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
  • C09D11/30—Inkjet printing inks
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
• • 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
  • B41J2/21—Ink jet for multi-colour printing
  • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
• • 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
  • C09D11/10—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
  • C09D11/104—Polyesters
• • 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
  • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat

Definitions

• the present invention relates to an aqueous composition 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.
• Examples disclose a block copolymer and a graft copolymer containing methacrylic acid as a dispersant.
• Patent Literature 2 JP-T-2016-505651 discloses that a problem of extending the storage life of a self-crosslinkable pigment ink is to crosslink a pigment, a polymer containing a carboxyl group, and a carboxyl group. Dispersions containing a novel crosslinking agent, an inhibitor containing a tertiary amine, and a liquid carrier, and an ink containing the same are disclosed.
• polymer containing a carboxyl group styrene-acryl copolymer, styrene-methacrylic acid copolymer, maleic resin, maleic anhydride-modified polymer, carboxylated polyurethane, carboxylated styrene-butadiene block copolymer, carboxylated styrene-butadiene-styrene block A copolymer, a carboxylated styrene-isoprene-styrene block copolymer, and a carboxylated polyolefin are disclosed, and a water-dispersible polymer containing a carbodiimide group as a crosslinking agent is disclosed.
• the present invention relates to an aqueous composition for inkjet recording, comprising a carbodiimide compound, a polyester resin, and water.
• 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.
• the present invention relates to an aqueous composition for inkjet recording, an ink set for inkjet recording, and an inkjet recording method capable of obtaining a printed matter having excellent scratch resistance.
• an aqueous composition containing a carbodiimide compound, a polyester resin, and water can improve the scratch resistance of a printed matter obtained by inkjet recording. That is, the present invention relates to the following [1] to [4].
• An aqueous composition for inkjet recording comprising a carbodiimide compound, a polyester resin, and water.
• An ink set for inkjet recording comprising: an aqueous composition a containing a carbodiimide compound and water; and an aqueous composition b containing a polyester resin and water.
• An ink set for inkjet recording comprising the aqueous composition for inkjet recording according to [1] and an aqueous ink containing a colorant.
• An inkjet recording method including the following steps 1 and 2. Step 1: a step of discharging a carbodiimide compound, a polyester resin, a colorant, and water onto the surface of a recording medium by an inkjet method to obtain a recorded image. Step 2: converting the recorded image obtained in the step 1 to a temperature of 50 ° C. or more and 200 ° C. Step of heat treatment at a temperature of below °C
• an aqueous composition for ink jet recording an ink set for ink jet recording, and an ink jet recording method capable of obtaining a printed material having excellent scratch resistance.
• Aqueous composition for inkjet recording of the present invention (hereinafter, also simply referred to as “aqueous composition”) is an aqueous composition containing a carbodiimide compound, a polyester resin, and water.
• the second embodiment is a combination including an aqueous composition a containing a carbodiimide compound and water and an aqueous composition b containing a polyester resin and water.
• the abrasion resistance of the obtained printed matter is improved by mixing the aqueous composition and the aqueous ink containing a colorant on the surface of the recording medium, or by further adding a colorant to the aqueous composition. be able to.
• a colorant can be contained in at least one of the aqueous composition a and the aqueous composition b, and a printed matter obtained by mixing the aqueous composition a and the aqueous composition b on the recording medium surface Can be improved in scratch resistance.
• 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 accounts for the largest proportion in the medium contained in the aqueous composition.
• the aqueous composition of the present invention a printed matter having excellent scratch resistance can be obtained.
• the reason is not clear, but is considered as follows. Normally, when ink jet recording is performed, after the ink has landed on the surface of a non-water-absorbing recording medium such as a resin film, the colorant particles do not permeate into the inside, but remain on and adhere to the recording medium surface.
• the aqueous composition comes into contact with the ink, the carbodiimide compound contained in the aqueous composition and the polyester resin undergo a crosslinking reaction, and an ink film having a strong crosslinked structure can be formed on the recording medium. Conceivable.
• the use of the polyester resin enhances the adhesion of the base material to the recording medium, and can form an ink film that does not easily swell with alcohol or the like. It is considered that the colorant 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.
• aqueous composition of the present invention by using a carbodiimide compound and a polyester resin in combination, while maintaining the storage stability of the aqueous composition, to form a strong film on the recording medium, the scratch resistance of the printed matter 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 aqueous composition of the present invention contains a polyester resin from the viewpoint of improving the scratch resistance of the printed matter. It is considered that the carbodiimide compound undergoes a cross-linking reaction with the polyester resin to form a strong film, thereby improving the scratch resistance of the printed matter.
• the polyester resin contains a structural unit derived from an alcohol component and a structural unit derived from a carboxylic acid, and can be obtained by polycondensing an alcohol component and a carboxylic acid component.
• Alcohol component examples of the alcohol component, which is a raw material monomer of the polyester resin, include polyols such as aromatic polyols and aliphatic polyols, and preferably include aromatic diols.
• aromatic diol an alkylene oxide adduct of bisphenol A is preferable.
• the alkylene oxide adduct of bisphenol A refers to a compound having a structure in which an oxyalkylene group is added to 2,2-bis (4-hydroxyphenyl) propane.
• the alkylene oxide adduct of bisphenol A is preferably a compound represented by the following general formula (I-1).
• OR 1 and R 2 O are both oxyalkylene groups, preferably each independently an oxyalkylene group having 1 to 4 carbon atoms, more preferably an oxyethylene group or It is an oxypropylene group.
• x and y correspond to the number of moles of the alkylene oxide added. Further, from the viewpoint of reactivity with the carboxylic acid component, the average value of the sum of x and y is preferably 2 or more, and is preferably 7 or less, more preferably 5 or less, and further preferably 3 or less. .
• x OR 1 and y R 2 O may be the same or different, but are preferably the same from the viewpoint of adhesion to the recording medium.
• the alkylene oxide adduct of bisphenol A may be used alone or in combination of two or more.
• the alkylene oxide adduct of bisphenol A is preferably a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A, and more preferably a propylene oxide adduct of bisphenol A.
• the content of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol%, from the viewpoint of improving the scratch resistance of the obtained printed matter. And preferably 100 mol% or less.
• alcohol component which is a raw material monomer of the polyester resin
• other alcohol components may be used in addition to the alkylene oxide adduct of bisphenol A.
• Other alcohol components include ethylene glycol, propylene glycol (1,2-propanediol), glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or their alkylene (2 to 4 carbon atoms) oxides Adducts (average number of moles of 1 to 16) and the like.
• the other alcohol components can be used alone or in combination of two or more.
• the carboxylic acid component which is a raw material monomer of the polyester resin, includes carboxylic acids, anhydrides of these acids, and alkyl (1 to 3 carbon atoms) esters thereof.
• Examples of the carboxylic acid component include an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a trivalent or higher polycarboxylic acid, and one kind selected from the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid.
• the above is preferred.
• the aromatic dicarboxylic acid phthalic acid, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
• the aliphatic dicarboxylic acid examples include unsaturated aliphatic dicarboxylic acids and saturated aliphatic dicarboxylic acids.
• the unsaturated aliphatic dicarboxylic acids are preferably fumaric acid and maleic acid, more preferably fumaric acid, and saturated aliphatic dicarboxylic acids.
• As the acid adipic acid and succinic acid are preferred.
• As the alicyclic dicarboxylic acid cyclohexanedicarboxylic acid, decalindicarboxylic acid, and tetrahydrophthalic acid are preferable, and as the trivalent or higher polycarboxylic acid, trimellitic acid and pyromellitic acid are preferable.
• the carboxylic acid components can be used alone or in combination of two or more.
• aromatic dicarboxylic acids and aliphatic dicarboxylic acids are preferred, aliphatic dicarboxylic acids are more preferred, unsaturated aliphatic dicarboxylic acids are still more preferred, and fumaric acid is even more preferred.
• the content of the unsaturated aliphatic dicarboxylic acid in the carboxylic acid component is preferably at least 25 mol%, more preferably at least 40 mol%, still more preferably at least 60 mol%, even more preferably at least 70 mol%, And it is preferably 100 mol% or less.
• the polyester resin can be obtained by polycondensing at least an alcohol component and a carboxylic acid component.
• it can be produced by subjecting the alcohol component and the carboxylic acid component to polycondensation at a temperature of 180 ° C. or more and 250 ° C. or less in an inert gas atmosphere using an esterification catalyst as necessary.
• Preferred embodiments and preferred contents of the alcohol component and the carboxylic acid component are as described above, respectively.
• the polyester resin preferably has a sharp molecular weight distribution, and it is preferable to carry out polycondensation using an esterification catalyst.
• esterification catalyst examples include a tin catalyst, a titanium catalyst, a metal compound such as antimony trioxide, zinc acetate, and germanium dioxide. From the viewpoint of esterification reaction efficiency, a tin catalyst is preferable.
• a tin catalyst dibutyltin oxide, di (2-ethylhexanoate) tin (II), a salt thereof or the like is preferable, and tin (II-ethylhexanoate) (II) is more preferable.
• an esterification co-catalyst such as 3,4,5-trihydroxybenzoic acid may be used, or a radical polymerization inhibitor such as 4-tert-butylcatechol or hydroquinone may be used in combination. Good.
• the acid value of the polyester resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 70 mgKOH / g from the viewpoint of improving the scratch resistance of the printed matter. Or less, more preferably 55 mgKOH / g or less, still more preferably 45 mgKOH / g or less, and still more preferably 35 mgKOH / g or less.
• the softening point of the polyester resin is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, even more preferably 90 ° C. or higher, and preferably 160 ° C.
• the glass transition temperature of the polyester resin is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and preferably 90 ° C. or lower, more preferably 80 ° C. or lower, from the viewpoint of improving the scratch resistance of the printed matter. It is preferably at most 75 ° C, more preferably at most 70 ° C.
• the weight-average molecular weight of the polyester resin is preferably 5,000 or more, more preferably 7,500 or more, and still more preferably 10,000 or more, from the viewpoint of improving the scratch resistance of the printed matter.
• the desired acid value, softening point, glass transition temperature, and weight average molecular weight can be obtained by appropriately adjusting the type, blending ratio, polycondensation temperature, and reaction time of the monomers used.
• the acid value, softening point, glass transition temperature and weight average molecular weight of the polyester resin are measured by the methods described in Examples.
• ⁇ Other resins> another resin having a reactive group capable of undergoing a cross-linking reaction with the carbodiimide compound (hereinafter, also referred to as “resin C”) may be used in combination with the polyester resin.
• resin C By using the resin C together, the crosslinking density of the ink film is further 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 examples include a polyurethane resin, a (meth) acrylic resin, a styrene- (meth) acrylic resin, and a (meth) acryl-urethane resin.
• a polyurethane resin having a carboxy group is preferable.
• the resin C is a copolymer, any of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer may be used.
• “(meth) acryl” means at least one kind selected from acryl and methacryl.
• the polyurethane resin having a carboxy group can be obtained, for example, by subjecting a polyisocyanate to an organic compound (polyol) having two or more alcoholic hydroxyl groups in one molecule containing a dialkanolcarboxylic acid and a polyisocyanate.
• the dialkanolcarboxylic acid include dimethylolbutanoic acid, dimethylolpropionic acid, and salts thereof.
• the polyol is not particularly limited as long as it is a compound having two or more alcoholic hydroxyl groups in one molecule, and examples thereof include a polycarbonate polyol, a polyester polyol, and a polyether polyol.
• the polyisocyanate include aliphatic diisocyanates having a chain or cyclic structure, aliphatic diisocyanates having an aromatic ring, aromatic diisocyanates, and modified products of these diisocyanates.
• the polyurethane resin is preferably used as an emulsion dispersed in an aqueous medium, and the emulsion may optionally contain a dispersant such as a surfactant.
• a dispersant such as a surfactant.
• Commercially available polyurethane resins include Super Flex Series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sun Cure Series (manufactured by Lubrizol), Takelac W Series (manufactured by Mitsui Chemicals, Inc.); Permarine Series (manufactured by Sanyo Chemical Industries, Ltd.) ADEO Bon Titer HUX series (ADEKA Corporation), NeoRez R series (DSM Coating Resins), and the like.
• the aqueous composition of the present invention can contain a coloring agent described below.
• a pigment and a hydrophobic dye are preferable from the viewpoint of improving the water resistance of the obtained printed matter, and it is preferable to use a pigment to exhibit high weather resistance.
• an aqueous ink described below may be used.
• the aqueous composition of the present invention may contain a fixing aid polymer (Ib) described below in order to fix the colorant on the recording medium.
• the aqueous composition of the present invention may further contain 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.
• a 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 composition.
• 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 content of each component of the aqueous composition is as follows from the viewpoint of improving the storage stability of the aqueous composition and the abrasion resistance of the printed matter.
• the content of the carbodiimide compound in the aqueous composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 10% by mass or more. Or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.
• the content of the polyester resin in the aqueous composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably 25% by mass or less, more preferably Is 20% by mass or less, more preferably 15% by mass or less.
• the mass ratio of the carbodiimide compound to the polyester resin (carbodiimide compound / polyester resin) is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, and preferably 0.5 or less. , More preferably 0.4 or less, still more preferably 0.3 or less.
• the content of the resin C in the aqueous composition 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 more. Or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.
• the content of the water-soluble organic solvent in the aqueous composition is preferably 7% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and preferably 48% by mass or less, more preferably Is 46% by mass or less, more preferably 44% by mass or less.
• the content of water in the aqueous composition is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less. %, More preferably 70% by mass or less, even more preferably 60% by mass or less.
• the content of the colorant in the aqueous composition is preferably 1% by mass or less, more preferably 0.1% by mass or less, further preferably 0.01% by mass or less, and still more preferably 0% by mass. If the aqueous composition is substantially free of colorants, it will not affect the hue of the ink when printed with an aqueous ink.
• the aqueous composition of the present invention contains a dispersant, 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. be able to.
• the ink set for ink jet recording contains at least two or more aqueous compositions.
• the aqueous composition may be an aqueous ink.
• the ink set for inkjet recording of the present invention (hereinafter, also simply referred to as “ink set”) includes, as an aqueous composition, an aqueous composition a containing a carbodiimide compound and water, and an aqueous composition b containing a polyester resin and water.
• a colorant can be added to at least one of the aqueous composition a and the aqueous composition b, preferably to the aqueous composition b, to obtain an aqueous ink containing the colorant.
• the ink set for ink jet recording of the present invention comprises an aqueous ink composition for ink jet recording containing a carbodiimide compound, a polyester resin, and water, and a water-based ink containing a colorant (hereinafter, simply referred to as “water-based ink” or “ink”). ).
• the ink set includes, for example, (i) an aqueous composition a containing a carbodiimide compound and water, a polyester resin and water in an ink cartridge for each color of an inkjet recording apparatus, and further containing a colorant as necessary.
• the contained aqueous composition b can be filled in an ink cartridge, and printed by discharging ink droplets from each discharge nozzle corresponding to each ink cartridge. Further, (ii) an ink jet recording aqueous composition containing a carbodiimide compound, a polyester resin, and water, and a water-based ink containing a colorant are filled in ink cartridges, and each ejection nozzle corresponding to each ink cartridge is filled. Therefore, printing can be performed by ejecting each ink droplet.
• the water-based ink can be used alone or in combination of two or more hues.
• the aqueous ink according to the present invention is an aqueous composition containing a colorant.
• a colorant As the colorant of the aqueous ink according to the present invention, a pigment and a hydrophobic dye are preferable from the viewpoint of the water resistance of the printed matter. Above all, it is preferable to use a pigment in order to exhibit high weather resistance.
• 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 examples include silica, calcium carbonate, talc and the like.
• the above pigments can be used alone or in combination of two or more.
• the pigment may be contained in the aqueous ink in the form of a self-dispersible pigment, a pigment dispersed with a polymer dispersant, or a polymer particle containing a pigment.
• the hydrophobic dye is preferably one that can be contained in the polymer particles.
• the hydrophobic dye include an oil-soluble dye and a disperse dye, and among these, an oil-soluble dye is preferable.
• the hydrophobic dye has a solubility of preferably 2 g / L or more, more preferably 20 to 500 g, in the organic solvent used in the production of the aqueous dispersion. / L is preferred.
• the oil-soluble dye is not particularly limited, but for example, C.I. I. Solvent Black 3, 7, 27, 29, 34, 45; I. Solvent Yellow 14, 16, 29, 56, 82, 83: 1; I.
• Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73; I. Solvent Violet 3; C.I. I. Solvent Blue 2, 4, 11, 44, 64, 70; C.I. I. Solvent Green 3, 7, 7; C.I. I. Solvent Orange 2 and the like, and a dye obtained by making a water-soluble dye oil-soluble may also be used.
• C.I. I. Solvent Yellow 29 and 30, C.I. I. Solvent Blue 70, C.I. as magenta. I. Solvent Red 18 and 49, C.I. I. Solvent Black 3, 7 and black dyes based on nigrosine are preferred.
• the above colorants can be used alone or in combination of two or more.
• Colorant-dispersed polymer (Ia) As the colorant-dispersed polymer (Ia) for dispersing the colorant, from the viewpoint of improving the dispersibility of the colorant and the abrasion resistance of the printed matter, condensation resins such as polyester resins and polyurethane resins; vinyl monomers ( And vinyl compounds obtained by addition polymerization of a vinyl compound, a vinylidene compound, and a vinylene compound. Among these, at least one selected from a polyester resin and a vinyl resin is preferable, and a polyester resin is more preferable.
• the colorant-dispersed polymer (Ia) a polymer appropriately synthesized may be used, or a commercially available product may be used.
• the colorant-dispersed polymer (Ia) is preferably used as an aqueous dispersion.
• the polyester resin can be used as a colorant-dispersed polymer (Ia) by being contained in the aqueous composition.
• the polyester resin is obtained by polycondensing an alcohol component and a carboxylic acid component.
• the aqueous dispersion of the polyester resin may optionally contain a dispersant such as a surfactant.
• the aqueous dispersion of the polyester resin can be obtained by a method of adding the polyester resin to an aqueous medium and performing a dispersion treatment with a disperser or the like, a method of gradually adding an aqueous medium to the polyester resin, and performing phase inversion emulsification.
• the phase inversion emulsification method is preferable from the viewpoint of productivity and dispersion stability of the polymer particles.
• Examples of the phase inversion emulsification method include a method described in JP-A-2016-222896. First, a polyester resin is dissolved in an organic solvent, and then an aqueous medium is added to perform phase inversion. The removal method is preferred.
• the vinyl resin has at least one selected from a structural unit derived from an ionic monomer, a structural unit derived from a hydrophobic monomer, and a structural unit derived from a hydrophilic nonionic monomer (hereinafter, also referred to as “nonionic monomer”). It is preferable to have two or more of these constituent units. For example, a combination of an ionic monomer and a hydrophobic monomer, a combination of an ionic monomer, a hydrophobic monomer, and a nonionic monomer may be used.
• the vinyl resin can be obtained by, for example, addition polymerization of a monomer mixture containing an ionic monomer, a hydrophobic monomer, and a nonionic monomer by a known method.
• the vinyl resin used in the water-based ink is preferably a (meth) acrylate having a structural unit derived from one or more ionic monomers selected from acrylic acid and methacrylic acid, and a hydrocarbon group derived from an aliphatic alcohol, and an aromatic resin.
• the weight average molecular weight of the vinyl resin is preferably 5,000 or more, more preferably 10,000 or more, and still more preferably 30,000 or more, from the viewpoint of improving the dispersibility of the colorant and the abrasion resistance of the printed matter. And preferably 100,000 or less, more preferably 80,000 or less, and still more preferably 60,000 or less.
• the acid value of the vinyl resin is preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, and further preferably 150 mgKOH / g or more, from the viewpoint of improving dispersibility.
• vinyl resins include, for example, polyacrylic acid such as “Alon AC-10SL” (manufactured by Toagosei Co., Ltd.), "Johncryl 67", “Johncryl 611", “Johncryl 678”, and “Johncryl 678". Styrene-acrylic resin such as “Crill 680”, “John Crill 690”, and “John Crill 819” (all manufactured by BASF Japan Ltd.). The weight average molecular weight and the acid value of the vinyl resin are measured by the methods described in Examples.
• the aqueous ink used in the present invention may contain a fixing aid polymer (Ib) for fixing the colorant to the recording medium.
• the fixing aid polymer (Ib) is preferably used as polymer particles containing no coloring agent.
• the components include condensation resins such as polyurethane resins and polyester resins; acrylic resins, styrene resins, styrene-acryl resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, vinyl acetate resins and A vinyl resin such as an acrylic silicone resin may be used.
• the fixing aid polymer (Ib) is preferably used as an aqueous dispersion containing polymer particles from the viewpoint of improving the productivity of the aqueous ink.
• the fixing aid polymer (Ib) a polymer synthesized appropriately or a commercially available product may be used.
• fixing aid polymers (Ib) include, for example, polyester resins such as “Elitel KA” series and “Elitel KZA” series manufactured by Unitika Ltd., and polyurethane resins such as “WBR” series manufactured by Taisei Fine Chemical Co., Ltd.
• Acrylic resins such as "Neocryl A-1127” manufactured by DSM Coating Resins, "John Krill” series manufactured by BASF Japan, styrene-butadiene resin such as "SR” series manufactured by A & L Japan, and Nissin Examples include vinyl chloride resins such as "ViniBran” series manufactured by Chemical Industry Co., Ltd.
• the weight average molecular weight of the fixing aid polymer (Ib) is preferably 10,000 or more, more preferably 15,000 or more, and preferably 100,000 or less, from the viewpoint of improving the scratch resistance of the printed matter. More preferably, it is 50,000 or less.
• the average particle size of the fixing aid polymer (Ib) particles in the aqueous composition containing the fixing aid polymer (Ib) particles or in the ink is preferably 10 nm or more, more preferably 30 nm or more, from the storage stability of the ink. And more preferably 50 nm or more, and preferably 300 nm or less, more preferably 200 nm or less, further preferably 150 nm or less, and still more preferably 130 nm or less.
• the weight average molecular weight and the average particle size of the fixing aid polymer (Ib) are measured by the methods described in Examples.
• the water-based ink preferably contains water-insoluble polymer particles containing a colorant, particularly a pigment (hereinafter, also simply referred to as “pigment-containing polymer particles”), from the viewpoints of dispersion stability and ejection stability of the ink.
• the pigment-containing polymer particles may be any particles formed by the pigment and the water-insoluble polymer.
• the pigment-containing polymer particles can be efficiently produced by a method having the following steps 1 and 2 as an aqueous dispersion.
• Step 1 a step of dispersing a mixture containing a pigment and a polymer, and further containing an organic solvent and water to obtain a dispersion of the pigment-containing polymer particles
• Step 2 a dispersion of the pigment-containing polymer particles obtained in the step 1 Removing an organic solvent from water to obtain an aqueous dispersion of pigment-containing polymer particles
• the pigment-dispersed polymer for dispersing the pigment is, as described above, at least one selected from a polyester resin and a vinyl resin. Is preferable, and a polyester resin is more preferable.
• a polyester resin is more preferable.
• step 1 first, a polyester resin is dissolved in an organic solvent, and then, a pigment, water, and a neutralizing agent, a surfactant, and the like, if necessary, are added to the organic solvent solution and mixed.
• the method of obtaining the body is preferred.
• the organic solvent in which the polyester resin is dissolved but ketones, ethers, esters, aliphatic alcohols having 1 to 3 carbon atoms and the like are preferable, and ketones are more preferable.
• the polyester resin is synthesized by a solution polymerization method, the solvent used in the polymerization may be used as it is.
• the polyester resin has an acid group, the acid group may be neutralized using a neutralizing agent.
• the neutralizing agent include bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia and various amines, and preferably sodium hydroxide.
• the polyester resin may be neutralized in advance.
• the equivalent (mol%) of the neutralizing agent to the acid group in the polyester resin is preferably 10 mol% or more, more preferably 20 mol% or more, from the viewpoint of the dispersion stability of the polyester resin in an aqueous medium. It is preferably at least 30 mol%, and more preferably at most 300 mol%, more preferably at most 200 mol%, even more preferably at most 150 mol%.
• the use equivalent (mol%) of a neutralizing agent can be calculated
• the equivalent of the neutralizing agent is 100 mol% or less, it is synonymous with the degree of neutralization. It means that it is in excess with respect to the group, and the degree of neutralization of the polyester PA at this time is regarded as 100 mol%.
• Use equivalent (mol%) of neutralizer [ ⁇ addition amount of neutralizer (g) / equivalent of neutralizer] / [ ⁇ acid value of polyester PA (mg KOH / g) ⁇ weight of polyester PA (g) ⁇ / (56 ⁇ 1000)]]] ⁇ 100
• the dispersing method in Step 1 is not particularly limited.
• the average particle size of the pigment-containing polymer particles can be reduced to a desired particle size only by the main dispersion, but it is preferable that the pre-dispersion is performed, and then the main dispersion is performed by further applying a shear stress to the pigment-containing polymer.
• the average particle size of the particles is controlled to a desired particle size.
• the means for pre-dispersing is preferably a commonly used mixing and stirring device such as an anchor blade or a disper blade, and particularly preferably a high-speed stirring and mixing device.
• Means for applying the shear stress of the dispersion include, for example, a kneader such as a roll mill and a kneader, a high-pressure homogenizer such as a microfluidizer (trade name, manufactured by Microfluidics), a media disperser such as a paint shaker, and a bead mill. These devices can also be used in combination. Among these, a high-pressure homogenizer is preferable.
• the dispersion pressure is preferably 50 MPa or more, more preferably 100 MPa or more, further preferably 120 MPa or more, and preferably 250 MPa or less, from the viewpoint of reducing the particle diameter of the pigment-containing polymer particles and the dispersion treatment efficiency. Preferably it is 200 MPa or less.
• the organic solvent in the aqueous dispersion containing the pigment-containing polymer particles obtained in the step 1 is preferably substantially removed, but remains as long as the object of the present invention is not impaired. Is also good.
• the aqueous dispersion of the pigment-containing polymer particles is one in which the pigment-containing polyester resin particles are dispersed in an aqueous medium having water as a main medium.
• examples of the form of the particles include a particle form in which the pigment is included in the polymer, a particle form in which the pigment is uniformly dispersed in the polymer, and a particle form in which the pigment is exposed on the surface of the polymer particle. And mixtures thereof.
• 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.
• the aqueous ink may contain a colorant, a colorant-dispersed polymer (Ia), and if necessary, a fixing aid polymer (Ib) and an organic solvent.
• organic solvent those exemplified as the water-soluble organic solvent used in the above aqueous composition are preferable.
• the water-based ink may contain, as optional components, various additives such as a humectant, a wetting agent, a penetrant, a surfactant, a viscosity modifier, an antifoaming agent, a preservative, a fungicide, and a rust inhibitor. .
• the aqueous ink can be obtained by mixing a colorant, a colorant-dispersed polymer (Ia), water, and if necessary, a neutralizing agent, a surfactant, an organic solvent, and the like, and stirring the mixture.
• a colorant-dispersed polymer Ia
• water if necessary, a neutralizing agent, a surfactant, an organic solvent, and the like
• the pigment and the pigment-dispersed polymer may be subjected to dispersion treatment in advance to obtain a dispersion of the pigment-containing polymer particles, and then may be blended with the ink.
• the content of each component of the water-based ink is as follows.
• the content of the pigment is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more in the ink from the viewpoint of the print density of the printed matter. From the viewpoint of improvement, the content is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and still more preferably 6% by mass or less.
• the content of the resin I is determined by the sum of the pigment-dispersing polymer (Ia) and the fixing aid polymer (Ib). Quantity.
• the content of water is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and more preferably 80% by mass in the ink, from the viewpoint of improving the scratch resistance of the printed matter. % By mass, more preferably 75% by mass or less, further preferably 70% by mass or less.
• the content of the organic solvent is preferably 5% by mass or more, more preferably 10% by mass or more in the ink, from the viewpoint of improving the ejection property of the ink and the scratch resistance of the printed matter. , More preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
• 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 polyester resin, a colorant, and water onto the surface of a recording medium by an inkjet method to obtain a recorded image.
• Step 2 converting the recorded image obtained in the step 1 to a temperature of 50 ° C. or more and 200 ° C.
• the aqueous composition of the first embodiment (carbodiimide compound, polyester resin, and water) discharged from one discharge head (Aqueous composition containing a carbodiimide compound and water, and an aqueous composition containing a polyester resin and water).
• Aqueous composition containing a carbodiimide compound and water and an aqueous composition containing a polyester resin and water.
• Combination with composition b When using the combination of the aqueous compositions of the second embodiment, the respective aqueous compositions a and b are mixed on the surface of the recording medium.
• an aqueous ink containing a colorant can be used as the aqueous composition.
• Step 1 is a step of discharging a carbodiimide compound, a polyester resin, a colorant, and water onto the surface of a recording medium by an inkjet method to obtain a recorded image.
• Step 1 preferably includes a step 1a of discharging an aqueous ink onto a recording medium by an ink jet method and a step 1b of discharging an aqueous composition onto a recording medium by an ink jet method, wherein step 1a is performed before step 1b or in step 1b. It is more preferable to perform the step at the same time, and it is further preferable to perform step 1a before step 1b. By performing the step 1a before the step 1b, a printed matter having excellent scratch resistance can be obtained more effectively.
• 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 colorant 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 polyester resin 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 composition containing a carbodiimide compound and a polyester resin and an aqueous ink are preferable.
• a piezo method is preferable from the viewpoint of dischargeability.
• the amount of the aqueous composition applied to the recording medium is preferably 0.1 g / m 2 or more, more preferably 0.75 g / m 2 or more, more preferably 0.7 g / m 2 or more, in terms of solid content, from the viewpoint of improving the scratch resistance of the printed matter.
• 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. Thereby, 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.
• the crosslinking reaction of the recorded image and the attachment by shrinkage of the film can be performed simultaneously in one step by heating while the shrink film is attached to the object to be attached.
• 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 (above, 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.
• a sample obtained by freeze-drying the aqueous dispersion at ⁇ 10 ° C. for 9 hours using a freeze dryer “FDU-2100” manufactured by Tokyo Rika Kikai Co., Ltd. was used as a sample.
• -Measuring device Tosoh Corporation, "CO-8010" -Analytical column: “GMHXL” + “G3000HXL” manufactured by Tosoh Corporation -Tetrahydrofuran was flowed at a flow rate of 1 mL / min as a solution, and the column was stabilized in a constant temperature bath at 40 ° C. 100 ⁇ L of the sample solution was injected thereinto and the measurement was performed.
• the sample has a weight average molecular weight of several types of monodisperse polystyrene [monodisperse polystyrene manufactured by Tosoh Corporation; 2.63 ⁇ 10 3 , 2.06 ⁇ 10 4 , 1.02 ⁇ 10 5 (weight average molecular weight (Mw) ), Monodisperse polystyrene manufactured by GL Sciences Inc .; 2.10 ⁇ 10 3 , 7.00 ⁇ 10 3 , 5.04 ⁇ 10 4 (weight average molecular weight (Mw))] Calculated based on the line.
• Weight average molecular weight (Mw) of styrene-acrylic resin A solution obtained by dissolving phosphoric acid and lithium bromide in N, N-dimethylformamide at a concentration of 60 mmol / L and 50 mmol / L, respectively, was used as an eluent by gel permeation chromatography [GPC device (HLC manufactured by Tosoh Corporation) Monodisperse polystyrene kit [PStQuick B (PStQuick B) with a known molecular weight as a standard substance using a column manufactured by Tosoh Corporation (TSKgel SuperAWM-H, TSKgel SuperAW3000, TSKgel guardcolumn Super AW-H), flow rate: 0.5 mL / min].
• 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.
• polyester resins P-1 and P-2 Production of polyester resins P-1 and P-2
• a raw material monomer (alcohol component and carboxylic acid component), an esterification catalyst, and an esterification cocatalyst were mixed in the proportions shown in Table 1, and a 10 L internal volume equipped with a thermometer, a stirrer, a falling condenser, and a nitrogen inlet tube was provided.
• the mixture was placed in a four-necked flask, reacted at 210 ° C. for 10 hours using a mantle heater in a nitrogen atmosphere, and further reacted at ⁇ 8.3 kPa (G) until the softening point reached the temperature shown in Table 1.
• polyester resins P-1 and P-2 were obtained.
• Table 1 shows the physical properties of the obtained polyester resin.
• Step 1 (pigment dispersion step)
• MEK methyl ethyl ketone
• 5N is added thereto so that 85 mol% of the acid value of the polyester resin P-1 is neutralized.
• An aqueous sodium hydroxide solution was added.
• 390.5 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 concentration step
• the whole amount of the obtained aqueous pigment dispersion is placed in a 2 L eggplant-shaped flask, ion-exchanged water is added so as to have a solid concentration of 15%, and a rotary distillation apparatus (manufactured by Tokyo Rika Kikai Co., Ltd., “Rotary evaporator N- 1000S "), 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.
• a rotary distillation apparatus manufactured by Tokyo Rika Kikai Co., Ltd., “Rotary evaporator N- 1000S "
• 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 a concentrate.
• the obtained concentrate is put into a 500 mL angle rotor, and centrifuged at 3,660 r / min for 20 minutes using a high-speed cooling centrifuge (“Himac CR22G”, manufactured by Hitachi Koki Co., Ltd., set temperature: 20 ° C.).
• Himac CR22G high-speed cooling centrifuge
• the liquid layer was filtered through a membrane filter (“Minisart”, manufactured by Sartorius, Inc.) having a pore size of 5 ⁇ m, and diluted with water to a solid content of 22% to obtain an aqueous dispersion 1 of pigment-containing polyester resin particles. .
• the average particle size of the obtained pigment-containing polyester resin particles was 97 nm.
• Preparation Examples A2 to A6 (Preparation of aqueous dispersions 2 to 6 of pigment-containing polyester resin particles) Aqueous dispersions 2 to 6 of pigment-containing polyester resin particles were obtained in the same manner as in Preparation Example A1, except that the polyester resin and the pigment were changed. Table 2 shows the results.
• Preparation Example A7 (Preparation of aqueous dispersion 7 of styrene-acrylic resin particles containing pigment) 150 parts of carbon black (Monarch 717, manufactured by Cabot Corporation) and a styrene-acrylic resin (manufactured by BASF, Joncryl 690, 60% neutralized sodium hydroxide, weight-average molecular weight 16500, acid value 240 mg KOH) as a polymer dispersant / G) as a solid content was mixed with 45 parts of an aqueous solution, and the mixture was dispersed using a zirconia bead to obtain an aqueous dispersion 7 having a solid content concentration of 19.5%. Table 2 shows the results.
• Preparation Example A8 (Preparation of aqueous dispersion 8 of styrene-acrylic resin particles containing pigment)
• 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 an aqueous dispersion 8 was obtained in the same manner as in Preparation Example A7.
• Table 2 shows the results.
• Preparation Examples B1 to B9 (Preparation of aqueous inks 1 to 9)
• the aqueous dispersions 1 to 8 obtained in Preparation Examples A1 to A8, a commercially available aqueous pigment dispersion, an organic solvent, a surfactant, and ion-exchanged water were blended (100% in total amount) as shown in Table 3.
• water-based inks 1 to 9 were obtained.
• the amount of the pigment aqueous dispersion in Table 3 is the solid content.
• aqueous pigment dispersion Self-dispersion type carbon black aqueous dispersion, manufactured by SENSIENT, SENSIJET BLACK SDP100 ⁇ 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 Example B10 (Preparation of water-based ink 10) A commercially available cyan dye ink, XKI-N11XLC, manufactured by Canon Inc. was used as an aqueous ink 10.
• Preparation Example C1 (Production of Pigment-Free Polyester Resin P-2 Emulsion)
• a four-necked flask equipped with a nitrogen inlet tube, a reflux condenser, a stirrer, and a thermocouple 1700 g of polyester resin P-2 and 1700 g of methyl ethyl ketone (MEK) were placed and dissolved at 60 ° C. in MEK. Then, it cooled to 25 degreeC.
• 408 g of a 5% aqueous sodium hydroxide solution was added as a neutralizing agent, and 5100 g of deionized water was added under stirring at 25 ° C., to obtain a dispersion of polyester resin particles containing no pigment.
• the resulting dispersion was stirred in a four-necked flask and kept at 60 ° C. while depressurizing to distill off MEK and water. After cooling to room temperature, ion-exchanged water was added so that the solid content concentration became 30%, and the mixture was filtered through a 200-mesh wire net to obtain a pigment-free polyester resin P-2 emulsion.
• the average particle size of the obtained polyester resin particles was 87 nm.
• Preparation Examples D1 to D4 (Preparation of aqueous compositions 1 to 4)
• the carbodiimide compound shown in Table 4, the polyester resin P-2 emulsion obtained in Preparation Example C1, the separately prepared emulsion of Joncryl 690, an organic solvent, a surfactant, and ion-exchanged water were compounded as shown in Table 4. (100% in total) to obtain aqueous compositions 1 to 4.
• the blending amounts of the carbodiimide compound, polyester resin P-2 emulsion and Joncryl 690 emulsion in Table 4 are solid contents.
• carbodiimide compound and the like in Table 4 are as follows.
• -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 15 and Comparative Examples 1 to 4 (recording by ink set) An ink set obtained by combining the aqueous compositions shown in Tables 4 and 5 with the aqueous inks shown in Table 3 was loaded into an inkjet printer (IPSiO SG2010L, manufactured by Ricoh Co., Ltd.), and a polyethylene terephthalate (PET) film (PET) film was used as a recording medium. Solid printing of 10 cm ⁇ 10 cm was performed using Lumirror (registered trademark) T60 manufactured by Toray Industries, Inc.
• Example 1 to 5 11 to 15 and Comparative Examples 2 to 4, the two liquids of the aqueous composition and the water-based ink were loaded into an ink jet printer and ejected from the two ink jet heads with the same droplet size, and the recording medium was discharged. Printing was performed so that the two were mixed above.
• 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.
• 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 for a 100% density 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 and 11 are examples of the second aspect
• Examples 6 to 10 and 12 to 15 are examples of the first aspect. From Table 5, it can be seen that according to the aqueous composition using the carbodiimide compound and the polyester resin, the ink set, and the inkjet recording method, it is possible to obtain a printed matter having excellent scratch resistance. On the other hand, it can be seen that in Comparative Examples in which no carbodiimide compound or polyester resin was used, it was not possible to obtain printed matter having excellent scratch resistance.
• a printed matter having excellent scratch 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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