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
  • C09D11/54—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
  • 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
• • 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

Definitions

• the present invention relates to an aqueous composition for inkjet recording, a coating liquid for inkjet recording, an ink set for inkjet recording, and an inkjet recording method.
• inks using pigments as colorants have been proposed.
• the pigment particles remain on the surface of the recording medium after printing. Therefore, pigment particles are easily peeled off from the recording medium when stimulation is applied to the surface of the printed material, and the image fastness of the printed material tends to be lower than when a dye that does not remain in the form of particles on the surface of the recording medium is used as a colorant. It is in. Therefore, in order to improve the image fastness of the printed matter with the pigment ink, an aqueous composition such as a coating liquid used in combination with the pigment ink has been developed.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2017-149812
• Patent Document 2 describes a water-dispersible resin as an object to improve fastness such as friction fastness and washing fastness of pigment ink without impairing ejection reliability.
• Patent Document 2 includes a step of applying an ink containing polymer-encapsulated pigment particles and an aqueous medium to a substrate by an inkjet printer, and the polymer-encapsulated pigment particles are used as a second crosslinking agent.
• a method for printing an image on a substrate comprising the steps of: cross-linking with an ink and a second cross-linking agent when they are ejected from different nozzles onto the substrate. Methods are disclosed that occur in air or on a substrate.
• the second crosslinking agent is a compound having two or more groups selected from carbodiimide, oxazoline, isocyanate group and the like.
• Patent Documents 1 and 2 there are examples of crosslinking agents such as blocked isocyanate compounds, carbodiimide compounds, and oxazoline compounds, but specifically, only one type of compound is used, and a plurality of coating agents are used in the coating liquid.
• crosslinking agents such as blocked isocyanate compounds, carbodiimide compounds, and oxazoline compounds
• There is no exemplification containing a cross-linking agent and it has not been studied.
• the type of the crosslinking agent there is also a problem that the storage stability of the coating solution is poor.
• the ink jet recording method is more suitable for a small amount of various kinds of printed matter than an analog printing method such as a gravure printing method, and it is desired to expand the application range of a recording medium by the ink jet recording method.
• substrate adhesion For example, heat-shrinkable resin films are widely used as packaging bases for containers used in food and medical fields such as plastic bottles and plastic cases.
• product information such as booklet, usage method, expiration date, lot number, etc.
• package design important information such as product information such as booklet, usage method, expiration date, lot number, etc. is printed, so printed matter using a heat-shrinkable resin film In this case, improvement in scratch resistance, solvent resistance, and substrate adhesion is desired.
• the present invention can provide an aqueous composition for inkjet recording having excellent storage stability, and further, when the aqueous composition contains a resin or is used together with a water-based ink containing a resin, the scratch resistance, Aqueous composition for ink jet recording capable of obtaining printed matter having excellent solvent and substrate adhesion, ink jet recording coating liquid containing the aqueous composition, and ink set for ink jet recording comprising the aqueous composition and water-based ink And an ink jet recording method using the aqueous composition and a water-based ink.
• low water absorption is a concept including low water absorption and non-water absorption, and the water absorption amount of the recording medium at a contact time of 100 msec between the recording medium and pure water is 0 g / m. means that two or more 10 g / m 2 or less.
• the water absorption can be measured by the method described in the examples.
• printing is a concept including printing and printing for recording characters and images
• printed material is a concept including printed materials and printing materials on which characters and images are recorded.
• the inventors have obtained an aqueous composition excellent in storage stability by using a block type isocyanate and at least one compound selected from a carbodiimide compound and an oxazoline compound, and the aqueous composition is combined with an aqueous ink. It has been found that by using it, the scratch resistance, solvent resistance and substrate adhesion of the printed matter can be improved. That is, the present invention relates to the following [1] to [4].
• a coating liquid for ink jet recording containing the aqueous composition for ink jet recording described in [1].
• An ink set for ink-jet recording comprising the aqueous composition for ink-jet recording according to [1] and an aqueous ink containing a pigment.
• An ink set for ink-jet recording wherein at least one of the water-based composition for ink-jet recording and the water-based ink contains a resin having at least a reactive group that undergoes a crosslinking reaction with compound B.
• At least one of the aqueous composition for inkjet recording and the water-based ink contains a resin having a reactive group that undergoes a crosslinking reaction with at least compound B;
• An ink jet recording method comprising the following step 1 and step 2.
• Step 1 A step of ejecting the aqueous composition for inkjet recording and the water-based ink onto the surface of a recording medium by an inkjet method to obtain a recorded image
• Step 2 Block type isocyanate A of the recorded image obtained in Step 1 , A step of cross-linking the compound B and the resin
• the aqueous composition for inkjet recording which is excellent in storage stability can be provided, Furthermore, when this aqueous composition contains resin or it uses with the aqueous ink containing resin, it is scratch-resistant.
• An aqueous composition for ink jet recording capable of obtaining a printed matter excellent in solvent resistance and substrate adhesion, a coating liquid for ink jet recording containing the aqueous composition, an ink set comprising the aqueous composition and an aqueous ink,
• an inkjet recording method using the aqueous composition and a water-based ink can be provided.
• the aqueous composition comes into contact with the ink, and a block type isocyanate, at least one compound selected from a carbodiimide compound and an oxazoline compound, and a resin contained in the aqueous composition or water-based ink undergo a crosslinking reaction.
• Block type isocyanate has high reactivity with respect to the compound which has active hydrogen because active isocyanate is regenerated by dissociation of a blocking agent.
• the carbodiimide compound or the oxazoline compound is bridged with the reactive group in the aqueous composition or the resin contained in the ink as the water evaporates.
• dissociation of the blocking agent from the blocked isocyanate proceeds, and the regenerated active isocyanates form a self-crosslinking structure to form an interpenetrating polymer network (IPN).
• IPN interpenetrating polymer network
• Isocyanate A is formed by blocking an isocyanate group in a polyisocyanate compound with a blocking agent. Since the isocyanate group is stabilized by blocking the highly reactive isocyanate group, it is possible to form a strong ink film after the crosslinking reaction while improving the storage stability of the aqueous composition.
• the polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. Examples of the polyisocyanate compound include aliphatic isocyanates, alicyclic isocyanates, araliphatic isocyanates, aromatic isocyanates, and modifications thereof. The body is mentioned. Examples of modified polyisocyanate compounds include multimers such as isocyanurates; burettes; adducts of trimethylolpropane and pentaerythritol with polyhydric alcohols.
• tetramethylene diisocyanate pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethyl And hexamethylene diisocyanate.
• HDI hexamethylene diisocyanate
• octamethylene diisocyanate decamethylene diisocyanate
• dodecamethylene diisocyanate 2,2,4- or 2,4,4-trimethyl And hexamethylene diisocyanate.
• an isocyanate group equivalent means the mass of the isocyanate A per mol of isocyanate groups.
• Isocyanate A Commercially available products of Isocyanate A include Trixene blocked isocynates Aqua BI200, Aqua BI220, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (above, Baxenden, trade name); DM-6400, Meikanate DM- 3031CONC, Meikanate DM-35HC, Meikanate TP-10, Meikanate CX, SU-268A, NBP-873D, NBP-211 (above, trade name, manufactured by Meisei Chemical Industry Co., Ltd.); Elastron BN-69, BN-77, BN -27, BN-11 (above, trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.); Takenate WB-700, WB-770, WB-920 (above, trade name, Mitsui Chemicals Polyurethane Co., Ltd.); Lanate MF-K
• the carbodiimide group-containing polymer for example, a polymer obtained by sealing a terminal isocyanate group of a condensation reaction product obtained by a decarboxylation condensation reaction in the presence of a carbodiimidization catalyst of a diisocyanate with a hydrophilic group is preferable.
• diisocyanates used in the decarboxylation condensation reaction include aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), decamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; 4,4′-dicyclohexylmethane diisocyanate (H12MDI), Isophorone diisocyanate (IPDI), 2,5- or 2,6-norbornane diisocyanate, hydrogenated xylylene diisocyanate (H6XDI), hydrogenated tolylene diisocyanate, 2,4-bis- (8-isocyanate octyl) -1,3- Alicyclic diisocyanates such as dioctylcyclobutane (OCDI); aromatic fats such as m- or p-xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI) Diis
• the compound that seals the terminal isocyanate group of the condensation reaction product is a compound having a functional group capable of reacting with the isocyanate group, and examples thereof include polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether.
• polyethylene glycol monomethyl ether is preferable from the viewpoints of compounding of a carbodiimide group-containing polymer into an aqueous composition and storage stability of the aqueous composition.
• the number of moles of ethylene oxide added to the polyethylene glycol monomethyl ether can be adjusted, and the resulting carbodiimide group-containing polymer can be blended into the aqueous composition as an emulsion or an aqueous solution.
• the carbodiimide group equivalent of the carbodiimide group-containing polymer is preferably 200 or more, more preferably 300 or more, from the viewpoint of scratch resistance, solvent resistance and substrate adhesion, and from the viewpoint of storage stability of the aqueous composition. Therefore, it is preferably 650 or less, more preferably 500 or less, and still more preferably 400 or less.
• the carbodiimide group equivalent means the mass of the carbodiimide group-containing polymer per mole of carbodiimide group.
• the carbodiimide compound is preferably formulated into an aqueous composition as an aqueous solution or emulsion from the viewpoint of storage stability, scratch resistance, solvent resistance, and substrate adhesion of the aqueous composition.
• carbodiimide group-containing polymers include Carbodilite E-02, Carbodilite E-03A, Carbodilite E-05, Carbodilite V-02, Carbodilite V-02-L2, Carbodilite V-04 (above, manufactured by Nisshinbo Chemical Co., Ltd., Product name).
• the oxazoline compound is preferably a polyoxazoline compound having two or more oxazoline groups in one molecule from the viewpoints of storage stability, scratch resistance, solvent resistance, and substrate adhesion of the aqueous composition.
• a polymer containing an oxazoline group hereinafter, also referred to as “oxazoline group-containing polymer”.
• the number average molecular weight of the oxazoline group-containing polymer is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and preferably 1,000,000 from the viewpoint of increasing reactivity.
• oxazoline group-containing polymer a polymer having an acrylic skeleton as a main chain, a polymer having a styrene-acryl skeleton as a main chain, a polymer having a styrene skeleton as a main chain, and a polymer having an acrylonitrile-styrene skeleton as a main chain can be used.
• the oxazoline group equivalent of the oxazoline group-containing polymer is preferably 120 or more, more preferably 160 or more, from the viewpoint of improving the storage stability, scratch resistance, solvent resistance and substrate adhesion of the aqueous composition, and , Preferably 800 or less, more preferably 600 or less, still more preferably 300 or less.
• the oxazoline group equivalent means the mass of the oxazoline group-containing polymer per mole of oxazoline group.
• Epocross WS series such as “Epocross WS-300”, “Epocross WS-500”, “Epocross WS-700” (above, Nippon Shokubai Co., Ltd., water-soluble type)
• Epocross K series trade name, emulsion type, manufactured by Nippon Shokubai Co., Ltd.
• the combination of isocyanate A and compound B is preferably a combination of isocyanate A and carbodiimide compound, or isocyanate A from the viewpoint of improving scratch resistance, solvent resistance and substrate adhesion.
• an oxazoline compound more preferably a combination of isocyanate A and a carbodiimide compound, and still more preferably at least one isocyanate A selected from aliphatic diisocyanates, alicyclic diisocyanates, and modified products thereof.
• hexamethylene diisocyanate HDI
• isophorone diisocyanate IPDI
• hydrogenated xylylene diisocyanate H6XDI
• dicyclohexane preferably hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate (H6XDI), dicyclohexane.
• HDI hexamethylene diisocyanate
• IPDI isophorone diisocyanate
• H6XDI hydrogenated xylylene diisocyanate
• H12MDI silmethane diisocyanate
• HDI hexamethylene diisocyanate
• the aqueous composition of the present invention may further contain a resin having a reactive group that undergoes a crosslinking reaction with at least one selected from isocyanate A and compound B (hereinafter also referred to as “resin C”).
• the reactive group may be a reactive group that undergoes a crosslinking 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.
• the resin C is preferably a resin having a reactive group that undergoes a crosslinking reaction with at least the compound B.
• the reactive group is preferably a functional group that undergoes a crosslinking reaction with at least one selected from a carbodiimide group and an oxazoline group, and examples thereof include a carboxy group, a hydroxy group, an amino group, and a thiol group.
• a carboxy group at least one selected from a carboxy group and a hydroxy group is preferable, and a carboxy group (—COOM) is more preferable.
• the carboxy group include groups that exhibit acidity by dissociation and release of hydrogen ions, or their dissociated ion form (—COO ⁇ ).
• M represents a hydrogen atom, an alkali metal, ammonium or organic ammonium.
• a 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 dialkanol carboxylic acid.
• the dialkanol carboxylic 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 polycarbonate polyol, polyester polyol, and polyether polyol.
• polyisocyanates include chain aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane Aliphatic diisocyanates having a cyclic structure such as 4,4′-diisocyanate; Aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate and tetramethylxylylene diisocyanate; Aromatic diisocyanates such as tolylene diisocyanate and diphen
• reaction solvent for the polyaddition reaction examples include acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, toluene, xylene and the like.
• a chain extender or a reaction terminator may be used in combination as necessary.
• the molecular weight can be further increased by using a chain extender.
• the chain extender examples include polyols and polyamines, and examples of the reaction terminator include monoalcohols and monoamines.
• the polyurethane resin is preferably used as a dispersion (also referred to as an emulsion) dispersed in an aqueous medium, and the emulsion may contain a dispersant such as a surfactant as necessary.
• the acid value of the polyurethane 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 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, Preferably it is 20 mgKOH / g or less.
• the aqueous composition of the present invention suppresses droplet flow due to a difference in osmotic pressure when it comes in contact with ink, as well as improving storage stability and ejectability when the aqueous composition is ejected by an inkjet ejection method. From the viewpoint of improving scratch resistance, solvent resistance and substrate adhesion by obtaining a uniform ink film while obtaining a uniform image, it is preferable to further contain a water-soluble organic solvent D.
• the “water-soluble organic solvent” refers to an organic solvent having a dissolution amount of 10 mL or more when the organic solvent is dissolved in 100 mL of water at 25 ° C.
• the boiling point of the water-soluble organic solvent D is preferably 150 ° C. or higher, more preferably 160 ° C. or higher, further preferably 170 ° C. or higher, still more preferably 180 ° C. or higher, and preferably 240 ° C. or lower, more preferably It is 230 degrees C or less, More preferably, it is 220 degrees C or less, More preferably, it is 210 degrees C or less.
• the boiling point of the water-soluble organic solvent D is a weighted average value weighted by the content (% by mass) of each water-soluble organic solvent. .
• 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 (boiling
• 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 alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, trialkylene glycol monoalkyl ether and the like. Specifically, 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 (boil
• triethylene glycol monobutyl ether (boiling point 276 ° C.) and the like can be mentioned.
• a compound having a boiling point higher than 240 ° C. it is preferably used in combination with a compound having a boiling point lower than 240 ° C.
• the water-soluble organic solvent D is more preferably a polyhydric alcohol from the viewpoint of improving scratch resistance, solvent resistance and substrate adhesion, and among the polyhydric alcohols, more preferably 3 to 6 carbon atoms.
• a diol more preferably a diol having 3 or 4 carbon atoms, and still more preferably propylene glycol.
• the content of the polyhydric alcohol in the water-soluble organic solvent D 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, scratch resistance, solvent resistance, and substrate adhesion of the aqueous composition.
• the content of isocyanate A in the aqueous composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15%. It is 10 mass% or less, More preferably, it is 10 mass% or less.
• the content of Compound B 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.
• 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, still more preferably 0.5% by mass or more, and preferably 10% by mass.
• it is more preferably 5% by mass or less, and further preferably 3% by mass or less.
• the content of the water-soluble organic solvent D 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 in the aqueous composition.
• it is 46 mass% or less, More preferably, it is 44 mass% or less.
• the water content 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, and still more preferably 60% by mass or less.
• the mass ratio (A / B) of the content of isocyanate A to the content of compound B in the aqueous composition is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15 Hereinafter, it is more preferably 12 or less, and still more preferably 10 or less.
• the aqueous composition can be obtained by mixing and stirring at least one compound B selected from isocyanate A, a carbodiimide compound and an oxazoline compound, water, and, if necessary, the other components described above.
• the isocyanate A, carbodiimide compound, and oxazoline compound are preferably blended as an aqueous solution or an emulsion, respectively.
• the aqueous composition of the present invention is used as an ink set for inkjet recording (hereinafter also simply referred to as “ink set”) together with a water-based ink containing pigment (hereinafter also simply referred to as “water-based ink” or “ink”).
• the ink set is an ink set including the aqueous composition and a water-based ink containing a pigment from the viewpoint of improving scratch resistance, solvent resistance, and substrate adhesion, and the water-based composition and the water-based ink. It is preferable that at least one of the inks contains at least a resin having a reactive group that undergoes a crosslinking reaction with the compound B.
• the pigment used in the present invention may be either an inorganic pigment or an organic pigment, and a lake pigment or a fluorescent pigment can also be used. If necessary, they can be used in combination with extender pigments.
• Specific examples of the inorganic pigment include metal oxides such as carbon black, titanium oxide, iron oxide, bengara and chromium oxide, and pearlescent pigments. Particularly for black ink, carbon black is preferred. 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 and chelate azo pigments; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, And polycyclic pigments such as linone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, and selenium pigments.
• azo pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments and chelate azo pigments
• phthalocyanine pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments and chelate azo pigments
• phthalocyanine pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments and chelate azo 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, C.I. I. Pigment Red, C.I. I. Pigment orange, C.I. I. Pigment violet, C.I. I. Pigment blue, and C.I. I.
• extender pigments include silica, calcium carbonate, and talc. The above pigments can be used alone or in admixture of two or more.
• the pigment may be contained in the water-based ink in the form of a self-dispersing pigment, a pigment dispersed with a dispersant, or water-insoluble polymer particles containing the pigment (hereinafter also simply referred to as “pigment-containing polymer particles”).
• water-insoluble in the pigment-containing polymer particles means that the polymer constituting the pigment-containing polymer particles is dried at 105 ° C. for 2 hours to reach a constant weight, and then the polymer is saturated with 100 g of water at 25 ° C. This means that the dissolved amount is less than 10 g, and the dissolved amount of the polymer constituting the pigment-containing polymer particles is preferably 5 g or less, more preferably 1 g or less.
• the ink used in the present invention is at least a resin having a reactive group that undergoes a crosslinking reaction with compound B (hereinafter referred to as “resin (I)”) from the viewpoint of improving scratch resistance, solvent resistance, and substrate adhesion. ) Is preferably contained.
• the reactive group is preferably a functional group that undergoes a crosslinking reaction with at least one selected from a carbodiimide group and an oxazoline group, and examples thereof include a carboxy group, a hydroxy group, an amino group, and a thiol group. Among these, a carboxy group is preferable.
• Examples of the carboxy group include groups that exhibit acidity by dissociation and release of hydrogen ions, or their dissociated ion forms, as in the case of the resin C described above.
• the reactive group is a functional group that also undergoes a crosslinking reaction with isocyanate A
• the regenerated active isocyanate undergoes a self-crosslinking reaction as well as a bridging reaction with resin I, resulting in scratch resistance, solvent resistance, and substrate.
• Adhesion can be improved.
• the resin I can be used as a pigment dispersion polymer (Ia) for dispersing the pigment and a fixing aid polymer (Ib) for improving the scratch resistance of the printed matter, and these may be used in combination.
• the water-based ink preferably contains at least one selected from the pigment dispersion polymer (Ia) and the fixing aid polymer (Ib) from the viewpoint of the dispersibility of the pigment and the scratch resistance of the printed matter. More preferably, it contains (Ib), and further preferably contains a pigment dispersion polymer (Ia) and a fixing aid polymer (Ib).
• the pigment dispersion polymer (Ia) for dispersing the pigment examples include condensation resins such as polyester resins and polyurethane resins; vinyl resins obtained by addition polymerization of vinyl monomers (vinyl compounds, vinylidene compounds, vinylene compounds), etc. Is mentioned. Among these, at least one selected from polyester resins and vinyl resins is preferable, and polyester resins are more preferable from the viewpoint of improving scratch resistance, solvent resistance, and substrate adhesion.
• condensation resins such as polyester resins and polyurethane resins
• vinyl resins obtained by addition polymerization of vinyl monomers vinyl compounds, vinylidene compounds, vinylene compounds
• polyester resins are more preferable from the viewpoint of improving scratch resistance, solvent resistance, and substrate adhesion.
• the pigment dispersion polymer (Ia) an appropriately synthesized product or a commercially available product may be used.
• polyester resin used for the pigment dispersion polymer (Ia) contains a structural unit derived from an alcohol component and a structural unit derived from a carboxylic acid component, and is obtained by polycondensation of an alcohol component and a carboxylic acid component.
• the alcohol component which is a raw material monomer of the polyester resin preferably contains an aromatic diol.
• an aromatic diol an alkylene oxide adduct of bisphenol A is preferable.
• the alkylene oxide adduct of bisphenol A means the entire 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 added moles of alkylene oxide.
• 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 even more 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 at least one selected from 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, from the viewpoints of pigment dispersibility, scratch resistance, solvent resistance and substrate adhesion. More preferably, it is 70 mol% or more, and preferably 100 mol% or less.
• the alcohol component which is a raw material monomer of the polyester resin, may contain the following other alcohol components.
• the alcohol component may contain the following other alcohol components.
• the other alcohol components may be used alone or in combination of two or more.
• the carboxylic acid component that is a raw material monomer of the polyester resin includes carboxylic acids, anhydrides of those acids, and alkyl (1 to 3 carbon atoms) esters thereof.
• Examples of the carboxylic acid component include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trivalent or higher polyvalent carboxylic acids.
• aromatic dicarboxylic acid phthalic acid, isophthalic acid, and terephthalic acid are preferable, and terephthalic acid is more preferable.
• the aliphatic dicarboxylic acid include unsaturated aliphatic dicarboxylic acid and saturated aliphatic dicarboxylic acid.
• the unsaturated aliphatic dicarboxylic acid fumaric acid and maleic acid are preferable, fumaric acid is more preferable, and saturated aliphatic dicarboxylic acid.
• the acid adipic acid and succinic acid are preferable.
• the cycloaliphatic dicarboxylic acid is preferably cyclohexane dicarboxylic acid, decalin dicarboxylic acid, or tetrahydrophthalic acid, and the trivalent or higher polyvalent carboxylic acid is preferably trimellitic acid or pyromellitic acid.
• the polyester resin can be obtained by performing polycondensation by a known method in the presence of an esterification catalyst or the like, and specifically, can be obtained according to the method described in Examples.
• the acid value of the polyester resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 15 mgKOH / g, from the viewpoints of pigment dispersibility, scratch resistance, solvent resistance, and substrate adhesion. It is above, and is preferably 45 mgKOH / g or less, more preferably 40 mgKOH / g or less, 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.
• 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, from the viewpoint of scratch resistance, solvent resistance and substrate adhesion. 80 ° C. or lower, more preferably 75 ° C. or lower, and still more preferably 70 ° C. or lower.
• the weight average molecular weight of the polyester resin is preferably 5,000 or more, more preferably 7,500 or more, still more preferably 10,000 or more, from the viewpoint of scratch resistance, solvent resistance and substrate adhesion. From the viewpoint of dispersion stability of the pigment, it is preferably 100,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less.
• the acid value, softening point, glass transition temperature, and weight average molecular weight can all be obtained by appropriately adjusting the type of monomer used, the blending ratio, the polycondensation temperature, and the reaction time. Moreover, the acid value of a polyester resin, a softening point, a glass transition temperature, and a weight average molecular weight are measured by the method as described in an Example.
• the vinyl resin used in the pigment dispersion polymer (Ia) is composed of a structural unit derived from an ionic monomer, a structural unit derived from a hydrophobic monomer, and a hydrophilic nonionic monomer (hereinafter also referred to as “nonionic monomer”). It is preferable to have one or more selected from units, and it is more preferable to have two or more of these structural units. For example, the combination of an ionic monomer and a hydrophobic monomer, the combination of an ionic monomer, a hydrophobic monomer, and a nonionic monomer is mentioned.
• the vinyl resin can be obtained, for example, by addition polymerization of a monomer mixture containing an ionic monomer, a hydrophobic monomer, and a nonionic monomer by a known method.
• the ionic monomer examples include anionic monomers such as carboxylic acid monomers, sulfonic acid monomers, and phosphoric acid monomers; and cationic monomers such as N, N-dimethylaminoethyl methacrylate and N, N-dimethylaminoethylacrylamide.
• anionic monomers such as carboxylic acid monomers, sulfonic acid monomers, and phosphoric acid monomers
• cationic monomers such as N, N-dimethylaminoethyl methacrylate and N, N-dimethylaminoethylacrylamide.
• an anionic monomer is preferable, a carboxylic acid monomer is more preferable, and (meth) acrylic acid is still more preferable.
• the ionic monomer includes a monomer that becomes an ion under acidic or alkaline conditions, even if it is a neutral non-ionic monomer such as an acid or an amine.
• hydrophobic monomer examples include (meth) acrylates having a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms; aromatic group-containing monomers such as styrene monomers and aromatic group-containing (meth) acrylates; A macromer.
• the molecular weight of the aromatic group-containing monomer preferably a styrenic monomer, is preferably less than 500.
• the styrenic macromonomer is a compound having a polymerizable functional group at one end and a number average molecular weight of 500 or more and 100,000 or less.
• Nonionic monomers include polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate; alkoxy polyalkylene glycol mono (such as methoxy polyethylene glycol mono (meth) acrylate and octoxypolyethylene glycol mono (meth) acrylate) And (meth) acrylate.
• “(Meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.
• the “(meth) acrylate” means at least one selected from acrylate and methacrylate.
• each monomer of the vinyl resin may be used alone or in combination of two or more.
• 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, aromatic
• a vinyl resin containing a structural unit derived from one or more hydrophobic monomers selected from an aromatic group-containing monomer and a styrene macromer more preferably a vinyl resin containing a structural unit derived from a nonionic monomer. It is.
• the content of each monomer in the monomer mixture at the time of vinyl resin production (content as an unneutralized amount; the same applies hereinafter) or a structural unit derived from an ionic monomer or a structural unit derived from a hydrophobic monomer in a vinyl resin
• the content of the structural unit derived from the nonionic monomer is as follows from the viewpoint of improving the dispersion stability of the pigment.
• the content of the ionic monomer component is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less. More preferably, it is 20 mass% or less.
• the content of the hydrophobic monomer component is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less. More preferably, it is 70 mass% or less.
• the content of the nonionic monomer component is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 40% by mass. Hereinafter, it is more preferably 35% by mass or less, and further preferably 30% by mass or less.
• 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 from the viewpoints of pigment dispersibility, scratch resistance, solvent resistance, and substrate adhesion. , 000 or more, and preferably 100,000 or less, more preferably 80,000 or less, and further preferably 60,000 or less.
• Examples of commercially available vinyl resins include polyacrylic acid such as “Aron AC-10SL” (manufactured by Toa Gosei Co., Ltd.), “John Crill 67”, “John Crill 611”, “John Crill 678”, “John Examples thereof include styrene-acrylic resins such as “Krill 680”, “Jonkrill 690”, and “Jonkrill 819” (above, manufactured by BASF Japan Ltd.). The weight average molecular weight of the vinyl resin is measured by the method described in Examples.
• the water-based ink preferably contains the fixing aid polymer (Ib) from the viewpoint of scratch resistance, solvent resistance, and substrate adhesion, and the fixing aid polymer (Ib) is a polymer particle containing no pigment. It is preferable to use it.
• the polymer component of the polymer particles not containing the pigment, that is, the fixing aid polymer (Ib) includes: condensation resins such as polyurethane resins and polyester resins; acrylic resins, styrene resins, styrene-acrylic resins, butadiene resins, Examples thereof include vinyl resins such as styrene-butadiene resin, vinyl chloride resin, vinyl acetate resin, and acrylic silicone resin.
• the fixing aid polymer (Ib) is preferably used as an aqueous dispersion containing polymer particles not containing a pigment from the viewpoint of improving the productivity of the water-based ink.
• the fixing assistant polymer (Ib) a suitably synthesized one may be used, or a commercially available product may be used.
• the water-based ink preferably contains water-insoluble polymer particles containing a pigment (hereinafter also simply referred to as “pigment-containing polymer particles”) from the viewpoints of dispersion stability and ejection stability of the ink. That is, in the water-based ink, the pigment is preferably contained in the form of pigment-containing polymer particles from the same viewpoint as described above.
• the pigment-containing polymer particles need only be formed of a pigment and a water-insoluble polymer, and are particles formed by adsorbing a water-insoluble polymer to a pigment in an aqueous ink.
• the pigment-containing polymer particles can be obtained by dispersing the pigment, the pigment-dispersed polymer (Ia), and if necessary, a neutralizing agent, a surfactant and the like by a known method.
• the average particle size of the pigment-containing polymer particles is preferably 10 nm or more, more preferably 30 nm, from the viewpoints of ink dispersion stability and ejection stability, and from the viewpoint of improving scratch resistance, solvent resistance, and substrate adhesion.
• the water-based ink may further contain an organic solvent as a component other than the pigment, the resin I, and water as necessary.
• an organic solvent what is mentioned by the water-soluble organic solvent D used for the above-mentioned aqueous composition is preferable.
• Water-based inks also contain various additives such as humectants, wetting agents, penetrating agents, dispersants, surfactants, viscosity modifiers, antifoaming agents, antiseptics, antifungal agents, and rust inhibitors as optional components. May be included.
• the water-based ink can be obtained by mixing and stirring the pigment, resin I, water and, if necessary, a neutralizing agent, a surfactant, an organic solvent, and the like.
• the content of each component of the water-based ink is as follows.
• pigment and resin I preferably pigment and pigment-dispersed polymer (Ia)
• the dispersion of the pigment-containing polymer particles is a dispersion polymer (before the dispersion treatment) from the viewpoints of dispersion stability and ejection stability of the ink, and improvement of scratch resistance, solvent resistance, and substrate adhesion. More preferably, Ia) is dissolved in an organic solvent and dispersed together with the pigment, and then the organic solvent is removed.
• the water content is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more in the water-based ink from the viewpoint of scratch resistance, solvent resistance, and substrate adhesion. And, it is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.
• the content of the organic solvent is preferably 5% by mass or more in the water-based ink from the viewpoints of ink ejection properties, scratch resistance, solvent resistance, and substrate adhesion.
• it is 10 mass% or more, More preferably, it is 20 mass% or more, Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 40 mass% or less.
• the aqueous composition may be applied to a region to which the water-based ink has been applied by an inkjet discharge method on the surface of the recording medium.
• a water-based ink may be applied to the region by an inkjet discharge method.
• There are no particular restrictions on the method of applying the aqueous composition Known methods such as a coating method, a dipping method, and a method using an ink jet discharge method can be used. Among these, an inkjet discharge method is preferable.
• the ink jet recording method of the present invention when at least one of the aqueous composition and the water-based ink contains a resin having a reactive group that undergoes a crosslinking reaction with at least Compound B, the scratch resistance, solvent resistance, and substrate adhesion From a viewpoint of property, Preferably, it has the following process 1 and process 2.
• Step 1 A step of ejecting the aqueous composition and the water-based ink onto the surface of a recording medium by an inkjet method to obtain a recorded image
• Step 2 Isocyanate A of the recorded image obtained in Step 1, Compound B, Cross-linking reaction with the resin
• Step 1 is a step of obtaining a recorded image by ejecting the aqueous composition and the water-based ink onto the surface of a recording medium by an ink jet method.
• Step 1 includes a step 1-1 (hereinafter also referred to as “step 1-1”) in which water-based ink is ejected onto a recording medium by an ink jet method, and a step 1-2 (in which an aqueous composition is ejected onto a recording medium by an ink jet method.
• step 1-1 is performed before step 1-2 or simultaneously with step 1-2, and step 1-1 is performed as step 1-. More preferably, it is performed before 2.
• step 1-1 before step 1-2 a printed matter having excellent scratch resistance, solvent resistance and substrate adhesion can be obtained more effectively.
• the time from application of the water-based ink to the recording medium to application of the aqueous composition to the recording medium is not particularly limited.
• a piezo method is preferable from the viewpoint of discharge properties.
• 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 in terms of solid content from the viewpoint of scratch resistance, solvent resistance and substrate adhesion. Or more, more preferably 1.5 g / m 2 or more, and preferably 5.0 g / m 2 or less, more preferably 3.5 g / m 2 or less, still more preferably 2.0 g / m 2 or less. .
• the amount of 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 in terms of solid content from the viewpoint of scratch resistance, solvent resistance and substrate adhesion. More preferably, it is 2.0 g / m 2 or more, 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 in which the isocyanate A, the compound B, and the resin contained in the aqueous composition or water-based ink of the recorded image obtained in Step 1 are subjected to a crosslinking reaction. Thereby, a strong ink film is formed. In the crosslinking reaction, it is preferable to heat-treat the recording medium on which the recorded image is formed.
• the heating temperature is preferably equal to or higher than the dissociation temperature of isocyanate A. Specifically, it is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 120 ° C. or higher, and preferably 200 ° C. or lower, more preferably 190 ° C.
• the heating temperature is preferably less than the temperature at which the recording medium is deformed. In the case where the recording medium is a shrink film, the temperature is preferably equal to or lower than a temperature at which the printed material can be used without any problem even if shrinkage occurs. Furthermore, when the recording medium is a shrink film, heating can be performed while the shrink film is attached to an object to be pasted, and the cross-linking reaction of the recorded image and the pasting by shrinking the film can be simultaneously performed in one step.
• the heating time is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, and preferably 30 minutes or less, more preferably 20 minutes or less, and even more preferably 15 minutes or less.
• step 2 is a step of drying the recorded image obtained in the step 1 (hereinafter referred to as “step 2-2”) before performing the step of heating above the dissociation temperature of the isocyanate A (hereinafter also referred to as “step 2-2”). It is also preferable to have “step 2-1”.
• step 2-1 the crosslinking reaction of compound B and the resin contained in the aqueous composition or water-based ink proceeds, and in step 2-2, the crosslinking reaction of isocyanate A proceeds. Can be done efficiently.
• the temperature in step 2-1 is preferably less than the dissociation temperature of isocyanate A. Specifically, it is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, further preferably 45 ° C.
• the time of step 2-1 is preferably 1 minute or more, more preferably 2 minutes or more, and preferably 20 minutes or less, more preferably 10 minutes or less, and even more preferably 5 minutes or less.
• the recording medium used for the inkjet recording method of the present invention is not particularly limited.
• the recording medium include plain paper with high water absorption, coated paper with low water absorption, and non-water-absorbent resin film. From the viewpoint of scratch resistance, solvent resistance and substrate adhesion, low water absorption recording.
• a medium is preferable, a low water-absorbing coated paper and a non-water-absorbing resin film are more preferable, and a non-water-absorbing resin film is more preferable.
• 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.
• shrink films include Space Clean S7042 (manufactured by Toyobo Co., Ltd.), DXL series, Hishippet series, PLABIO, Hybrex DL (manufactured by Mitsubishi Chemical Corporation), Bonset series (manufactured by Takiron Sea Eye Co., Ltd.), Fancy Wrap PET series (manufactured by Gunze Co., Ltd.) and the like.
• Glass transition temperature of polyester resin Using a differential scanning calorimeter “Pyris 6 DSC” (manufactured by Perkin Elmer), 5 mg of a sample was weighed in an aluminum pan, heated to 200 ° C., and cooled to 0 ° C. at a temperature decreasing rate of 10 ° C./min. . Next, the sample was heated at a heating rate of 10 ° C./min. The glass transition temperature was defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent indicating the maximum slope from the peak rising portion to the peak apex.
• 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.
• the weight average molecular weight of the sample is the following monodispersed polystyrene [monodispersed polystyrene manufactured by Tosoh Corporation; 2.63 ⁇ 10 3 , 2.06 ⁇ 10 4 , 1.02 ⁇ 10 5 (weight average molecular weight (Mw)) GL Sciences, Inc.
• sample solution a solution obtained by dissolving a vinyl resin in N, N-dimethylformamide so as to have a concentration of 0.3% was used.
• Measurement conditions Measuring device: “HLC-8120GPC” (manufactured by Tosoh Corporation)
• the measurement conditions were a temperature of 25 ° C., an angle between incident light and a detector of 90 °, and an integration count of 100.
• the refractive index of water (1.333) was input as the refractive index of the dispersion solvent.
• the measurement concentration was 5 ⁇ 10 ⁇ 3 %.
• the pigments, organic solvents, surfactants and pH adjusters used in the following production examples, examples and comparative examples are as follows.
• Black pigment PB7 (carbon black, manufactured by Cabot)
• Organic solvent -BDG: Diethylene glycol monobutyl ether (Wako Pure Chemical Industries, Ltd.)
• PG Propylene glycol (Wako Pure Chemical Industries, Ltd.)
• KF6011 Alkylene glycol modified polydimethylsiloxane (trade name “KF-6011”, manufactured by Shin-Etsu Chemical Co., Ltd., nonionic surfactant)
• PH adjuster MDEA: N-methyldiethanolamine (Wako Pure Chemical Industries, Ltd.)
• “Drip monomer solution 2” in the dropping funnel 2 was gradually dropped into the reaction vessel over 2 hours. After completion of dropping, the mixed solution in the reaction vessel was stirred at 77 ° C. for 0.5 hour. Next, a polymerization initiator solution in which 0.6 parts by mass of the polymerization initiator was dissolved in 27.0 parts by mass of MEK was prepared, added to the mixed solution, and aged by stirring at 77 ° C. for 1 hour. Preparation, addition and aging of the polymerization initiator solution were further performed 5 times. Next, the reaction solution in the reaction vessel was maintained at 80 ° C. for 1 hour, and MEK was added to obtain a vinyl resin P-3 solution (solid content concentration 40.8%). The weight average molecular weight (Mw) of the obtained vinyl resin P-3 was 52,700.
• Production Example 2-1 (Production of aqueous dispersion D-1 of polyester resin particles containing a pigment)
• Pigment dispersion step In a container with an internal volume of 2 L, 66.7 g of the polyester resin P-1 as the pigment dispersion polymer (Ia) is dissolved in 156.4 g of methyl ethyl ketone (MEK), and 5N hydroxide is used as a neutralizing agent therein. 5.36 g of an aqueous sodium solution and 430 g of ion-exchanged water were added, and the neutralization degree with sodium hydroxide was adjusted to 85 mol% with respect to the acid value of the polyester resin P-1, and 10 ° C. or higher and 15 ° C.
• MEK methyl ethyl ketone
• the mixture was stirred and mixed at 2,000 r / min for 15 minutes using a disper blade. Next, 100 g of a black pigment was added, and the mixture was stirred and mixed at 7,000 r / min for 2 hours at 10 to 15 ° C. using a disper blade. The obtained pre-dispersion was filtered through 150 mesh and 36.1 g of ion-exchanged water was added to dilute it. A 15-pass dispersion treatment was performed under pressure to obtain a dispersion of pigment-containing polyester resin particles.
• the obtained concentrate was 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.)
• the liquid layer portion was filtered through a membrane filter “Minisart” (Sartorius) having a pore diameter of 5 ⁇ m to obtain an aqueous dispersion 1 of pigment-containing polyester resin particles.
• Ion exchange water was added so that the solid content concentration of the obtained aqueous dispersion 1 was 22.0%, and “Proxel (registered trademark) LV (S)” (manufactured by Lonza Japan KK: preservative, effective Min. 20%) 0.76 g was added and stirred at 70 ° C. for 2 hours. After cooling to 25 ° C., the mixture was filtered through a filter having a pore size of 5 ⁇ m, and ion-exchanged water was further added to obtain an aqueous dispersion D-1 of pigment-containing polyester resin particles (solid content concentration 22.0%). The average particle diameter of the pigment-containing polyester resin particles of the aqueous dispersion D-1 was 90 nm.
• Production Example 2-2 (Production of aqueous dispersion D-2 of vinyl resin particles containing pigment) (1)
• Pigment dispersion step 157.6 g of a vinyl resin P-3 solution (solid concentration 40.8%) as a pigment dispersion polymer (Ia) is mixed with 60.7 g of methyl ethyl ketone (MEK) to give a vinyl resin P -3 MEK solution was obtained.
• a MEK solution of vinyl resin P-3 is put into a container having an internal volume of 2 L, and 446.9 g of ion-exchanged water and a 5N sodium hydroxide aqueous solution 22 are stirred using a disper blade at 1,400 r / min.
• the obtained concentrate was put into a 500 mL angle rotor, and centrifuged at 7,000 r / min for 20 minutes using a high-speed cooling centrifuge “himac CR22G” (manufactured by Hitachi Koki Co., Ltd., set temperature 20 ° C.)
• the liquid layer portion was filtered through a membrane filter “Minisart” (manufactured by Sartorius) having a pore diameter of 5 ⁇ m to obtain an aqueous dispersion 2 of pigment-containing vinyl resin particles.
• the mixture is filtered through the filter having a pore size of 5 ⁇ m, and ion-exchanged water is further added to the aqueous dispersion D-2 of the pigment-containing vinyl resin particles (crosslinking rate 40 mol%, solid content concentration 22.0%).
• crosslinking rate 40 mol%, solid content concentration 22.0% 40 mol%, solid content concentration 22.0%.
• the average particle diameter of the pigment-containing vinyl resin particles of the aqueous dispersion D-2 was 93.1 nm.
• Production Example 3-1 (Production of aqueous dispersion d-1 of polyester resin particles containing no pigment)
• polyester resin P-2 as a fixing aid polymer (Ib) and methyl ethyl ketone (MEK) as an organic solvent were blended as shown in Table 3. And dissolved in MEK at 25 ° C.
• a 5N aqueous sodium hydroxide solution was added as a neutralizing agent, and deionized water was added with stirring to obtain a dispersion of polyester resin particles containing no pigment.
• the resulting dispersion was decompressed while being kept at 60 ° C.
• aqueous dispersion d-1 of polyester resin particles containing no pigment (solid content concentration 40.0%).
• Table 3 shows the physical properties of the aqueous dispersion d-1.
• Production Example 3-2 (Production of aqueous dispersion d-2 of vinyl resin particles containing no pigment)
• aqueous dispersion d-2 of vinyl resin particles containing no pigment In a 1000 mL separable flask, 145 parts of methyl methacrylate (Wako Pure Chemical Industries, Ltd.), 50 parts of 2-ethylhexyl acrylate (Wako Pure Chemical Industries, Ltd.), 5 parts of methacrylic acid (Wako Pure Chemical Industries, Ltd.), Latemul E-118B (Kao Corporation, emulsifier, effective 26%) 18.5 parts, ion-exchange water 96 parts, potassium persulfate (Wako Pure Chemical Industries, Ltd.) was charged and stirred with a stirring blade ( 300 rpm) A monomer emulsion was obtained.
• Ink production examples 1 and 2 The mixture was mixed according to the formulation shown in Table 4 below, and the resulting mixture was filtered through a membrane filter “Minisart” (manufactured by Sartorius) having a pore size of 1.2 ⁇ m to obtain water-based inks X and Y, respectively.
• a membrane filter “Minisart” manufactured by Sartorius
• Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 The mixture was mixed according to the formulation shown in Table 5 below, and the obtained mixed solution was filtered through a membrane filter “Minisart” (manufactured by Sartorius) having a pore size of 1.2 ⁇ m to obtain aqueous compositions 1 to 10.
• the obtained aqueous composition was stored in a constant temperature environment at 60 ° C., and the viscosity of the aqueous composition after storage was measured.
• C The viscosity change rate of the aqueous composition after storage for 1 week was 90% or more and 110% or less, but the viscosity change rate after exceeding 1 week was less than 90% or more than 110%.
• D The viscosity change rate of the aqueous composition was less than 90% or more than 110% after storage for less than 1 week.
• Aqua BI200 blocked isocyanate (isocyanate type: HDI trimer, blocking agent: 3,5-dimethylpyrazole, reaction temperature (dissociation temperature) 110 ° C. or higher, isocyanate group equivalent 933, effective content 40%, solvent: water / NMP, Baxenden, trade name “Trixene blocked isoquanates Aqua BI200”)
• AquaBI220 Blocked isocyanate (isocyanate type: HDI trimer, blocking agent: 3,5-dimethylpyrazole, reaction temperature (dissociation temperature) 110 ° C.
• solvent water / coazole (Coasol), manufactured by Baxenden, trade name “Trixene blocked isoquanates Aqua BI220”)
• Elastrone BN77 Blocked isocyanate (reaction temperature (dissociation temperature) of 120 ° C.
• Carbodilite V-04 polycarbodiimide compound (appearance: aqueous solution, carbodiimide group equivalent 335, effective 40%, Nisshinbo Chemical Co., Ltd., trade name)
• Carbodilite E-02 polycarbodiimide compound (appearance: emulsion, carbodiimide group equivalent 445, effective 40%, Nisshinbo Chemical Co., Ltd., trade name)
• Epocross WS-700 Oxazoline group-containing polymer (oxazoline group equivalent 220, effective 25%, Nippon Shokubai Co., Ltd., trade name)
• Superflex 870 Aromatic isocyanate-ester polyurethane resin (effective 30%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name)
• Denacol EX-212 1,6-hexanediol diglycidyl
• Examples 2-1 to 2-9 and comparative examples 2-1 to 2-4 A combination of an aqueous composition and water-based ink shown in Table 6 below is used as an ink set, and Lumirror (registered trademark) T60 (manufactured by Toray Industries, Inc., polyethylene terephthalate (PET) film, water absorption 2.3 g / m 2 ) is used as a recording medium. ), Space Clean (registered trademark) S7042 (manufactured by Toyobo Co., Ltd., shrink PET film, thermal shrinkage (90 ° C., 10 seconds): 60%, water absorption 10 g / m 2 or less), and printed matter by the following method The following evaluation was performed about each printed matter obtained. The results are also shown in Table 6.
• Printing evaluation equipped with an inkjet head (Kyocera Corporation, product name “KJ4B-YH”, piezo type) and an under heater that heats the recording medium from the back side of the recording medium facing the inkjet head
• the apparatus was filled with a water-based ink and an aqueous composition.
• the distance between the underheater and the recording medium was set to 0.2 mm
• the distance between the inkjet head and the recording medium was set to 2.0 mm
• the surface temperature of the underheater was set to 40 ° C. Under an environment of a temperature of 25 ⁇ 1 ° C.
• the aqueous composition of the present invention is excellent in storage stability. According to an ink set comprising the aqueous composition and a water-based ink, and an ink jet recording method using the water-based composition and the water-based ink, a non-water-absorbing recording medium or a shrinkage is obtained. Even when printing is performed on a recording medium having the property, a printed matter having excellent scratch resistance, solvent resistance and substrate adhesion can be obtained.

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• 2019
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  • 2019-04-23 ES ES19793638T patent/ES2945574T3/es active Active
  • 2019-04-23 CN CN201980026644.9A patent/CN112020441B/zh active Active
  • 2019-04-23 US US17/049,140 patent/US20210238437A1/en not_active Abandoned
  • 2019-04-23 WO PCT/JP2019/017235 patent/WO2019208567A1/ja not_active Ceased

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