WO2023074788A1 - 水性樹脂組成物、画像形成方法及び印刷物 - Google Patents

水性樹脂組成物、画像形成方法及び印刷物 Download PDF

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Publication number
WO2023074788A1
WO2023074788A1 PCT/JP2022/040125 JP2022040125W WO2023074788A1 WO 2023074788 A1 WO2023074788 A1 WO 2023074788A1 JP 2022040125 W JP2022040125 W JP 2022040125W WO 2023074788 A1 WO2023074788 A1 WO 2023074788A1
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Prior art keywords
resin composition
aqueous resin
less
polyurethane resin
cross
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Ceased
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PCT/JP2022/040125
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English (en)
French (fr)
Japanese (ja)
Inventor
章照 藤井
宇清 徐
幸子 澤田
祐也 平本
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to EP22887113.3A priority Critical patent/EP4424788A1/en
Priority to JP2023556628A priority patent/JPWO2023074788A1/ja
Priority to CN202280069499.4A priority patent/CN118119683A/zh
Publication of WO2023074788A1 publication Critical patent/WO2023074788A1/ja
Priority to US18/645,590 priority patent/US20240368377A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • 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
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5281—Polyurethanes or polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/24—Reactive compound reacting in image receiving layer other than leuco dyes or mordants

Definitions

  • the present invention relates to a water-based resin composition that is applied onto printing media.
  • the present invention also relates to an image forming method and printed matter using this aqueous resin composition.
  • an adhesive layer also known as an undercoat layer or a primer layer
  • a water-based resin composition is preferably used as the coating liquid for the adhesive layer.
  • Patent Document 1 a water-soluble resin such as polyethyleneimine (Patent Document 1), a dispersion of an acrylic resin or a polyurethane resin (Patent Document 2), a dispersion of a specific polyurethane resin and a carbodiimide cross-linking agent. (Patent Document 3) has been proposed.
  • Patent Document 3 a water-soluble resin such as polyethyleneimine (Patent Document 1), a dispersion of an acrylic resin or a polyurethane resin (Patent Document 2), a dispersion of a specific polyurethane resin and a carbodiimide cross-linking agent.
  • Patent Document 3 When conventional water-based resin compositions were used, durability such as water resistance, heat resistance, and solvent resistance of printed matter after coating was insufficient. Therefore, in such an aqueous resin composition, studies have been conducted to improve the water resistance and solvent resistance of the coating layer by causing a cross-linking action in the coating layer after coating (Patent Document 3). .
  • a water-based resin composition used for an adhesive layer for digital printing is required to have liquid stability not only during transportation and storage, but also when a liquid that has been used once is used repeatedly.
  • It is possible to improve the liquid stability during transportation and storage by making it a two-component type in which the resin component and the cross-linking agent component are separated. Cannot be used repeatedly. Therefore, the liquid after use is discarded, which is economically inefficient.
  • the one-liquid type in which the resin component and the cross-linking agent component are mixed in advance it is difficult to maintain liquid stability under temperature changes during transportation and storage, especially at high temperatures of 40° C. or higher.
  • the object of the first embodiment of the present invention is to exhibit good durability and image quality in the printed matter after coating, suppress odor during printing, and have good liquid stability, that is, at 40 ° C. or higher
  • the fluidity of the liquid can be maintained even after a certain period of time has passed under high temperature conditions, and in addition, good adhesion to printed matter even after a certain period of time has passed under high temperature conditions of 40°C or higher. It is to provide an aqueous resin composition from which is obtained.
  • the object of the second embodiment of the present invention is to exhibit good durability and image quality in the printed matter after coating, and to have good liquid stability, that is, after a certain period of time has passed under high temperature conditions of 40 ° C. or higher.
  • An object of the present invention is to provide a water-based resin composition which can maintain the fluidity of the liquid even when it is heated.
  • the object of the third embodiment of the present invention is to exhibit good durability and image quality in the printed matter after coating, and to have good liquid stability, that is, after a certain period of time has passed under high temperature conditions of 40 ° C. or higher.
  • An object of the present invention is to provide a water-based resin composition which can maintain the fluidity of the liquid even when it is heated.
  • a first embodiment of the present invention is an aqueous resin composition containing at least a polyurethane resin having a carboxylate group, a cross-linking agent having at least two carbodiimide groups per molecule, and a surfactant, , an amine compound in which the molar ratio of the carbodiimide groups of the cross-linking agent to the carboxylate groups of the polyurethane resin is 0.1 or more and 5.0 or less, and the pKb is 3.5 or more and 4.7 or less.
  • a second embodiment of the present invention is an aqueous resin composition containing at least a polyurethane resin having a carboxylate group, a cross-linking agent having at least two carbodiimide groups per molecule, and a surfactant, , the polyurethane resin is a polyether polyurethane resin, and the molar ratio of the carbodiimide groups of the cross-linking agent to the carboxylate groups of the polyurethane resin is 0.1 or more and 2.9 or less, A water-based resin composition is proposed.
  • a third embodiment of the present invention is an aqueous resin composition containing at least a polyurethane resin having a carboxylate group, a cross-linking agent having at least two carbodiimide groups per molecule, and a surfactant, , the carbodiimide group equivalent of the cross-linking agent is 400 mol ⁇ 1 or more and 700 mol ⁇ 1 or less, and the molar ratio of the carbodiimide groups of the cross-linking agent to the carboxylate groups of the polyurethane resin is 0.4 or more.
  • aqueous resin composition containing at least a polyurethane resin having a carboxylate group, a cross-linking agent having at least two carbodiimide groups per molecule, and a surfactant, the molar ratio of the carbodiimide groups of the cross-linking agent to the carboxylate groups of the polyurethane resin is 0.1 or more and 5.0 or less; An aqueous resin composition further comprising an amine compound having a pKb of 3.5 or more and 4.7 or less.
  • An aqueous resin composition containing at least a polyurethane resin having a carboxylate group, a cross-linking agent having at least two carbodiimide groups per molecule, and a surfactant,
  • the polyurethane resin is a polyether polyurethane resin
  • the water-based resin composition wherein the molar ratio of the carbodiimide groups of the cross-linking agent to the carboxylate groups of the polyurethane resin is 0.1 or more and 2.9 or less.
  • An aqueous resin composition containing at least a polyurethane resin having a carboxylate group, a cross-linking agent having at least two carbodiimide groups per molecule, and a surfactant,
  • the carbodiimide group equivalent of the cross-linking agent is 400 mol -1 or more and 700 mol -1 or less
  • An aqueous resin composition, wherein the molar ratio of the carbodiimide groups of the cross-linking agent to the carboxylate groups of the polyurethane resin is 0.4 or more.
  • ⁇ 4> The aqueous resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polyurethane resin is a saturated hydrocarbon-based polyether polyurethane resin and has an ammonium carboxylate group.
  • ⁇ 5> The aqueous resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the carbodiimide group equivalent of the cross-linking agent is 500 mol -1 or more and 700 mol -1 or less.
  • ⁇ 6> The aqueous resin composition according to ⁇ 1>, ⁇ 4> or ⁇ 5>, wherein the amine compound has a boiling point of 151° C. or higher.
  • an ink layer is formed with an ink containing a resin having a carboxy group.
  • a digital printing method for forming an image ⁇ 8> An image forming method using a digital printing method in which an adhesive layer is formed by coating an aqueous resin composition on a printing medium, and then an ink layer is formed with an ink, An image forming method, wherein the aqueous resin composition contains a polyurethane resin having a carboxylate group and a cross-linking agent having at least two carbodiimide groups per molecule.
  • a printed material having an adhesive layer and an ink layer on a printing medium The printed matter, wherein the adhesive layer has a crosslinked structure of a polyurethane resin having a carboxylate group and a crosslinking agent having a carbodiimide group.
  • the aqueous resin composition proposed by the first embodiment of the present invention exhibits good durability and image quality in printed matter after coating, suppresses odor during printing, and has good liquid stability. , The fluidity of the liquid can be maintained even after a certain period of time has passed under high temperature conditions of 40 ° C or higher, and in addition, even if it is coated after a certain period of time has passed under high temperature conditions of 40 ° C or higher, printed matter Good adhesion can be obtained in The aqueous resin composition proposed by the second embodiment of the present invention exhibits good durability and image quality in the printed matter after coating, and has good liquid stability, that is, under high temperature conditions of 40 ° C. or higher. The fluidity of the liquid can be maintained even after a certain period of time has passed.
  • the aqueous resin composition proposed by the third embodiment of the present invention exhibits good durability and image quality in printed matter after coating, and has good liquid stability, that is, under high temperature conditions of 40 ° C. or higher.
  • the fluidity of the liquid can be maintained even after a certain period of time has passed.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of an electrophotographic digital printer to which the present invention is applied;
  • the aqueous resin composition of the first embodiment of the present invention is a representative example of the embodiment of the present invention, and can be modified as appropriate without departing from the scope of the present invention. Unless otherwise specified in the following description, measurements of various physical properties and operation steps are based on normal temperature and normal pressure conditions.
  • the aqueous resin composition of the first embodiment of the present invention, the aqueous resin composition of the second embodiment, and the aqueous resin composition of the third embodiment are collectively referred to as "the aqueous resin composition of the present invention. "things”.
  • the water-based resin composition of the present invention can be suitably used as a water-based coating liquid. It can be suitably used as a water-based coating liquid for In other words, the aqueous resin composition of the present invention can be suitably used as a primer for forming a primer layer.
  • the aqueous resin composition of the first embodiment of the present invention comprises a polyurethane resin having a carboxylate group, a cross-linking agent having at least two carbodiimide groups per molecule, a surfactant, and a pKb of 3.5. and an amine compound having a ratio of at least 4.7 and not more than 4.7.
  • the aqueous resin composition of the second embodiment and the third embodiment of the present invention comprises a polyurethane resin having a carboxylate group, a cross-linking agent having at least two carbodiimide groups per molecule, and an interface and an active agent.
  • Water-based resin compositions used in adhesive layers for digital printing require durability such as adhesion between the adhesive layer and printing media, adhesion between the adhesive layer and the ink layer, and water resistance and solvent resistance of the adhesive layer. be done.
  • the polyurethane resin and the cross-linking agent undergo a cross-linking reaction to improve adhesion between the adhesive layer and the printing medium, and durability such as water resistance and solvent resistance of the adhesive layer. can be improved.
  • the cross-linking fixes the state in which the adhesive layer is in close contact with the printing medium, and has the effect of suppressing the intrusion of water and solvents.
  • the reaction between the cross-linking agent contained in the adhesive layer and the resin contained in the ink layer and/or the improvement in chemical affinity between the two can improve the adhesion between the adhesive layer and the ink layer. can.
  • the water-based resin composition used for the adhesive layer for digital printing has liquid stability during transportation and storage, and also liquid stability when the liquid used once is repeatedly used afterwards. Desired.
  • the former it is necessary to suppress changes in liquid properties such as an increase in liquid viscosity, gelation, and an increase in the particle size of resin particles due to the reaction between the polyurethane resin and the cross-linking agent. If such a change in liquid property occurs, it may not be possible to coat uniformly during coating, the coating film thickness may not be constant, or the liquid property may deviate from the appropriate liquid property for coating, and the coating itself may not be possible. have a nature.
  • the latter includes not only the reuse of the residual liquid after it has been used for coating, but also the mixing of the residual liquid and the new liquid. In these cases, it is necessary that the liquid property, coating quality, and performance as an adhesive layer after coating do not deteriorate as compared with the case of using a completely new liquid. When these performances deteriorate and the residual liquid becomes unusable, it must be discarded, which is disadvantageous in terms of cost.
  • the aqueous resin composition of the present invention exhibits good liquid stability during transportation, storage, and repeated use.
  • the reason for this is presumed as follows.
  • the carboxylate group-containing polyurethane resin used in the present invention is dispersed in the form of particles in the coating liquid and is stabilized by counter ions and an amine compound.
  • a cross-linking agent having a carbodiimide group usually reacts with a carboxylate group at room temperature. By being spatially and electrically repulsively isolated from the resin, the cross-linking reaction in the liquid is minimized, and at least the cross-linking between the polyurethane resin particles in the liquid is suppressed, so the liquid stability is enhanced. Conceivable.
  • the non-volatile component concentration of the aqueous resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. On the other hand, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
  • the concentration of non-volatile components means the ratio (% by mass) of the total amount of components that are solid at 25°C and components that are liquid at 25°C and have a boiling point of 150°C or higher to the total amount of the aqueous resin composition. .
  • the viscosity of the aqueous resin composition of the present invention is preferably 1 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more, and even more preferably 10 mPa ⁇ s or more. On the other hand, it is preferably 200 mPa ⁇ s or less, more preferably 100 mPa ⁇ s or less, and even more preferably 50 mPa ⁇ s or less.
  • the viscosity of the aqueous resin composition is the viscosity at 25°C.
  • the viscosity of the aqueous resin composition can be measured using, for example, a Brookfield viscometer.
  • the polyurethane resin contained in the aqueous resin composition of the present invention examples include water-soluble polyurethane resins and dispersible polyurethane resins. Dispersible polyurethane resin is preferred from the viewpoint of performance and liquid stability.
  • “dispersible” means water-dispersible or suspendable, and means water-insoluble. That is, it is preferable that the polyurethane resin is stably dispersed as particles in the aqueous resin composition of the present invention.
  • the polyurethane resin is preferably self-dispersible.
  • the polyurethane resin is obtained by chain-extending polyurethane obtained by reacting polyol and polyisocyanate with a low-molecular-weight compound having two or more active hydrogens such as diol, diamine, and dicarboxylic acid. preferable.
  • a polyurethane resin using a polyol component having a carboxylate group is preferably used as part of the polyol component.
  • by neutralizing the carboxylate group with a basic component good dispersibility in water can be maintained.
  • the polyurethane resin is preferably a polyether polyurethane resin from the viewpoint of adhesion to various printing media and smoothness during coating. Among them, a saturated hydrocarbon-based polyether polyurethane resin is more preferable.
  • the polyurethane resin is a polyether polyurethane resin, preferably a saturated hydrocarbon-based polyether polyurethane resin.
  • polyol examples of polyhydric alcohols that are precursors of polyol components include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane.
  • propylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and cyclohexanedimethanol are preferred from the viewpoint of adhesion to polyolefin-based printing media, and 1,6-hexanediol and cyclohexane are preferred. Dimethanol is more preferred.
  • These polyhydric alcohols may be used alone or in combination of two or more.
  • polyester polyol, polyether polyol, and polycarbonate polyol are preferable from the viewpoint of durability such as water resistance, and among them, polyether polyol and polycarbonate polyol are more preferable.
  • Polyether polyols are more preferred. These polyols can be used alone or in combination of two or more.
  • polyether polyols examples include saturated hydrocarbon polyether polyols obtained by addition polymerization of saturated hydrocarbon alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to the above polyhydric alcohols, and aromatic compounds such as styrene oxide. and aromatic polyether polyols obtained by addition polymerization of alkylene oxides.
  • saturated hydrocarbon-based polyether polyols are preferable from the viewpoint of adhesion to polyolefin-based printing media.
  • saturated hydrocarbon-based polyether polyols examples include polyethylene glycol, polypropylene glycol, and poly(1,6-hexanediol). Among these, polyethylene glycol and polypropylene glycol are preferred, and polypropylene glycol is more preferred, from the viewpoint of ease of production and flexibility.
  • polycarbonate polyols examples include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, polydecamethylene carbonate diol, poly-3-methyl-1,5-pentane carbonate diol, and poly-1,4-cyclohexanedimethylene carbonate diol. etc. Among these, polytetramethylene carbonate diol and polyhexamethylene carbonate diol are preferable from the viewpoint of durability.
  • polyisocyanate examples include saturated hydrocarbon diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and 4,4′-methylenebis(cyclohexylisocyanate); aromatic diisocyanates such as metaxylene diisocyanate and tolylene diisocyanate; Examples include saturated hydrocarbon diisocyanates and reaction products of these compounds with polyhydric alcohols. Among these, saturated hydrocarbon-based diisocyanates are preferred from the viewpoint of adhesion to various printing media. In addition, these can be used individually or in combination of 2 or more types.
  • an acid value (amount of potassium hydroxide required for neutralization, unit: mgKOH/g) can be used.
  • the acid value of the polyurethane resin of the present invention is preferably 2 mgKOH/g or more, more preferably 5 mgKOH/g or more, and even more preferably 10 mgKOH/g or more. On the other hand, it is preferably 50 mgKOH/g or less, more preferably 20 mgKOH/g or less, and even more preferably 15 mgKOH/g or less.
  • the acid value is at least the above lower limit, cross-linking after coating and drying proceeds easily.
  • the acid value is equal to or less than the upper limit, an increase in the particle size of the polyurethane resin particles and an increase in the viscosity of the coating liquid can be suppressed.
  • the carboxylate groups possessed by the polyurethane resin of the present invention may have hydrogen ions as counter ions in a state of being dispersed in water. may have. Therefore, the acid value of the polyurethane resin of the present invention is determined by volatilizing the ammonia or amine compound from the aqueous dispersion of the polyurethane resin to make the counter ions of the carboxylate groups completely hydrogen ions, and then volatilizing the water to remove the resin. It can be measured quantitatively by drying, completely dissolving the dried resin in a solvent, and titrating with an aqueous solution of potassium hydroxide (KOH). Examples of the solvent that can be used include ethanol, isopropanol, and acetone.
  • KOH potassium hydroxide
  • the carboxylate groups of the polyurethane resin of the present invention may have hydrogen ions or quaternary ammonium ions as counter ions when dispersed in water.
  • the polyurethane resin of the present invention may have carboxyl groups or ammonium carboxylate groups in the state of being dispersed in water.
  • Polyurethane resins having ammonium carboxylate groups can be produced, for example, by using ammonia as a neutralizing agent during production.
  • the water-based resin composition of the present invention is required to have uniform film-forming properties after coating.
  • the particle diameter of the polyurethane resin particles is preferably 200 nm or less, more preferably 100 nm or less. More preferably, it is 50 nm or less.
  • the content of the polyurethane resin of the present invention in the aqueous resin composition is preferably 18% by mass or more, more preferably 20% by mass or more. On the other hand, it is preferably 35% by mass or less, more preferably 30% by mass or less.
  • the content of the polyurethane resin is at least the above lower limit, it is possible to prevent deterioration of adhesion and durability due to insufficient drying after coating. If the content of the polyurethane resin is equal to or less than the above upper limit, the liquid stability will be good.
  • a cross-linking agent contained in the aqueous resin composition of the present invention a cross-linking agent containing at least two carbodiimide groups per molecule is used from the viewpoint of safety to the human body and low-temperature reactivity. If the number of carbodiimide groups is less than 2 per molecule, the carboxylate groups of the polyurethane resin cannot be sufficiently crosslinked, making it difficult to obtain desired performance.
  • the cross-linking agent is preferably not completely water-soluble, and preferably has a micellar structure surrounded by sterically bulky hydrophilic groups. . Since the cross-linking agent has a bulky structure that causes steric hindrance, it is possible to reduce the chance of contact with the polyurethane resin.
  • a known carbodiimide compound can be used as the cross-linking agent in the aqueous resin composition of the present invention.
  • the carbodiimide compound can be obtained, for example, by synthesizing an isocyanate-terminated polycarbodiimide compound by a condensation reaction involving decarbonation of an organic diisocyanate compound, and then reacting the highly hydrophilic organic compound with the isocyanate terminus.
  • highly hydrophilic organic compounds include polyalkylene oxides terminally blocked with an alkoxy group or phenoxy group, dialkylamino alcohols, hydroxycarboxylic acid alkyl esters, dialkylaminoalkylamines, and alkylsulfonates.
  • a polyalkylene oxide terminally blocked with an alkoxy group or a phenoxy group is preferable from the viewpoint of spatially isolating the carbodiimide groups from the polyurethane resin by stable micelle formation in water.
  • stable micelles with a particle size of about 10 nm covered with hydrophilic groups are formed, and good liquid stability is exhibited.
  • the carbodiimide compound is preferably polycarbodiimide obtained by polymerizing two or more molecules of a diisocyanate compound. Further, aliphatic or aromatic carbodiimide compounds are preferred, and aliphatic carbodiimide compounds are more preferred.
  • the degree of polymerization of the carbodiimide compound is preferably 2 or more. On the other hand, the degree of polymerization of the carbodiimide compound is preferably 100 or less, more preferably 10 or less.
  • Polymerized units of aliphatic carbodiimide compounds include 4,4'-dicyclohexylmethanecarbodiimide, diisophoronemethanecarbodiimide, cyclohexylcarbodiimide, isopropylcarbodiimide, methylcarbodiimide, isobutylcarbodiimide, octylcarbodiimide, t-butylcarbodiimide, and the like.
  • Polymerization units of aromatic carbodiimide compounds include phenylcarbodiimide, ⁇ -naphthylcarbodiimide, tetramethylxylylenecarbodiimide, and the like. Among these, tetramethylxylylenecarbodiimide is preferred from the viewpoint of low toxicity and liquid stability.
  • These carbodiimide compounds may be used alone or in combination of two or more.
  • (Carbodiimide group equivalent) (chemical formula weight of structural unit of carbodiimide compound per mole of carbodiimide group) (unit: mol -1 ) It means that the smaller the carbodiimide group equivalent, the larger the amount of carbodiimide groups contained in one molecule, and conversely, the larger the carbodiimide group equivalent, the smaller the amount of carbodiimide groups contained in one molecule. .
  • the carbodiimide group equivalent of the cross-linking agent is preferably 300 mol -1 or more, more preferably 400 mol -1 or more, and still more preferably 500 mol ⁇ 1 or more. On the other hand, it is preferably 800 mol -1 or less, more preferably 700 mol -1 or less.
  • the carbodiimide group equivalent is at least the lower limit, the liquid stability is improved. If the carbodiimide group equivalent is equal to or less than the upper limit, the crosslinkability is improved.
  • the carbodiimide group equivalent of the cross-linking agent is 400 mol -1 or more and 700 mol -1 or less, preferably 500 mol -1 or more and 700 mol -1 or less.
  • the content of the cross-linking agent in the aqueous resin composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more. On the other hand, it is preferably 10% by mass or less, more preferably 5% by mass or less.
  • the content of the cross-linking agent is at least the above lower limit value, sufficient cross-linking is achieved and adhesion and durability are improved.
  • the content of the cross-linking agent is equal to or less than the upper limit, the liquid stability is improved.
  • the aqueous resin composition has a molar ratio of carbodiimide groups of the cross-linking agent to carboxylate groups of the polyurethane resin of 0.1 or more and 5.0 or less.
  • the molar ratio is 5.0 or less, that is, when the amount of carbodiimide groups is not too large relative to the amount of carboxylate groups, the liquid stability of the aqueous resin composition is excellent, and the non-printing portion to the contact member during printing. Contamination such as adhesion due to migration of the carbodiimide compound and deterioration in the quality of printed images caused thereby are prevented.
  • the molar ratio of the carbodiimide groups of the cross-linking agent to the carboxylate groups of the polyurethane resin is 0.1 or more, preferably 0.2 or more, and more preferably 0.3 or more. More preferably, 0.5 or more is even more preferable. On the other hand, it is 5.0 or less, preferably 3.0 or less, more preferably 2.0 or less, further preferably 1.5 or less, and particularly preferably 1.0 or less.
  • the aqueous resin composition has a molar ratio of carbodiimide groups of the cross-linking agent to carboxylate groups of the polyurethane resin of 0.1 or more and 2.9 or less. Among them, 0.2 or more is preferable, 0.3 or more is more preferable, and 0.5 or more is even more preferable. On the other hand, it is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.0 or less.
  • the aqueous resin composition has a molar ratio of carbodiimide groups of the cross-linking agent to carboxylate groups of the polyurethane resin of 0.4 or more.
  • 0.5 or more is preferable.
  • it is preferably 5.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, particularly preferably 1.5 or less, and particularly preferably 1.0 or less.
  • the carboxylate group weight of the polyurethane resin can be converted from the acid value described above, and the carbodiimide group weight of the cross-linking agent can be converted from the carbodiimide group equivalent weight described above.
  • the content ratio (mass ratio) of the cross-linking agent to the polyurethane resin is preferably 0.010 or more, more preferably 0.030 or more, from the viewpoint of adhesion and durability. On the other hand, it is preferably 0.400 or less, more preferably 0.200 or less, even more preferably 0.150 or less, and particularly preferably 0.100 or less, from the viewpoint of liquid stability, member contamination, and image quality.
  • the aqueous resin composition contains an amine compound.
  • the aqueous resin composition preferably contains an amine compound.
  • the amine compound contained in the aqueous resin composition of the first embodiment of the present invention has a pKb of 3.5 or more and 4.7 or less. Among them, 4.0 or more is preferable, while 4.5 or less is preferable, and 4.2 or less is more preferable.
  • the amine compound contained in the aqueous resin composition of the second and third embodiments of the present invention preferably has a pKb of 3.5 or more and 5.0 or less. Among them, it is more preferably 4.0 or more, while it is more preferably 4.7 or less, further preferably 4.5 or less, and particularly preferably 4.2 or less.
  • pKb means base dissociation constant, and is generally used as an indicator of base strength. A smaller pKb value indicates a stronger base.
  • Ammonia (pKb: 4.75) is usually preferably used as a neutralizing agent when producing a polyurethane resin dispersion.
  • the aqueous resin composition of the present invention preferably contains, separately from this, an amine compound added during the production of the aqueous resin composition.
  • an amine compound added during the production of the aqueous resin composition.
  • ammonia is highly volatile, even if it is used during the production of the polyurethane resin dispersion, it tends to disappear outside the aqueous resin composition during the production of the aqueous resin composition.
  • the polyurethane resin is not neutralized, resulting in a decrease in self-dispersibility, which contributes to a decrease in liquid stability. Therefore, when an amine compound is added during the production of the aqueous resin composition, the amine compound stably protects the carboxylate groups of the polyurethane resin, or forms hydrogen bonds with urethane bonding groups, etc., thereby allowing the polyurethane resin to remain in the liquid. Be able to distribute stably.
  • the presence of the amine compound in the form of an electric double layer around the dispersed polyurethane resin particles causes electrical repulsion with the carbodiimide group-containing cross-linking agent in the liquid, and the polyurethane resin in the liquid.
  • the effect of lowering the reaction rate between and the cross-linking agent can also be obtained.
  • the pKb of the amine compound is smaller than the lower limit, it is not preferable in terms of safety to the human body. If the pKb is higher than the upper limit, the liquid stabilization effect may be reduced.
  • the boiling point of the amine compound is preferably 130°C or higher, more preferably 151°C or higher. If the boiling point is 130° C. or higher, the odor is less likely to leak during printing, and when used in a printing machine having a mechanism for recovering and reusing the solvent, the recovered solvent is mixed with an amine compound and an odor is generated. It is possible to suppress the deterioration of print quality.
  • Suitable amine compounds include monoethanolamine (pKb: 4.56, boiling point: 170°C), N,N-diethylethanolamine (pKb: 4.13, boiling point: 163°C), 2-amino-2 -methyl-1-propanol (pKb: 4.70, boiling point: 165.5°C), 2-(dimethylamino)ethanol (pKb: 4.77, boiling point: 133°C), and the like.
  • N,N-diethylethanolamine and 2-amino-2-methyl-1-propanol are preferred, and N,N-diethylethanolamine is more preferred, from the viewpoint of odor and liquid stability.
  • These amine compounds may be used alone or in combination of two or more.
  • the content of the amine compound in the aqueous resin composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. On the other hand, it is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • the content of the amine compound is at least the above lower limit, the liquid stability effect is enhanced.
  • the content of the amine compound is equal to or less than the above upper limit, it is preferable from the viewpoint of safety to the human body.
  • the content ratio (mass ratio) of the amine compound to the polyurethane resin is preferably 0.01 or more, more preferably 0.02 or more.
  • the content ratio (mass ratio) of the amine compound to the polyurethane resin is preferably 0.01 or more, more preferably 0.02 or more.
  • it is preferably 0.1 or less, more preferably 0.06 or less.
  • the content ratio (mass ratio) of the amine compound to the cross-linking agent is preferably 0.01 or more, more preferably 0.02 or more.
  • it is preferably 0.3 or less, more preferably 0.2 or less.
  • the aqueous resin composition of the present invention further contains a surfactant.
  • surfactants specifically, anionic surfactants, cationic surfactants, and nonionic surfactants can be used. Among them, nonionic surfactants are preferred from the viewpoint of liquid stability.
  • nonionic surfactants include polyethylene glycol fatty acid esters, sorbitan fatty acid esters, sorbit fatty acid esters, glycerin fatty acid esters, pentaerythritol fatty acid esters, POE alkyl ethers, POE alkylphenyl ethers, POE acetylene glycols, tetraPOE/tetra POP ethylenediamine condensates, POE castor oil hydrogenated castor oil derivatives, POE beeswax derivatives, POE lanolin derivatives, alkanolamides and the like can be mentioned. These nonionic surfactants can be used alone or in combination of two or more.
  • POE alkylphenyl ethers POE acetylene glycols, and tetraPOE/tetraPOP ethylenediamine condensates are preferable, and POE acetylene glycols are more preferable, from the viewpoint of dispersion stability as an aqueous resin composition.
  • POE is an abbreviation for "polyoxyethylene”
  • POP is an abbreviation for "polyoxypropylene”.
  • the number average molecular weight of the surfactant is preferably 400 or more and 3000 or less.
  • the content of the surfactant in the aqueous resin composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. On the other hand, it is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less.
  • the content of the surfactant is at least the above lower limit, the uniformity and adhesion of the coating film are improved.
  • the content of the surfactant is equal to or less than the above upper limit value, the liquid stability is improved.
  • the content ratio (mass ratio) of the surfactant to the polyurethane resin is preferably 0.001 or more, more preferably 0.005 or more, from the viewpoint of uniformity and adhesion during drying. On the other hand, from the viewpoint of liquid stability, it is preferably 0.1 or less, more preferably 0.05 or less.
  • the content ratio (mass ratio) of the surfactant to the cross-linking agent is preferably 0.01 or more, more preferably 0.02 or more, from the viewpoint of coating homogeneity of the cross-linking agent. On the other hand, it is preferably 0.5 or less, more preferably 0.3 or less, from the viewpoint of the stability of the cross-linking agent in liquid.
  • the "aqueous resin composition” in the present invention means a composition containing a resin and an aqueous medium.
  • the "aqueous coating liquid” in the present invention means a coating liquid containing an aqueous medium.
  • the aqueous medium is water and/or a water-soluble organic solvent.
  • the aqueous medium used in the present invention preferably contains only water, that is, does not contain a water-soluble organic solvent.
  • a water-soluble organic solvent in the present invention means a compound having solubility in water.
  • solubility of the water-soluble organic solvent in water is not limited, compounds that can be dissolved in water at any ratio are preferred.
  • it can be used as a solvent by being uniformly mixed with water. For example, it is included in a water-soluble organic solvent.
  • Water-soluble organic solvents include methanol, ethanol, propanol, ethylene glycol, propylene glycol, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, N-methylpyrrolidone, N,N-dimethylformamide and the like. These water-soluble organic solvents may be used alone or in combination of two or more.
  • the aqueous resin composition of the present invention contains antioxidants, antifungal agents, ultraviolet absorbers, dispersing aids, wetting agents (moisturizing agents), fixing agents, pH adjusters, Thickeners, colorants, deodorants, perfumes and the like can be added.
  • a known production method can be applied to the production of the aqueous resin composition of the present invention.
  • a method for producing the aqueous resin composition of the present invention it is preferable to first prepare a polyurethane resin dispersion, add a cross-linking agent and an amine compound thereto, and mix them.
  • the method for producing the polyurethane resin dispersion is not particularly limited, it is preferably produced through a prepolymer production process, an emulsification process, and a chain elongation process. At that time, it is preferable to use a neutralizing agent in order to neutralize the carboxylate groups in the polyurethane structure in the emulsification step and express the self-emulsifiability.
  • a neutralizing agent it is preferable to use ammonia or an amine compound, and among them, it is preferable to use ammonia.
  • a known technique can be applied to the mixing technique in the production of the aqueous resin composition of the present invention.
  • a stirring and mixing method using a general anchor blade or turbine blade, a homogenizer, a homomixer, an attritor, a sand grinder, or a dispersive mixing method such as high-pressure liquid impingement that applies a shearing force can be used.
  • a method of stirring and mixing without application of shearing force is preferable.
  • the temperature at which each raw material is mixed in the production of the aqueous resin composition is preferably 10°C or higher and 40°C or lower, more preferably 15°C or higher and 30°C or lower.
  • the water-based resin composition of the present invention is applied, for example, to a part or the entire surface of a printing medium in order to form an adhesive layer before printing, that is, before ink or toner is applied.
  • an adhesive layer before printing that is, before ink or toner is applied.
  • rubber roll coating, die coating, micro gravure coating, slit reverse coating, anilox roll coating and the like are preferably used for forming a uniform coating film at high speed.
  • drying temperature is set according to the appropriate blowing intensity setting or the heat resistance of the printing media.
  • the drying temperature is preferably 50°C or higher, more preferably 60°C or higher.
  • 80° C. or lower is preferable, and 70° C. or lower is more preferable.
  • the film thickness of the adhesive layer after drying is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 0.15 ⁇ m or more. On the other hand, it is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.6 ⁇ m or less.
  • Printing media to be coated or printed include metal substrates such as aluminum, nickel, stainless steel, steel, and magnesium; polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyurethane, polyvinyl chloride, thermoplastic elastomers; Flexible substrates; laminates thereof with aluminum foil, evaporated aluminum, evaporated silicon oxide; glass or natural materials; paper coated with resin such as polyethylene coated paper; In the case of a flexible substrate, it may be an elongated body, a porous body, a foamed body, or the like.
  • the ink or toner used for printing preferably contains a resin having a carboxy group.
  • the resin having a carboxyl group is the main component of the ink or toner.
  • the “main component” means that 50% by mass or more of the resin contained in the ink or toner is the resin.
  • Examples of the resin having a carboxyl group include poly(ethylene/methacrylic acid) resins, poly(ethylene/acrylic acid) resins, polyester resins, poly(styrene/acrylic acid) resins, and polymethyl acrylate resins. Among them, poly(ethylene/methacrylic acid) resins and poly(ethylene/acrylic acid) resins are preferred.
  • the softening point of the resin having a carboxyl group is preferably 120°C or lower, more preferably 100°C or lower, from the viewpoint of fixing to various printing media.
  • the softening point is 120° C. or lower, problems such as heat deformation or heat melting of the print medium can be suppressed when the ink is fixed on the print medium.
  • the carrier liquid for the ink it is preferable to use a high-boiling aliphatic hydrocarbon-based organic solvent with a boiling point of about 200°C.
  • the aqueous resin composition of the present invention is used, for example, in an electrophotographic digital printer as shown in FIG. 1, and printed to produce a printed matter after an adhesive layer is formed with the aqueous resin composition.
  • a digital printing press is formed from, for example, a printing media unwinding unit 10, an adhesive layer coating unit 1, a printing unit 2, a printing press control unit 100, and a printing media take-up unit 111.
  • a printing method using the digital printer shown in FIG. 1 will be described below.
  • the printing medium 11 unwound from the printing medium unwinding unit 10 is subjected to corona treatment in the corona treatment unit 12 in the adhesive layer coating unit 1 to correct the surface energy to be suitable for printing.
  • the water-based resin composition is applied onto the printing medium 11 from the coating bath 13 containing the water-based resin composition 14 via the coating rolls 15 to 17, and dried in the drying unit 18 to obtain a predetermined film thickness.
  • An adhesive layer is formed.
  • the digital image data of the printer control unit 100 is converted into a light pattern by the exposure device 102, and the photosensitive member 105, which has been uniformly charged by the charging device 101 in advance, is irradiated with the light pattern.
  • the electrostatic latent image thus formed is developed on the photosensitive member 105 by the developing device 104 with ink, which is the developer supplied from the developer tank 103 .
  • the developer developed on the photosensitive member 105 is primarily transferred to the intermediate transfer member 107 by electrostatic force. After the developer is transferred to the intermediate transfer member 107, the photosensitive member 105 is cleaned by the cleaning device 106 to remove excess developer, and the next image formation is started.
  • the developer primarily transferred from the photosensitive member 105 onto the intermediate transfer member 107 is dried and melted by the internal heater 109 and the external heater 108 of the intermediate transfer member 107, and the pressure roller 110 forms the printing medium 11 on which the adhesive layer is formed.
  • a desired image is formed thereon by secondary transfer and fixation, and the printed material is taken up by the print media take-up unit 111 .
  • a solvent (carrier liquid) generated during drying of the ink used in the printing machine may be recovered in the machine and reused. At that time, it is necessary that the components of the aqueous resin composition of the present invention are not mixed into the recovered carrier liquid, and it is particularly important that the amine compound is not mixed.
  • an image forming method of a digital printing method in which an adhesive layer is formed by coating an aqueous resin composition on a printing medium and then an ink layer is formed with an ink, wherein the aqueous resin composition contains carboxyl
  • the durability, particularly solvent resistance, of printed matter after coating is improved.
  • An adhesive layer can be formed by coating the aqueous resin composition of the present invention on a printing medium and drying by heating. Furthermore, a printed matter can be obtained by applying ink on the adhesive layer or by drying after transfer to form an ink layer.
  • the adhesive layer has a crosslinked structure of a polyurethane resin having a carboxylate group and a crosslinking agent having a carbodiimide group. This makes it possible to develop durability, particularly solvent resistance, in printed matter.
  • the carbodiimide groups of the adhesive layer and the carboxyl groups of the resin of the ink layer are allowed to react with each other by contacting and partially mixing with the adhesive layer to form a crosslinked structure. may Thereby, the adhesion between the adhesive layer and the ink layer can be improved.
  • aqueous resin composition 1 777.1 g of a saturated hydrocarbon-based polyether polyurethane resin dispersion (product name: NeoRez R600, manufactured by DSM, solid content: 33%, acid value: 13 mgKOH/g, ammonia is used as a neutralizing agent during production); 80.1 g of an aliphatic carbodiimide compound (a mixture of Carbodilite SV-02 (trade name) and Carbodilite V-02-L2 (trade name) shown below at a mass ratio of 3:1) and N,N-diethylethanolamine as an amine compound (abbreviation DEEA, pKb: 4.13) 6.5 g, Surfynol 465 (abbreviation S465, manufactured by Nissin Chemical Industry Co., Ltd.) 5.0 g having a structure represented by the following formula (1) as a surfactant, and dilution water 131.3 g were mixed to produce 1000 g of aqueous
  • Carbodilite SV-02 manufactured by Nisshinbo Chemical Co., Ltd., solid content 40%, carbodiimide group equivalent 430 mol -1
  • Carbodilite V-02-L2 manufactured by Nisshinbo Chemical Co., Ltd., solid content 40%, carbodiimide group equivalent 385 mol -1
  • aqueous resin composition 2 Aqueous resin composition 1 except that the aliphatic carbodiimide compound was changed to 80.1 g of a mixture of the following trade name Carbodilite V-02 and trade name Carbodilite V-02-L2 at a mass ratio of 3: 1. 1000 g of aqueous resin composition 2 was produced in the same manner as in the production.
  • Carbodilite V-02 manufactured by Nisshinbo Chemical Co., Ltd., solid content 40%, carbodiimide group equivalent 590 mol -1
  • Carbodilite V-02-L2 manufactured by Nisshinbo Chemical Co., Ltd., solid content 40%, carbodiimide group equivalent 385 mol -1
  • aqueous resin composition 5 was produced in the same manner as the aqueous resin composition 4, except that the amine compound was changed to 6.5 g of N,N-dimethylethanolamine (abbreviation DMEA, pKb: 4.77). .
  • DMEA N,N-dimethylethanolamine
  • Aqueous resin compositions 11 to 14 were produced in an amount of 1000 g each in the same manner as the aqueous resin composition 1, except that the amount of each material added was changed to the amount shown in Table 1B.
  • aqueous resin composition 15 1000 g of an aqueous resin composition 15 was produced in the same manner as the aqueous resin composition 1, except that no amine compound was used and the amounts of other materials added were changed to the amounts shown in Table 1B.
  • aqueous resin composition 16 1000 g of aqueous resin composition 16 was produced in the same manner as aqueous resin composition 4, except that no amine compound was used and the amounts of other materials added were changed to the amounts shown in Table 1B.
  • aqueous resin composition 17 Aqueous resin composition 4 except that the amine compound was changed to N,N,N-triethanolamine (abbreviation TETA, pKb: 6.23) and the amount of each material added was changed to the amount shown in Table 1B. 1000 g of aqueous resin composition 17 was produced in the same manner as in the production.
  • TETA N,N,N-triethanolamine
  • aqueous resin composition 20 1000 g of an aqueous resin composition 20 was produced in the same manner as the aqueous resin composition 1, except that no cross-linking agent was used and the amount of each material added was changed to the amount shown in Table 1B.
  • aqueous resin composition 21 656.3 g of polyurethane resin dispersion containing aromatic polyester polyol as one of raw materials (trade name: Hydran AP201, manufactured by DIC Corporation, solid content: 23%, acid value: 25 mgKOH/g, triethylamine used as a neutralizing agent during production) and 218.9 g of an aliphatic carbodiimide compound (a mixture of the trade name Carbodilite SV-02 and the trade name Carbodilite V-02-L2 in a mass ratio of 1:1) as a cross-linking agent, and the surfactant of the formula (1 ) and 113.3 g of dilution water were mixed to prepare 1000 g of aqueous resin composition 21.
  • an aliphatic carbodiimide compound a mixture of the trade name Carbodilite SV-02 and the trade name Carbodilite V-02-L2 in a mass ratio of 1:1
  • aqueous resin composition 22 1000 g of an aqueous resin composition 22 was produced in the same manner as the aqueous resin composition 1, except that no surfactant was used and the amount of each material added was changed to the amount shown in Table 1B.
  • ⁇ Adhesion evaluation> The water-based resin composition obtained in the experimental example was coated on a BOPP film (film thickness: 20 ⁇ m, corona-treated, surface free energy: 38 mN/m or more) and a PET film (film thickness: 12 ⁇ m) using a bar coater. , air-dried, and further dried at 50° C. for 10 seconds to prepare an adhesive layer having a thickness of about 1 ⁇ m.
  • a black ink containing poly(ethylene/methacrylic acid) resin (trade name N1050H, manufactured by Dow Mitsui Polychemicals, softening point 95° C.) was applied on the adhesive layer to a film thickness of about 5 ⁇ m after drying. and dried at 60° C.
  • a masking tape manufactured by 3M, product name: Scotch (registered trademark) Mending Tape 810 was used for the obtained sample for evaluation, and a tape peeling test was performed in accordance with ASTM D3330 to check adhesion. Evaluation was made according to the criteria described later.
  • ⁇ Liquid stability evaluation (viscosity evaluation after storage)>
  • the aqueous resin composition obtained in the experimental example is placed in an oven at 40 ° C. and stored for 14 days, then taken out and left to stand, the aqueous resin composition is returned to room temperature, and the viscosity is measured with a B-type viscometer. The viscosity was measured and compared with the viscosity before heating, and the liquid stability was evaluated according to the criteria described later.
  • ⁇ Adhesion evaluation when using aqueous resin composition after storage> The aqueous resin composition obtained in the experimental example is placed in an oven at 40 ° C. and stored for 14 days, then taken out and left to stand, the aqueous resin composition is returned to room temperature, and the aqueous resin composition is used.
  • An evaluation sample was prepared in the same manner as in the adhesion test, and the adhesion to the BOPP film and PET film was evaluated according to the criteria described later.
  • the aqueous resin composition of the first embodiment of the present invention is applied to a printing medium to form an adhesive layer, and when printing is performed thereon, the printing medium and the adhesive layer, Also, it was found that the adhesion between the adhesive layer and the ink layer was good, the durability of the printed matter was good, and the image quality was also good. Further, even when the aqueous resin composition was stored at a high temperature, the aqueous resin composition did not increase in viscosity, and the adhesion of the printed matter was good even when applied after storage. Also, the odor during printing was at a level that did not pose a problem.
  • the aqueous resin composition of the second embodiment of the present invention is applied to a printing medium to form an adhesive layer, and when printing is performed thereon, the printing medium and the adhesive layer, Also, it was found that the adhesion between the adhesive layer and the ink layer was good, the durability of the printed matter was good, and the image quality was also good. Further, even when the aqueous resin composition was stored at a high temperature, the viscosity of the aqueous resin composition did not increase.
  • the aqueous resin composition of the third embodiment of the present invention is applied to a printing medium to form an adhesive layer, and when printing is performed thereon, the printing medium and the adhesive layer, Also, it was found that the adhesion between the adhesive layer and the ink layer was good, the durability of the printed matter was good, and the image quality was also good. Further, even when the aqueous resin composition was stored at a high temperature, the viscosity of the aqueous resin composition did not increase.
  • the water-based resin composition of the present invention is used for food and industrial applications such as painted/printed materials such as signs, advertisements, posters, signage, menu tables, seal labels, shrink labels, pouches, bags, etc., which require water resistance and heat resistance. It is used in the manufacturing and processing of decorative films for packaging materials, electronic products, vehicles and aircraft, building materials, ornaments, smartphones, etc.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024162244A1 (ja) * 2023-01-31 2024-08-08 三菱ケミカル株式会社 水性樹脂組成物、画像形成方法、水系塗工液及び水性樹脂組成物の製造方法
JP7713077B1 (ja) 2024-09-30 2025-07-24 第一工業製薬株式会社 水系プライマー及び積層体

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001226444A (ja) * 2000-02-10 2001-08-21 Nippon Polyurethane Ind Co Ltd 水性ポリウレタン樹脂の製造方法
US7470736B2 (en) 2004-05-03 2008-12-30 Michelman, Inc. Primer coating for enhancing adhesion of liquid toner to polymeric substrates
JP2011042896A (ja) * 2009-08-20 2011-03-03 Nicca Chemical Co Ltd 皮革用材の製造方法及び皮革用材
WO2019131414A1 (ja) 2017-12-26 2019-07-04 Dic株式会社 水性樹脂組成物、それを用いた積層体及び物品
JP2020109152A (ja) * 2018-12-28 2020-07-16 日華化学株式会社 発泡体形成用組成物、発泡体、発泡体の製造方法及び皮革用材
JP2021176671A (ja) 2020-05-04 2021-11-11 スカイブレイン フェアメーゲンスフェアヴァルトゥング ゲーエムベーハーSkybrain Vermogensverwaltungs GmbH ワークピースを加工するための搬送装置及びシステム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001226444A (ja) * 2000-02-10 2001-08-21 Nippon Polyurethane Ind Co Ltd 水性ポリウレタン樹脂の製造方法
US7470736B2 (en) 2004-05-03 2008-12-30 Michelman, Inc. Primer coating for enhancing adhesion of liquid toner to polymeric substrates
JP2011042896A (ja) * 2009-08-20 2011-03-03 Nicca Chemical Co Ltd 皮革用材の製造方法及び皮革用材
WO2019131414A1 (ja) 2017-12-26 2019-07-04 Dic株式会社 水性樹脂組成物、それを用いた積層体及び物品
JP2020109152A (ja) * 2018-12-28 2020-07-16 日華化学株式会社 発泡体形成用組成物、発泡体、発泡体の製造方法及び皮革用材
JP2021176671A (ja) 2020-05-04 2021-11-11 スカイブレイン フェアメーゲンスフェアヴァルトゥング ゲーエムベーハーSkybrain Vermogensverwaltungs GmbH ワークピースを加工するための搬送装置及びシステム

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024162244A1 (ja) * 2023-01-31 2024-08-08 三菱ケミカル株式会社 水性樹脂組成物、画像形成方法、水系塗工液及び水性樹脂組成物の製造方法
JP7713077B1 (ja) 2024-09-30 2025-07-24 第一工業製薬株式会社 水系プライマー及び積層体
WO2026070186A1 (ja) * 2024-09-30 2026-04-02 第一工業製薬株式会社 水系プライマー及び積層体
JP2026061080A (ja) * 2024-09-30 2026-04-09 第一工業製薬株式会社 水系プライマー及び積層体

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