 1,3-propanediol (boiling point: 210 ° C.), 2-methyl -1,3-propanediol (boiling point 214 ° C), 1,2-butanediol (boiling point 192 ° C), 1,3-butanediol (boiling point 208 ° C), 1,4-butanediol (boiling point 230 ° C), 3 -Methyl-1,3-butanediol (boiling point 203 ° C), 1,5-pentanediol (boiling point 242 ° C), 2-methyl-2,4-pentanediol (bo
• diethylene glycol (boiling point: 244 ° C.), polyethylene glycol, 1,6-hexanediol (boiling point: 250 ° C.), triethylene glycol (boiling point: 285 ° C.), tripropylene glycol (boiling point: 273 ° C.), glycerin (boiling point: 290 ° C.), etc. It can also be used.
• These compounds having a boiling point higher than 240 ° C. are preferably used in combination with a compound having a boiling point lower than 240 ° C.
• polyhydric alcohol alkyl ether examples include an alkylene glycol monoalkyl ether, a dialkylene glycol monoalkyl ether, and a trialkylene glycol monoalkyl ether.
• ethylene glycol monoethyl ether (boiling point 135 ° C.), ethylene glycol monobutyl ether (boiling point 171 ° C.), diethylene glycol monomethyl ether (boiling point 194 ° C.), diethylene glycol monoethyl ether (boiling point 202 ° C.), diethylene glycol monobutyl ether (boiling point 230 ° C), triethylene glycol monomethyl ether (boiling point 122 ° C), triethylene glycol monoisobutyl ether (boiling point 160 ° C), tetraethylene glycol monomethyl ether (boiling point 158 ° C), propylene glycol monoethyl ether (boiling point 1
• the water-soluble organic solvent preferably contains a polyhydric alcohol from the viewpoint of improving the scratch resistance of the printed matter, and among the polyhydric alcohols, preferably a diol having 3 to 6 carbon atoms, more preferably 3 or 4 carbon atoms. Diol, more preferably propylene glycol.
• the content of the polyhydric alcohol in the water-soluble organic solvent is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
• the aqueous ink of the present invention may contain a pigment-free vinyl polymer, a pigment-free polyester resin particle, a pigment-free polyurethane resin particle, and the like as a fixing aid polymer for fixing the pigment to a recording medium. it can.
• the aqueous ink of the invention may further contain another resin having a reactive group capable of undergoing a cross-linking reaction with the carbodiimide compound (hereinafter, also referred to as “resin C”). By containing the resin C, the crosslinking density of the ink film is increased by the mediation of the resin C, and a stronger film can be formed.
• the reactive group may be any reactive group that undergoes a cross-linking reaction with at least one selected from an isocyanate group, a carbodiimide group, and an oxazoline group.
• Specific examples include a carboxy group, a hydroxy group, an amino group, and a thiol group, and one or more selected from a carboxy group and a hydroxy group are preferable.
• the resin C include a polyurethane resin and a polyester resin having a carboxy group.
• the resin C is a copolymer, any of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer may be used.
• the water-based ink of the present invention may contain a surfactant, a viscosity modifier, an antifoaming agent, a preservative, an antifungal agent, a rust inhibitor and the like which are usually used in a coating liquid or the like discharged by an inkjet method. it can.
• the content of each component of the aqueous ink is as follows from the viewpoint of improving the storage stability of the aqueous ink and the abrasion resistance of the printed matter.
• the content of the carbodiimide compound in the aqueous ink is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 10% by mass or less. , More preferably 5% by mass or less, still more preferably 3% by mass or less.
• the content of the vinyl polymer in the aqueous ink is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and preferably 15% by mass or less, more preferably It is at most 12% by mass, more preferably at most 10% by mass.
• the mass ratio of the carbodiimide compound to the vinyl polymer is preferably at least 0.01, more preferably at least 0.1, even more preferably at least 0.3, and preferably at most 1.0. , More preferably 0.7 or less, still more preferably 0.5 or less.
• the content of the pigment in the ink is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less. , More preferably 9% by mass or less, even more preferably 8% by mass or less.
• the content (solid content) of the pigment-containing polymer particles in the ink is preferably 3.0% by mass or more, more preferably 4.0% by mass or more, still more preferably 6.0% by mass or more, and preferably Is 30% by mass or less, more preferably 20% by mass or less, still more preferably 18% by mass or less, and still more preferably 15% by mass or less.
• the content of water in the ink is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less. , More preferably 70% by mass or less.
• the content of the organic solvent in the ink is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably Is at most 60% by mass, more preferably at most 50% by mass, further preferably at most 40% by mass.
• the ink set for ink jet recording of the present invention (hereinafter also simply referred to as “ink set”) is an ink for ink jet recording comprising an aqueous composition containing a carbodiimide compound and water, and an aqueous ink containing a pigment and a vinyl polymer.
• the vinyl polymer is a polymer having a carboxy group having an acid value of 70 mgKOH / g or less
• the pigment is in the form of pigment-containing polymer particles.
• the ink set includes, for example, (i) an aqueous composition containing a carbodiimide compound and water, and a water-based ink containing a pigment and a vinyl polymer or vinyl polymer particles containing a pigment in an ink cartridge for each color of an inkjet recording apparatus. And a water-based ink containing is filled in each of the ink cartridges, and printing can be performed by discharging each of the ink droplets from each discharge nozzle corresponding to each ink cartridge.
• a water-based ink containing a carbodiimide compound, a pigment and a vinyl polymer or a vinyl polymer particle containing a pigment, and water is filled into an ink cartridge, and each of the water-based inks is discharged as an ink droplet from a discharge nozzle corresponding to the ink cartridge.
• the water-based ink can be used alone or in combination of two or more hues.
• the inkjet recording method of the present invention includes the following steps 1 and 2 from the viewpoint of improving the scratch resistance of the printed matter.
• Step 1 A step of discharging a carbodiimide compound, a pigment, a vinyl polymer, and water onto the surface of a recording medium by an inkjet method to obtain a recorded image
• the vinyl polymer is a polymer having a carboxy group having an acid value of 70 mgKOH / g or less.
• pigments are in the form of pigment-containing polymer particles.
• Step 2 a step of heating the recorded image obtained in Step 1 at a temperature of 50 ° C. or more and 200 ° C. or less.
• Step 1 is a step of discharging a carbodiimide compound, a pigment, a vinyl polymer, and water onto a recording medium surface by an inkjet method to obtain a recorded image.
• an aqueous ink containing a carbodiimide compound, polymer particles containing a pigment, and water is ejected onto a recording medium by an inkjet method.
• the method includes a step 1a of discharging an aqueous ink containing a pigment and a vinyl polymer or a polymer particle containing a pigment by an inkjet method, and a step 1b of discharging an aqueous composition containing a carbodiimide compound and water by an inkjet method.
• step 1a is preferably performed before step 1b or simultaneously with step 1b, and more preferably, step 1a is performed before step 1b.
• step 1a is performed before the step 1b.
• the time from application of the aqueous ink to the recording medium to application of the aqueous composition to the recording medium is not particularly limited.
• the pigment can be included in the aqueous ink
• the carbodiimide compound can be included in at least one of the aqueous ink and the aqueous composition
• the vinyl polymer can be included in at least one of the aqueous ink and the aqueous composition.
• a combination of an aqueous composition containing a carbodiimide compound and an aqueous ink containing a polyester resin, and a combination of an aqueous ink containing a carbodiimide compound and a vinyl polymer are preferable.
• a piezo method is preferable from the viewpoint of dischargeability.
• the amount of the water-based ink applied to the recording medium is preferably 0.5 g / m 2 or more, more preferably 1.5 g / m 2 or more, and still more preferably 2 g / m 2 or more, in terms of solid content, from the viewpoint of improving the scratch resistance of the printed matter.
• 0.0 g / m 2 or more and preferably 10 g / m 2 or less, more preferably 7.5 g / m 2 or less, and still more preferably 5.0 g / m 2 or less.
• Step 2 is a step of heating the recorded image obtained in step 1 at a temperature of 50 ° C. or more and 200 ° C. or less.
• a crosslinking reaction proceeds between the carbodiimide compound and the vinyl polymer having a carboxy group, and a strong ink film is formed.
• the heat treatment method there is no particular limitation on the heat treatment method, and (i) a method in which hot air is applied to the surface of the recorded image for heating, (ii) a method in which a heater is brought close to the surface of the recorded image, and (iii) a recorded image forming surface. And (iv) heating by steam curing using high-temperature steam at normal pressure or high pressure.
• the heating temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, even more preferably 110 ° C. or higher, and is preferably 200 ° C. or lower, more preferably 170 ° C. or lower, further preferably 150 ° C. or lower.
• the recording medium is a shrink film
• the heating time is preferably at least 1 minute, more preferably at least 3 minutes, even more preferably at least 5 minutes, and is preferably at most 30 minutes, more preferably at most 20 minutes, even more preferably at most 15 minutes.
• the drying temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and is preferably lower than 100 ° C., more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.
• the drying treatment also serves as the above-mentioned heating treatment.
• the drying time is preferably 1 minute or more, more preferably 2 minutes or more, and is preferably 20 minutes or less, more preferably 10 minutes or less, and even more preferably 5 minutes or less.
• the recording medium used in the inkjet recording method of the present invention is not particularly limited.
• Examples of the recording medium include plain paper with high water absorption, coated paper with low water absorption, and resin film. From the viewpoint of commercial printing and industrial printing, coated paper and resin film with low water absorption are preferable, and low water absorption. Is more preferable.
• Low water absorption of a recording medium is a concept including low water absorption and non-water absorption of water and / or ink, and low water absorption can be evaluated by water absorption of pure water.
• the water absorption of the recording medium at a contact time of 100 msec between the recording medium and pure water is 0 g / m 2 or more and 10 g / m 2 or less, preferably 0 g / m 2 or more and 6 g / m 2 or less. It means there is.
• the coated paper include general-purpose glossy paper and multicolor foam gloss paper.
• the resin film is preferably at least one selected from a polyester film, a polyvinyl chloride film, a polypropylene film, and a polyethylene film.
• the surface of the resin film on which a recorded image is formed may be corona-treated.
• resin films include Lumirror T60 (manufactured by Toray Industries, Inc., polyester), PVC80BP (manufactured by Lintec Corporation, vinyl chloride), Kinas KEE70CA (manufactured by Lintec Corporation, polyethylene), and Yupo SG90 PAT1 (manufactured by Lintec Corporation) , Polypropylene,), FOR, FOA (the above, polypropylene manufactured by Futamura Chemical Co., Ltd.), Bonyl RX (nylon, manufactured by Kojin Film & Chemicals Co., Ltd.), and the emblem ONBC (nylon, manufactured by Unitika Ltd.).
• the shrink film that shrinks when heated is selected from polyester resins; styrene resins such as polystyrene and styrene-butadiene copolymer; polylactic acid; olefin resins such as polyethylene and polypropylene; and thermoplastic resins such as vinyl chloride resins. And a laminated film of these.
• Commercially available shrink films include Space Clean S7042 (manufactured by Toyobo Co., Ltd.), DXL series, Hishipet series, PLABIO, HybrexDL (manufactured by Mitsubishi Chemical Corporation), Bonset series (manufactured by Takiron C.I. Co., Ltd.), Fancy Wrap PET series (manufactured by Gunze KK) and the like.
• the measurement sample is prepared by mixing 0.1 g of the resin with 10 mL of the above eluent in a glass vial, stirring the mixture with a magnetic stirrer at 25 ° C. for 10 hours, and using a syringe filter (DISMIC-13HP PTFE 0.2 ⁇ m, manufactured by Advantech Co., Ltd.). Used after filtration.
• Production Examples 1-2 (Production of water-insoluble vinyl polymers P-1 and P-2)
• the monomers, the solvent, and the polymerization chain transfer agent shown in “Initially charged monomer solution” in Table 1 or 2 were added and mixed, and nitrogen gas was replaced. A monomer solution was obtained.
• a monomer, a solvent, a polymerization initiator, and a polymerization chain transfer agent shown in “Dropped monomer solution 1” in Table 1 or 2 were mixed to obtain a dropped monomer solution 1, which was placed in a dropping funnel 1 and replaced with nitrogen gas. Was done.
• a monomer, a solvent, a polymerization initiator, and a polymerization chain transfer agent shown in “Dropped monomer solution 2” in Table 1 were mixed to obtain a dropped monomer solution 2, which was placed in a dropping funnel 2 and subjected to nitrogen gas replacement.
• the initially charged monomer solution in the reaction vessel was maintained at 77 ° C. with stirring, and the dropping monomer solution 1 in the dropping funnel 1 was gradually dropped into the reaction vessel over 3 hours.
• the dropping monomer solution 2 in the dropping funnel 2 was gradually dropped into the reaction vessel over 2 hours.
• the mixed solution in the reaction vessel was stirred at 77 ° C. for 0.5 hour.
• a polymerization initiator solution was prepared by dissolving 0.6 part of the polymerization initiator in 27.0 parts of methyl ethyl ketone, and the solution was added to the mixed solution, followed by aging by stirring at 77 ° C. for 1 hour. Preparation, addition and aging of the polymerization initiator solution were further performed 5 times. Then, the reaction solution in the reaction vessel was maintained at 80 ° C. for 1 hour, and methyl ethyl ketone was added to obtain a solution of water-insoluble polymer P-1 (solid content concentration: 40.8%).
• the weight-average molecular weight of the obtained water-insoluble vinyl polymer P-1 (Table 1) was 52,700, and the weight-average molecular weight of the water-insoluble vinyl polymer P-2 (Table 2) was 14,100.
• Step 1 (Preparation of aqueous dispersion 1 of pigment-containing polymer particles)
• Step 1 (Pigment dispersion step)
• MEK methyl ethyl ketone
• a 5N aqueous sodium hydroxide solution was added thereto so that 60 mol% of the polymer acid value was neutralized.
• 379.5 g of ion-exchanged water was dropped over 30 minutes, and the mixture was stirred and mixed at 1,500 r / min for 15 minutes at 10 ° C. or more and 15 ° C. or less using a disper blade.
• Step 2 organic solvent removal step
• the whole amount of the dispersion obtained in the step 1 is placed in a 2 L eggplant-shaped flask, ion-exchanged water is added so that the solid content concentration becomes 15%, and a rotary distillation apparatus ("Rotary evaporator N-1000S" manufactured by Tokyo Rikakiki Co., Ltd.) )), The organic solvent was removed at a rotation speed of 50 r / min in a warm bath adjusted to 32 ° C. at a pressure of 0.09 MPa (abs) for 3 hours. Further, the temperature of the warm bath was adjusted to 62 ° C., the pressure was reduced to 0.07 MPa (abs), and the mixture was concentrated until the solid content concentration became 25% to obtain an aqueous dispersion.
• Step 3 crosslinking treatment step
• the aqueous dispersion obtained in the step 2 is put into a 500 mL angle rotor, and the high-speed cooling centrifuge (“Himac CR22G”, manufactured by Hitachi Koki Co., Ltd., set temperature: 20 ° C.) is used at 3,660 r / min for 20 minutes. After centrifugation, ion-exchanged water was added to the obtained solid content to adjust the solid content concentration to 20%.
• Himac CR22G manufactured by Hitachi Koki Co., Ltd., set temperature: 20 ° C.
• aqueous dispersion 100 parts of the obtained aqueous dispersion is placed in a glass bottle with a screw hole, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Corporation, Denacol EX-321, molecular weight 302, water solubility 27%, epoxy value 140) is used as a crosslinking agent.
• trimethylolpropane polyglycidyl ether manufactured by Nagase ChemteX Corporation, Denacol EX-321, molecular weight 302, water solubility 27%, epoxy value 140
• Preparation Examples A2 to A4 (Preparation of aqueous dispersions 2 to 4 of pigment-containing polymer particles) Water dispersions 2 to 4 of pigment-containing polymer particles were obtained in the same manner as in Preparation Example A1, except that the pigment was changed in Preparation Example A1. Table 3 shows the results.
• Preparation Example A5 (Preparation of aqueous dispersion 5 of pigment-containing polymer particles)
• the polymer P-1 was changed to the polymer P-2, and the concentrate obtained in the step (2) was not subjected to the step (3), and the concentrate obtained in the step (2) was syringed with a 25 mL-capacity syringe equipped with a 5 ⁇ m filter.
• An aqueous dispersion 5 of pigment-containing polymer particles was obtained in the same manner as in Preparation Example A1, except that the mixture was filtered and ion-exchanged water was added to adjust the solid content to 20%. Table 3 shows the results.
• Preparation Example A6 (Preparation of aqueous dispersion 6 of pigment-containing polymer particles)
• a water-soluble styrene-acrylic acid polymer emulsion (Joncryl 690, manufactured by BASF Japan Ltd., solid content concentration 20%, weight average molecular weight 16500, acid value 240 mg KOH / g) as a resin having an anionic group was used. It is mixed with 78.6 parts of MEK, and 5.1 parts of a 5N aqueous sodium hydroxide solution (sodium hydroxide solid content: 16.9%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for volumetric titration) is added to have an anionic group.
• a water-soluble styrene-acrylic acid polymer emulsion (Joncryl 690, manufactured by BASF Japan Ltd., solid content concentration 20%, weight average molecular weight 16500, acid value 240 mg KOH / g) as a resin having an anionic group was
• the resin was neutralized so that the ratio of the number of moles of sodium hydroxide to the number of moles of anionic groups in the resin was 20% (degree of neutralization: 20%). Further, 400 parts of ion-exchanged water was added, and 75 parts of carbon black (Monarch 717, manufactured by Cabot Corporation) was added thereto, to obtain a pigment mixture. The obtained pigment mixture was stirred at 20 ° C.
• Preparation Example A7 (Preparation of aqueous dispersion 7 of pigment-containing polymer particles)
• carbon black was added to C.I. I. Pigment Blue 15: 3 (Chromium Fine Blue (CFB) 6338JC, manufactured by Dainichi Seika Kogyo Co., Ltd.), and a water dispersion 7 of pigment-containing polymer particles was obtained in the same manner as in Preparation Example A6.
• Table 3 shows the results.
• Preparation Examples B1 to B7 (Preparation of aqueous inks 1 to 7)
• the aqueous dispersions 1 to 7 obtained in Preparation Examples A1 to A7, an organic solvent, a surfactant, and ion-exchanged water were blended as shown in Table 4 (total amount: 100%), and aqueous inks 1 to 7 were prepared. Obtained.
• the amount of the aqueous pigment dispersion in Table 4 is the solid content.
• ⁇ PG Propylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd.) -BDG: diethylene glycol monobutyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• KF6011 alkylene glycol-modified polydimethylsiloxane (trade name “KF-6011”, manufactured by Shin-Etsu Chemical Co., Ltd., nonionic surfactant)
• Preparation Examples C1 and C2 (Preparation of aqueous compositions 1-2) A carbodiimide compound, an organic solvent, a surfactant, and ion-exchanged water shown in Table 5 were blended as shown in Table 5 (total amount: 100%) to obtain aqueous compositions 1-2.
• the compounding quantity of the carbodiimide compound in Table 5 is a solid content.
• -Carbodilite E-02 polycarbodiimide (appearance: emulsion, carbodiimide group equivalent 445, effective content 40%, manufactured by Nisshinbo Chemical Inc., trade name)
• -Carbodilite V-04 polycarbodiimide (appearance: aqueous solution, carbodiimide group equivalent: 335, effective content: 40%, manufactured by Nisshinbo Chemical Inc., trade name)
• ⁇ PG Propylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd.)
• KF6011 alkylene glycol-modified polydimethylsiloxane (trade name “KF-6011”, manufactured by Shin-Etsu Chemical Co., Ltd., nonionic surfactant)
• Examples 1 to 10 and Comparative Examples 1 to 3 (recording by ink set) An ink set comprising a combination of the aqueous composition and the aqueous ink shown in Table 6 was loaded into an inkjet printer (IPSiO SG2010L, manufactured by Ricoh Co., Ltd.), and a polyethylene terephthalate (PET) film (Lumirror, manufactured by Toray Industries, Inc.) was used as a recording medium. Solid printing of 10 cm ⁇ 10 cm was performed using (registered trademark) 75T60). Then, after drying at 60 ° C. for 10 minutes under normal pressure and heating at 120 ° C. for 10 minutes, it was left to dry at room temperature for 10 hours, and the scratch resistance of the printed matter was evaluated by the following method.
• IPSiO SG2010L manufactured by Ricoh Co., Ltd.
• PET polyethylene terephthalate
• Solid printing of 10 cm ⁇ 10 cm was performed using (registered trademark) 75T60). Then, after drying at 60 °
• Example 1 to 5 and Comparative Examples 2 and 3 two liquids of an aqueous composition and a water-based ink were loaded into an ink jet printer, and ejected from the two ink jet heads at the same droplet size, so that they were printed on a recording medium. Printing was performed so that both were mixed.
• the aqueous composition and the aqueous ink were mixed at a mass ratio of 1: 1 to prepare an aqueous ink containing a carbodiimide compound, a polyester resin, a pigment, and water, and an aqueous ink having the same composition was prepared.
• Comparative Example 1 Two aqueous inks having the same composition were prepared, and printing was performed by discharging the same ink droplet size from two inkjet heads as in Examples 6 to 10.
• the application amount of the aqueous composition is 0.2 to 1.2 g as a solid content per 1 m 2 for a 100% density solid image, and the ink application amount is 100% density for a solid image.
• the solid content was 1.0 to 2.0 g per m 2 .
• the printed surface of the obtained printed material is impregnated with 100% ethanol into a nonwoven fabric made of cellulose (Bencott (registered trademark) M3-II, manufactured by Asahi Kasei Fibers Corporation), and the printed surface of the obtained printed material is subjected to a load of 100 g / cm 2 . And the state of the printing surface and the nonwoven fabric was visually observed, and the number of times of rubbing until the color was transferred to the cellulose nonwoven fabric was measured. If the rub resistance (the number of rubs) is 5 or more, the rub resistance is sufficient.
• Examples 1 to 5 are examples of the second aspect
• Examples 6 to 10 are examples of the first aspect. From Table 6, it can be seen that according to the aqueous ink, the ink set, and the ink jet recording method using the carbodiimide compound and a vinyl polymer having a carboxy group having an acid value of 70 mgKOH / g or less, a printed matter having excellent scratch resistance can be obtained. On the other hand, in Comparative Examples in which the carbodiimide compound or the vinyl polymer having a carboxy group having an acid value of 70 mgKOH / g or less was used, it was found that a printed matter having excellent scratch resistance could not be obtained.
• the ink set and the ink jet recording method using the water-based ink of the present invention a printed matter excellent in abrasion resistance can be obtained even when printing is performed on a non-water-absorbing recording medium or a shrinkable recording medium.

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