WO2012111360A1 - Composition de résine uréthanne aqueuse, et matériau de revêtement, adhésif, liant pour encre d'impression par jet d'encre, encre pour impression par jet d'encre et matière imprimée contenant chacun la composition de résine uréthanne aqueuse - Google Patents

Composition de résine uréthanne aqueuse, et matériau de revêtement, adhésif, liant pour encre d'impression par jet d'encre, encre pour impression par jet d'encre et matière imprimée contenant chacun la composition de résine uréthanne aqueuse Download PDF

Info

Publication number
WO2012111360A1
WO2012111360A1 PCT/JP2012/050261 JP2012050261W WO2012111360A1 WO 2012111360 A1 WO2012111360 A1 WO 2012111360A1 JP 2012050261 W JP2012050261 W JP 2012050261W WO 2012111360 A1 WO2012111360 A1 WO 2012111360A1
Authority
WO
WIPO (PCT)
Prior art keywords
urethane resin
ink
resin composition
group
mass
Prior art date
Application number
PCT/JP2012/050261
Other languages
English (en)
Japanese (ja)
Inventor
定 永浜
龍一 松岡
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2012524035A priority Critical patent/JP5062502B2/ja
Publication of WO2012111360A1 publication Critical patent/WO2012111360A1/fr

Links

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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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

Definitions

  • the present invention relates to an aqueous urethane resin composition that can be used in various fields including coating agents, adhesives, and inks for ink jet printing.
  • Coating agents and adhesives are required to be able to form films with excellent adhesion to various substrates.
  • water-based coating agents and adhesives are generally inferior in terms of adhesion compared to solvent-based coating agents and the like, and from the industry, they are excellent in substrate adhesion and environmental impact. Development of a small amount of water-based coating agent is required.
  • the plastic base material is acrylonitrile-butadiene-styrene resin (ABS resin).
  • ABS resin acrylonitrile-butadiene-styrene resin
  • PS resin polystyrene resin
  • PMMA resin polymethyl methacrylate resin
  • a metal base material is conventionally used in many cases, and as a conventional metal base material, a primer layer containing chromate or the like, generally referred to as chromate treatment, is provided. Many are used.
  • aqueous coating agents and adhesives having excellent adhesion to various plastic substrates and metal substrates as described above include, for example, cationic polyurethanes having a cationic group as a hydrophilic group in the molecular side chain.
  • a cationic polyurethane resin aqueous dispersion in which the resin (B) is dispersed in an aqueous medium is known (for example, see Patent Document 1).
  • the film formed using the aqueous coating agent or the like is not sufficient in terms of adhesion to inorganic base materials such as metals and various plastic base materials, and may cause peeling of the film over time. there were.
  • the ink has good ejection stability and storage stability. Scratch resistance at a level that can prevent discoloration and deterioration of the printed image due to missing pigment due to friction that can occur when external force is applied to the surface of the printed image without damaging, and glass cleaner In recent years, durability such as alkali resistance at a level that does not cause bleeding or discoloration of a printed image when various cleaning agents adhere to the surface of the printed image has been strongly demanded.
  • the ink having excellent scratch resistance is obtained by, for example, reacting an organic diisocyanate with a diol having a polyoxyethylene structure in an inkjet recording ink containing a pigment, an aqueous resin, and an aqueous medium.
  • An ink for inkjet recording which is a polyurethane resin, has a carboxyl group and has a specific acid value, a number average molecular weight, and a specific amount of the polyoxyethylene structure is known ( For example, see Patent Document 2.)
  • the image obtained by printing using the ink jet recording ink had a certain degree of scratch resistance, such as preventing the pigment from dropping off due to rubbing between papers.
  • an image obtained by printing using the ink jet recording ink has a problem in that, for example, when an alkaline cleaning agent or the like adheres to the surface, the printing surface is floated or smeared.
  • the ink for ink jet printing that can form a printed image that has both excellent scratch resistance and excellent alkali resistance without impairing the good ejection stability and storage stability of the ink is industrially
  • an ink for ink jet printing provided with the ink jet ink and a binder for ink jet printing ink that can be used for producing the ink have not yet been found.
  • the problem to be solved by the present invention is to provide an aqueous urethane resin composition having excellent adhesion to various substrates such as metal substrates and plastic substrates.
  • the problem to be solved by the present invention is an inkjet printing ink capable of forming a printed image having excellent durability such as scratch resistance and alkali resistance without impairing the good ejection stability of the ink. It is to provide a binder for ink jet and an ink for ink jet printing containing the binder.
  • the present inventors have an anionic group as a hydrophilic group and a tertiary amino group that is not substantially neutralized or quaternized in the molecular side chain. If it is a water-based urethane resin composition containing a urethane resin, the affinity between the substrate and the film is improved, and a water-based urethane resin composition capable of forming a film having excellent adhesion to various substrates is obtained. I found.
  • the present invention is an aqueous urethane resin composition containing a urethane resin (A) having an anionic group [X] and a tertiary amino group [Y] and an aqueous medium (B), wherein the urethane resin ( A) relates to a water-based urethane resin composition, a coating agent and an adhesive, wherein the side chain has a tertiary amino group [Y].
  • the present invention is an aqueous urethane resin composition containing a urethane resin (A) having an anionic group [X] and a tertiary amino group [Y] and an aqueous medium (B), wherein the urethane resin ( A) has a tertiary amino group [Y] in the side chain, and relates to an inkjet printing ink binder, an inkjet printing ink containing the binder, and a printed matter containing the binder.
  • A urethane resin having an anionic group [X] and a tertiary amino group [Y]
  • B aqueous medium
  • the aqueous urethane resin composition of the present invention has excellent adhesion to various plastic substrates and metal substrates not subjected to surface treatment such as chromate treatment. It can be used for various applications such as an agent.
  • the ink for inkjet printing includes the binder for inkjet printing ink of the present invention
  • the ink does not lose good ejection stability, and does not cause the pigment to fall off even when a strong external force is applied.
  • High-definition printed images can be maintained and durability such as scratch resistance comparable to silver salt photographs and excellent alkali resistance can be imparted.
  • photo printing by inkjet printing or high-speed printing by inkjet printing Can be used in various scenes such as outdoor advertising.
  • the present invention is an aqueous urethane resin composition containing a urethane resin (A) having an anionic group [X] and a tertiary amino group [Y], an aqueous medium (B), and other additives as required.
  • the urethane resin (A) has a tertiary amino group [Y] in the side chain.
  • the urethane resin (A) is stably dispersed or dissolved in the aqueous medium (B) by the hydrophilic group which is an anionic group [X].
  • a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used.
  • a part or all of the carboxyl group and the sulfonic acid group are basic. It is preferable to use a carboxylate group or a sulfonate group neutralized with a compound or the like in order to impart good dispersion stability.
  • the anionic group [X] is preferably present in the range of 15 mmol / kg to 4000 mmol / kg, and more preferably in the range of 15 mmol / kg to 2500 mmol / kg with respect to the entire urethane resin (A). More preferably, the range is from 15 mmol / kg to 2000 mmol / kg, and the range from 15 mmol / kg to 1500 mmol / kg is an aqueous urethane resin composition excellent in dispersion stability in the aqueous medium (B). It is more preferable for obtaining a coating agent, an adhesive, and a binder for ink jet printing ink.
  • the binder for inkjet printing inks when used as a binder for inkjet printing inks, it is more preferably in the range of 15 mmol / kg to 2000 mmol / kg, and still more preferably in the range of 15 mmol / kg to 1500 mmol / kg.
  • the urethane resin (A) it is important to use a resin having a tertiary amino group [Y] in the side chain in order to provide adhesion to various substrates.
  • the nitrogen atom constituting the tertiary amino group [Y] which is formed by using N-methyldiethanolamine or the like, mainly contains the polyol (a1 described later).
  • Polyisocyanate (a2), a chain extender, etc. are not present in the main chain structure containing a urethane bond formed by reaction, but it is appropriate to use those present in the side chain. .
  • the tertiary amino group [Y] may be a group in which a nitrogen atom constituting the tertiary amino group [Y] is directly bonded to the main chain, such as a vinyl polymer chain grafted to the main chain structure. It may be present in the side chain structure.
  • a tertiary amino group instead of the urethane resin (A), in an aqueous urethane resin composition containing a urethane resin in which a nitrogen atom constituting the tertiary amino group [Y] is present in the main chain structure, a tertiary amino group
  • the degree of freedom may be limited by the main chain structure, and may not be sufficient in terms of adhesion to the substrate.
  • the tertiary amino group [Y] which the said urethane resin (A) has is the said urethane resin (A), a pigment, etc. Improving the affinity is essential for imparting excellent ejection stability to the resulting ink and imparting excellent scratch resistance to the resulting printed image.
  • the presence of the tertiary amino group [Y] in the side chain of the urethane resin (A) can further improve the scratch resistance of the resulting printed image.
  • the tertiary amino group [Y] is not neutralized or quaternized with a compound having an acid group or a quaternizing agent, for example. Does not contribute.
  • the ionicity is used. Due to the interaction with the anionic group [X], which is a group, the dispersion stability of the urethane resin in the aqueous medium (B) is remarkably lowered, which may cause gelation or the like.
  • the dispersion stability of the urethane resin in the aqueous medium (B) is remarkably lowered, which may cause gelation or the like.
  • it when it is used as a binder for inkjet printing ink, it also causes a significant decrease in the water dispersion stability and ejection stability of the ink, and a decrease in the scratch resistance and alkali resistance of the resulting printed image. There is a case.
  • the tertiary amino group [Y] is not neutralized or quaternized by the compound having an acid group or a quaternizing agent.
  • this invention does not exclude the case where a part of tertiary amino group [Y] which exists in the said urethane resin (A) is neutralized etc.
  • the favorable water-based urethane resin composition obtained From the viewpoint of maintaining high stability 80 mol% to 100 mol% of the total amount of the tertiary amino group [Y] is neutralized or quaternized by a compound having an acid group acid group or a quaternizing agent. It is preferable that it is not converted.
  • the tertiary amino group [Y] is preferably present in the range of 30 mmol / kg to 5500 mmol / kg, and in the range of 80 mmol / kg to 4500 mmol / kg with respect to the entire urethane resin (A). It is more preferable when obtaining the water-based urethane resin composition which can form the film etc. provided with the outstanding base-material adhesiveness.
  • the aqueous urethane resin composition is used as a binder for ink jet printing ink, it is possible to use a resin having a tertiary amino group [Y] within the above range without impairing excellent ejection stability. It is preferable for forming a printed image having excellent scratch resistance and alkali resistance.
  • the urethane resin (A) has a weight average molecular weight of 5,000 to 500,000 for obtaining an aqueous urethane resin composition capable of forming a film excellent in durability such as alkali resistance and substrate adhesion.
  • aqueous urethane resin composition capable of forming a film excellent in durability such as alkali resistance and substrate adhesion.
  • aqueous urethane resin composition is used as a binder for ink jet printing inks, it is preferable to use a urethane resin (A) having a weight average molecular weight of 5,000 to 200,000.
  • a material having a viscosity of 15,000 to 150,000 and a material having a resistance of 15,000 to 60,000 has excellent scratch resistance and alkali resistance without impairing excellent ejection stability. It is particularly preferable for obtaining a binder for ink jet printing ink capable of forming a printed image.
  • the urethane resin (A) those having an acid value in the range of 2 to 200 are preferably used, and in the range of 2 to 100, the water dispersion stability of the urethane resin (A) is good. It is preferable for improving the properties. Further, when the urethane resin composition is used for a coating agent or an adhesive, it is preferable to use a resin having an acid value of about 2 to 30 as the urethane resin (A).
  • the urethane resin (A) has an acid value in the range of 2 to 100. It is preferable for improving the dispersion stability of (A), and it is more preferable to use in the range of 8 to 60.
  • the acid value is preferably derived from a carboxyl group or a carboxylate group as the anionic group [X].
  • the acid value said by this invention is the theoretical value computed based on the usage-amount of the compound which has acid groups, such as the polyol which has a carboxyl group used for manufacture of the said urethane resin (A).
  • the urethane resin (A) for example, from the viewpoint of further improving the adhesion to various types of substrates, one of the following urethane resins (A-1) and urethane resins (A-2) or It is preferable to use two or more.
  • the urethane resin (A-1) shown below is used to form a printed image having excellent scratch resistance and alkali resistance without impairing excellent ejection stability. It is preferable to use one or more of urethane resin (A-2).
  • urethane resin (A-1) among the urethane resin (A) having the anionic group [X] and the tertiary amino group [Y], a nitrogen atom constituting the tertiary amino group [Y] , Present in the side chain structure grafted to the main chain structure composed of urethane bonds and the like.
  • a resin having a structural unit represented by the following general formula [I] is preferably used as the urethane resin (A-1).
  • R 1 represents an alkylene group, a residue of a dihydric phenol, or a polyoxyalkylene group
  • R 2 and R 3 each independently represent an alkyl group that may contain an aliphatic cyclic structure. Represents.
  • the urethane resin (A-1) may contain 10 g / equivalent to 1000 g / equivalent as an amine equivalent of the structure represented by the general formula [I] with respect to the total amount of the urethane resin (A-1). In view of improving good water dispersion stability and adhesion to the substrate, it is preferable to contain 20 g / equivalent to 800 g / equivalent.
  • the aqueous urethane resin composition is used as a binder for ink jet printing inks, the water dispersion stability of the ink, durability such as alkali resistance and water resistance, and ink ejection stability are improved. In doing so, it is preferably used within the above range.
  • the urethane resin (A-1) can be produced, for example, by reacting a polyol (a1) with a polyisocyanate (a2) and, if necessary, a chain extender and the like. It can be produced by using a polyol containing a polyol (a1-2) having a tertiary amino group in the chain and a polyol (a1-1) having the anionic group [X].
  • the urethane resin (A-2) is a vinyl polymer with respect to a main chain structure containing a urethane bond in the urethane resin (A) having an anionic group [X] and a tertiary amino group [Y]. It has a side chain consisting of a structure, and the vinyl polymer structure has a tertiary amino group [Y].
  • the urethane resin (A-2) has a side chain composed of the vinyl polymer structure in an amount of 1% by mass to the total amount of the urethane resin (A-2) in order to provide excellent substrate adhesion. It is preferable to use those containing 70% by mass, and it is more preferable to use those containing 5% by mass to 50% by mass.
  • the aqueous urethane resin composition is used as a binder for inkjet printing inks, it is possible to achieve both improvement in durability such as alkali resistance and water resistance of the formed printed image and excellent ink ejection stability. Moreover, it is preferable to use within the said range.
  • the urethane resin (A-2) can be produced, for example, by reacting a polyol (a1) with a polyisocyanate (a2) and, if necessary, a chain extender, and the like as the polyol (a1).
  • a polyol (a1) with a polyisocyanate (a2) and, if necessary, a chain extender, and the like as the polyol (a1).
  • Uses containing a vinyl polymer (a1-3) having two hydroxyl groups at its ends and a tertiary amino group in the molecule, and a polyol (a1-1) having an anionic group [X] Can be manufactured.
  • the urethane resin (A) it is preferable to use at least one selected from the group consisting of the urethane resin (A-1) and the urethane resin (A-2). From the viewpoint of improvement, it is more preferable to use those having a large amount of amino groups in the side chain. Specifically, it is particularly preferable to use the urethane resin (A-2), and it is more preferable to use the urethane resin (A-1).
  • the water-based urethane resin composition when used as a binder for inkjet printing inks, it is also necessary to use those having a large amount of amino groups in the side chain which is a molecular structure that can more effectively interact with the pigment. Is more preferable. Specifically, it is particularly preferable to use the urethane resin (A-2), and it is more preferable to use the urethane resin (A-1).
  • polyol (a1) and polyisocyanate (a2) used for producing the urethane resin (A) such as the urethane resins (A-1) and (A-2) will be described.
  • the polyol (a1) from the viewpoint of introducing the anionic group [X] into the urethane resin (A), for example, the polyol (a1-1) having the anionic group [X] can be used.
  • polyol (a1-1) having an anionic group for example, a polyol having a carboxyl group or a polyol having a sulfonic acid group can be used.
  • polyol having a carboxyl group examples include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid and the like. Among them, 2,2′-dimethylolpropionic acid is preferably used. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group react with various polycarboxylic acids can also be used.
  • polyol having a sulfonic acid group examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof, and the low molecular weight polyol.
  • dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof, and the low molecular weight polyol.
  • the polyester polyol obtained by reacting with can be used.
  • anionic group [X] it is preferable that part or all of a carboxyl group, a sulfonic acid group, and the like are neutralized with a basic compound or the like in order to develop good water dispersibility.
  • Examples of the basic compound include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine, and metal hydroxides including sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like. Things can be used.
  • the polyol (a1-1) having an anionic group [X] can be used by adjusting the acid value of the resulting urethane resin (A) to be in the above-mentioned range.
  • the urethane resin (A) It is preferable to use in the range of 2% by mass to 30% by mass with respect to the total mass of all the raw materials used for the production of.
  • the total mass of all the raw materials is a reactive compound such as a chain extender that requires a polyol (a1) and a polyisocyanate (a2), which will be described later, and can react with them to form a urethane resin (A). Is used, it refers to the total mass of the raw materials containing them.
  • the “total mass of all raw materials used for the production of the urethane resin (A)” described in the present specification is also the same as described above.
  • polyol (a1) in addition to the polyol (a1-1) having the anionic group [X], other polyols can be used in combination as required.
  • urethane resin (A-1) when used as the urethane resin (A), a polyol (a1-2) having a tertiary amino group in the side chain should be used. Is preferred.
  • Examples of the polyol (a1-2) having a tertiary amino group in the side chain include a compound having two epoxy groups in one molecule represented by the following general formula [II], a secondary amine, and 1 equivalent of an epoxy group. It can mix
  • R 1 is an alkylene chain, a residue of a dihydric phenol, or a polyoxyalkylene chain.
  • R 1 is an aliphatic alkyl chain such as ethylene, propylene, butene, or pentene, or an aliphatic cyclic structure such as cyclohexene.
  • polyoxyalkylene chains derived from polyethylene glycol, polypropylene glycol, and the like, and the like.
  • ethanediol-1,2-diglycidyl ether propanediol-1,2-diglycidyl ether, propanediol-1,3-diglycidyl ether, butanediol-1,4-diglycidyl ether, pentane Diol-1,5-diglycidyl ether, 3-methyl-pentanediol-1,5-diglycidyl ether, hexanediol-1,6-diglycidyl ether, polybutadiene glycol-diglycidyl ether, cyclohexanediol-1,4- Diglycidyl ether, diglycidyl ether of 2,2-bis (4-hydroxycyclohexyl) -propane (hydrogenated bisphenol A), isomer mixture of hydrogenated dihydroxydiphenylmethane (hydrogenated bisphenol F) Resorcinol-diglycidyl ether, hydroquinone-diglycid
  • the compound having two epoxy groups in one molecule includes diglycidyl ether of polyoxyalkylene glycol in which R 1 in the general formula [II] is a polyoxyalkylene chain, particularly polyoxyethylene glycol. It is preferred to use diglycidyl ether and / or polyoxypropylene glycol-diglycidyl ether and / or diglycidyl ether of ethylene oxide-propylene oxide copolymer.
  • the epoxy equivalent of the compound is preferably 1000 g / equivalent or less, and preferably 500 g / equivalent or less. It is more preferable that
  • examples of the secondary amine capable of reacting with the compound having two epoxy groups in one molecule include dimethylamine, Diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-sec-butylamine, di-n-pentylamine, di-n-peptylamine, di-n-octylamine, Diisooctylamine, dinonylamine, diisononylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di-n-pentadecylamine, di-n-octadecylamine, di-n- Nonadecylamine, di-n-eicosylamine and the like can be used.
  • an aliphatic secondary amine having 2 to 18 carbon atoms because it is difficult to volatilize when producing the polyol (a1-2) having a tertiary amino group in the side chain. It is more preferable to use an aliphatic secondary amine having 3 to 8 carbon atoms.
  • the polyol (a1-2) having a tertiary amino group in the side chain is 5% by mass to 50% with respect to the total mass of all raw materials used in the production of the urethane resin (A) in order to improve the substrate adhesion. It is preferable to use in the range of mass%.
  • the other polyol for example, when the urethane resin (A-2) is used as the urethane resin (A), it has two hydroxyl groups at one end and is tertiary in the molecule. It is preferable to use a vinyl polymer (a1-3) having an amino group.
  • the vinyl polymer (a1-3) is obtained, for example, by polymerizing the vinyl monomer containing a vinyl monomer having a tertiary amino group in the presence of a chain transfer agent having two hydroxyl groups.
  • a chain transfer agent having two hydroxyl groups can be used.
  • radical polymerization of the vinyl monomer containing a vinyl monomer having a tertiary amino group is performed in the presence of a chain transfer agent having two hydroxyl groups and a mercapto group, and the mercapto group is Examples of the starting point include those obtained by polymerizing the vinyl monomers.
  • the vinyl polymer (a1-3) for example, radical polymerization of the vinyl monomer is performed in the presence of a chain transfer agent having a carboxyl group and a mercapto group, and the vinyl monomer is originated from the mercapto group.
  • a product obtained by reacting a polymer with a compound having a hydroxyl group and a glycidyl group can be used.
  • the obtained vinyl polymer (a1-3) has two hydroxyl groups derived from the chain transfer agent at one end, an isocyanate group contained in the polyisocyanate (a2) described later as the various polyols (a1). To form a urethane bond.
  • the vinyl polymer (a1-3) having two hydroxyl groups at one end it is easy to control the viscosity when reacting with the polyisocyanate (a2), and the substrate adhesion of the resulting aqueous urethane resin composition
  • Examples of the chain transfer agent having two hydroxyl groups that can be used in the production of the vinyl polymer (a1-3) include a chain transfer agent having two hydroxyl groups and a mercapto group, and a carboxyl group and a mercapto group.
  • the chain transfer agent etc. which have can be used.
  • the use of a chain transfer agent having two hydroxyl groups and a mercapto group is preferred because the production of the vinyl polymer (a1-3) is simple.
  • Examples of the chain transfer agent having two hydroxyl groups and a mercapto group include 3-mercapto-1,2-propanediol (thioglycerin), 1-mercapto-1,1-methanediol, 1-mercapto-1, 1-ethanediol, 2-mercapto-1,3-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto- 2,3-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like can be used. Of these, it is preferable to use 3-mercapto-1,2-propanediol because it has less odor, is excellent in terms of workability and safety, and is versatile.
  • a vinyl monomer having a tertiary amino group is essential from the viewpoint of introducing a tertiary amino group into the side chain of the vinyl polymer (a1-3). If necessary, other vinyl monomers can be used in combination.
  • Examples of the vinyl monomer having a tertiary amino group include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth) acrylate, N- Methyl-N-ethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl-p-styrenesulfonamide, N, N-
  • (meth) acrylate refers to one or both of methacrylate and acrylate
  • (meth) acryloyl refers to one or both of methacryloyl or acryloyl.
  • a (meth) acrylic monomer having a tertiary amino group is preferably used as the vinyl monomer having a tertiary amino group.
  • a (meth) acrylic monomer having a tertiary amino group is preferably used as the vinyl monomer having a tertiary amino group.
  • 2- (dimethylalumino) ethyl (meth) acrylate or the like is preferably used as the vinyl monomer having a tertiary amino group.
  • vinyl monomer capable of reacting with the chain transfer agent if necessary, other vinyl monomers other than the vinyl monomer having a tertiary amino group may be used. Can be used in combination with a mer.
  • Examples of the other vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl.
  • Examples of the other vinyl monomers include (meth) acrylic acid and (meth) acrylic acid ⁇ -carboxyethyl for the purpose of introducing a hydrophilic group into the vinyl polymer (a1-3).
  • Vinyl having acid group or acid anhydride group such as 2- (meth) acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride Monomer
  • Vinyl polymers having a polyoxyethylene group such as polyoxyethylene monomethyl ether (meth) acrylate and polyoxyethylene monoethyl ether (meth) acrylate can be used.
  • (meth) acrylic acid refers to one or both of methacrylic acid and acrylic acid.
  • the other vinyl monomer for example, a vinyl monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate may be used.
  • the vinyl polymer (a1-3) has 2 Those having no other hydroxyl groups other than the individual hydroxyl groups are preferred. Therefore, as the other vinyl monomer, it is preferable not to use a vinyl monomer having a hydroxyl group as described above as much as possible.
  • the polymerization reaction between the chain transfer agent and the vinyl monomer containing a vinyl monomer having a tertiary amino group is carried out under a solvent such as toluene or methyl ethyl ketone adjusted to a temperature of about 50 ° C. to 100 ° C., for example. It can proceed by supplying the chain transfer agent and the vinyl monomer all at once or sequentially and radical polymerization. As a result, the vinyl polymer undergoes radical polymerization starting from, for example, a mercapto group of the chain transfer agent, has two hydroxyl groups at one end, and has a tertiary amino group in the molecule. (A1-3) can be produced. When the vinyl polymer (a1-3) is produced by the above method, a conventionally known polymerization initiator may be used if necessary.
  • a solvent such as toluene or methyl ethyl ketone adjusted to a temperature of about 50 ° C. to 100 ° C., for example. It
  • the vinyl polymer (a1-3) having two hydroxyl groups at one end and having a tertiary amino group in the molecule obtained by the above method is used as a starting material for the production of the urethane resin (A). It is preferably used in the range of 10% by mass to 80% by mass with respect to the total mass.
  • a polyol or the like can also be used.
  • polyether polyol polycarbonate polyol, polyester polyol, and polyester ether polyol
  • those having a number average molecular weight in the range of 500 to 3,000 are preferably used, and more preferably in the range of 500 to 2,500. preferable.
  • polyether polyol or polycarbonate polyol it is preferable to use.
  • polyether polyol for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
  • the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolethane, Trimethylolpropane and the like can be used.
  • alkylene oxide for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or the like can be used.
  • polyoxytetramethylene glycol polypropylene glycol, or polyethylene glycol
  • polyether polyol preferably has a number average molecular weight of 1000 to 3,000.
  • polycarbonate polyol for example, those obtained by reacting a carbonic acid ester and a polyol, or those obtained by reacting phosgene with bisphenol A or the like can be used.
  • carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.
  • polyol that can react with the carbonate ester examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-
  • polyester polyol examples include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ⁇ -caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyester obtained by the above, copolymerized polyesters thereof, and the like can be used.
  • the low molecular weight polyol for example, ethylene glycol, propylene glycol and the like can be used.
  • polycarboxylic acid for example, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof can be used.
  • polyester ether polyol for example, a reaction product of a polyether polyol obtained by adding the alkylene oxide to the initiator and a polycarboxylic acid can be used.
  • the initiator and the alkylene oxide the same ones exemplified as those usable when the polyether polyol is produced can be used.
  • said polycarboxylic acid the thing similar to what was illustrated as what can be used when manufacturing the said polyester polyol can be used.
  • One or more selected from the group consisting of polyether polyols, polycarbonate polyols, polyol polyester polyols and polyester ether polyols as the other polyols is the total of the polyols (a1) used for the production of the urethane resin (A). It is preferably used in the range of 30% by mass to 90% by mass with respect to the mass.
  • polyols having a relatively low molecular weight can be used in addition to those described above.
  • polyols having a cationic group such as those quaternized with a quaternizing agent such as dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride
  • a polyol having a nonionic group such as a polyalkylene glycol having a structural unit derived from ethylene oxide can also be used as long as the effects of the present invention are not impaired.
  • polyol (a1) examples include a polyol (a1-1) having the anionic group [X], a polyol (a1-2) having a tertiary amino group in the side chain, and the vinyl polymer (a1-3).
  • Etc. can also be used in combination. Accordingly, each of the polyol (a1-1) having the anionic group [X], the polyol (a1-2) having a tertiary amino group in the side chain, and the vinyl polymer (a1-3) has a structure. It is also possible to obtain an aqueous urethane resin composition containing a urethane resin comprising
  • polyisocyanate (a2) examples include aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate.
  • aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate.
  • aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, or polyisocyanates having an alicyclic structure can be used.
  • an aliphatic polyisocyanate from the viewpoint of preventing yellow discoloration, and from the viewpoint of improving the discoloration prevention, it is preferable to use a polyisocyanate having an aliphatic ring.
  • the urethane resin (A) is produced, for example, by reacting the polyol (a1) with the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent, and then the basic compound.
  • the urethane resin having an anionic group [X] formed by neutralizing with an aqueous medium (B) is mixed with an aqueous medium (B) to make it aqueous, if necessary, mixed with a chain extender, It can be produced by reacting.
  • the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5.
  • it is carried out in the range of 0.9 to 1.5.
  • the urethane resin (A-1) When the urethane resin (A-1) is used as the urethane resin (A), for example, in the absence of a solvent or in the presence of an organic solvent, the polyol (a1-1) having the anionic group and the By reacting the polyol (a1) containing the polyol (a1-2) having a tertiary amino group in the side chain with the polyisocyanate (a2), the nitrogen atom constituting the tertiary amino group [Y] is Producing a urethane resin (A-1) in the main chain structure of the urethane resin (A), and then neutralizing some or all of the anionic groups in the urethane resin (A-1), When mixing in the aqueous medium (B) to make it aqueous, it can be produced by mixing with a chain extender and reacting if necessary.
  • the polyol (a1-2) may be mixed and reacted together with the polyol (a1) such as the polyol (a1-1) having an anionic group and the polyisocyanate (a2).
  • a urethane prepolymer having an isocyanate group at the molecular end is prepared by previously reacting the polyol (a1-1) having a functional group with the polyisocyanate (a2), and then the urethane prepolymer and the polyol (a1- 2) may be mixed and reacted.
  • the urethane resin (A-2), which is the urethane resin (A), has a polyol (a1-1) having the anionic group as the polyol (a1) and two hydroxyl groups at one end.
  • a polymer containing a vinyl polymer (a1-3) having a tertiary amino group in the molecule is used.
  • Examples of the organic solvent that can be used in producing the urethane resin (A) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; Nitriles: Amides such as dimethylformamide, N-methylpyrrolidone and N-ethylpyrrolidone can be used alone or in combination of two or more.
  • a chain extender may be used as necessary.
  • a urea bond can be introduced into the structure by using a chain extender, so that a printed image having excellent scratch resistance can be formed. Can be suitably used.
  • chain extender that can be used for producing the urethane resin (A)
  • polyamine other compounds having active hydrogen atoms, and the like can be used.
  • polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; disuccinate Dorazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid
  • Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone And water can be used.
  • Glycols such as saccharose, methylene glycol, glycerin, sorbitol
  • phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A,
  • the chain extender is preferably used, for example, in a range where the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio), 0.3 to 1.0 (equivalent It is more preferable to use it in the range of the ratio.
  • an emulsifier is used as necessary from the viewpoint of improving dispersion stability of the urethane resin (A) in the aqueous medium (B). May be.
  • a machine such as a homogenizer may be used as necessary.
  • emulsifier examples include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc.
  • Anionic emulsifiers; cationic amines such as alkylamine salts, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts It is below.
  • an anionic or nonionic emulsifier it is basically preferable to use an anionic or nonionic emulsifier.
  • a cationic emulsifier and an amphoteric emulsifier may be used in combination as long as the mixing stability of the aqueous urethane resin composition of the present invention can be maintained.
  • a compound having a hydrophilic group may be used as an aid for assisting the water dispersibility of the urethane resin (A).
  • a compound having such a hydrophilic group a compound having an anionic group, a compound having an amphoteric group, or a compound having a nonionic group can be used, and the aqueous urethane resin composition, coating agent, and adhesive of the present invention can be used. From the viewpoint of maintaining the storage stability of the binder for inkjet printing inks, a compound having a nonionic group may be used.
  • Examples of the compound having a nonionic group include a group having at least one active hydrogen atom in the molecule and consisting of an ethylene oxide repeating unit, and an ethylene oxide repeating unit and another alkylene oxide repeating unit.
  • a compound having at least one functional group selected from the group consisting of can be used.
  • polyoxyethylene glycol or polyoxyethylene-polyoxyethylene having a number average molecular weight of 300 to 20,000 containing at least 30% by mass of ethylene oxide repeating units and having at least one active hydrogen atom in the polymer
  • Nonionic group-containing compounds such as propylene copolymer glycol, polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol, or monoalkyl ethers thereof, or obtained by copolymerization thereof It is possible to use compounds such as polyester polyether polyols.
  • the aqueous medium (B) used in the aqueous urethane resin composition of the present invention is a solvent in which the urethane resin (A) can be dispersed.
  • the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof.
  • the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like.
  • only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.
  • water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
  • the aqueous medium (B) is preferably contained in an amount of 50 to 90% by mass, more preferably 65 to 85% by mass, based on the total amount of the aqueous urethane resin composition.
  • aqueous urethane resin composition of the present invention may be used in combination with a curing agent or a curing catalyst as necessary, as long as the substrate adhesion, storage stability, ink ejection property and the like are not deteriorated.
  • Examples of the curing agent include a compound having a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, a polyisocyanate, and the like.
  • Examples of the curing catalyst include lithium hydroxide. Sodium hydroxide, potassium hydroxide and the like can be used.
  • the aqueous urethane resin composition of the present invention is 10 to 50 masses of the urethane resin (A) with respect to the total amount of the aqueous urethane resin composition, from the viewpoint of achieving both excellent substrate adhesion and water dispersion stability. %, Preferably 15% by mass to 35% by mass. The same applies when the aqueous urethane resin composition is used as a coating agent, an adhesive, or a binder for inkjet printing ink.
  • the aqueous urethane resin composition containing the urethane resin (A) and the aqueous medium (B) obtained by the above method is excellent in adhesion to various substrates and excellent in durability such as water resistance. Therefore, it can be used exclusively for coating agents and adhesives.
  • the coating agent and adhesive made of the aqueous urethane resin composition can be used for surface coating and adhesion of various substrates.
  • the base material examples include various plastics and films thereof, metal, glass, paper, and wood.
  • the coating agent of this invention has the outstanding adhesiveness with respect to a plastic base material or a metal base material.
  • plastic base material acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC Resin), ABS / PC resin, polystyrene resin (PS resin), polymethyl methacrylate resin (PMMA resin), acrylic resin, polypropylene resin, polyethylene resin, etc.
  • plastic film base materials include polyethylene terephthalate film, polyester film Polyethylene film, polypropylene film, TAC (triacetyl cellulose) film, polycarbonate film, polyvinyl chloride film, and the like can be used.
  • the coating agent can form a densely formed film capable of suppressing corrosion of the metal material itself, it can be suitably used as a coating agent for protecting the surface of a metal substrate.
  • metal substrates examples include galvanized steel sheets used for applications such as automobiles, home appliances, and building materials, and plated steel sheets such as aluminum-zinc alloy steel sheets, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, stainless steel plates, etc. Can be used.
  • a laminate in which a film formed using the coating agent on the surface of the metal substrate is excellent in solvent resistance without causing peeling of the film during processing. It can be used for applications such as paints, building material paints, and plastic paints.
  • the coating agent or adhesive can be applied to the surface of the substrate, dried, and cured to form a film or adhesive layer.
  • Examples of the coating method of the coating agent include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.
  • the drying may be natural drying at room temperature as long as the aqueous medium (B) contained in the coating layer can be evaporated and removed, but is preferably dried by heating.
  • the heat drying is usually preferably performed at 40 ° C. to 250 ° C. for about 1 second to 600 seconds.
  • the film or adhesive layer made of the coating agent or adhesive preferably has a thickness of about 1 ⁇ m to 30 ⁇ m.
  • the coating agent and the adhesive can form a film excellent in substrate adhesion and the like, for example, surface coating of various plastic members of electronic equipment, for example, surface coating of members constituting automobiles, railways, etc.
  • coating materials used for surface coating of light receiving surfaces such as photovoltaic power generation devices, surface coating of electronic components, wall coverings, flooring, window glass, glasses, etc. It can be used for various purposes.
  • the adhesive or pressure-sensitive adhesive containing the aqueous urethane resin composition of the present invention has excellent adhesion to various substrates, for example, fixing of components constituting automobiles, home appliances, etc. It can be used for adhesive sheets.
  • the aqueous urethane resin composition of the present invention is excellent in water dispersion stability because the tertiary amino group present in the side chain of the urethane resin (A) is excellent in affinity with pigments and the like. And since it is excellent also in the adhesiveness of the ink with respect to a printing surface, it can be used conveniently for manufacture of water-based inks, such as ink for inkjet printing, for example.
  • Ink jet printing ink ejected from an ink ejection nozzle usually requires good ejection stability, and a resin composition generally used for a coating agent or an adhesive is diverted to the ink jet printing ink.
  • a resin composition generally used for a coating agent or an adhesive is diverted to the ink jet printing ink.
  • the ink for inkjet printing generally contains a pigment, a dispersant for dispersing the pigment in an aqueous medium, and a binder resin and various additives depending on the others.
  • a dispersant for dispersing the pigment in an aqueous medium for example, an aqueous pigment dispersion in which a pigment is stably dispersed in an aqueous medium by the dispersant, and a binder resin and various additives are mixed together using various dispersing devices. Can be manufactured.
  • pigment aqueous dispersion As the pigment that can be used in the production of the pigment aqueous dispersion, known and commonly used inorganic pigments and organic pigments can be used.
  • the inorganic pigment for example, titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite and the like can be used.
  • organic pigments examples include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, Organic pigments such as diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments can be used.
  • These pigments can be used in combination of two or more. These pigments may be surface-treated and have a self-dispersing ability with respect to an aqueous medium.
  • the aqueous medium contained in the pigment aqueous dispersion can be the same as the aqueous medium (B) described above.
  • the dispersant that can be used for dispersing the pigment for example, an acrylic resin, a styrene-acrylic resin, or the like can be used, and any of a random type, a block type, and a graft type can be used. it can.
  • an acid or a base may be used in combination to neutralize the polymer dispersant.
  • the resin that can be used in the dispersant preferably has a weight average molecular weight of about 1,000 to 15,000, and preferably has a weight average molecular weight of 1,000 to 10,000. More preferred.
  • the pigment dispersant it is preferable to use the urethane resin composition of the present invention having an acid value of about 30 to 500 as the urethane resin (A). It is preferable for improving the above.
  • the acid value is preferably derived from a carboxyl group or a carboxylate group as the anionic group [X].
  • the pigment aqueous dispersion obtained by dispersing the pigment in an aqueous medium by using the dispersant can be used exclusively for producing various water-based inks. In particular, it can be used for the production of an aqueous inkjet printing ink.
  • the urethane resin (A) contained in the aqueous urethane resin composition of the present invention has excellent dispersion stability in an aqueous medium, and the tertiary amino group [Y] of the urethane resin (A) is compatible with the pigment.
  • Dispersant for dispersing the pigment in an aqueous medium because it has excellent properties and the degree of freedom is increased by being present in the side chain of the urethane resin (A), and the affinity with the pigment can be further improved. Can be suitably used.
  • the pigment aqueous dispersion containing the water-based urethane resin composition can also provide a water-based ink having excellent ink adhesion to the printing surface.
  • the pigment aqueous dispersion is prepared by, for example, mixing a kneaded product obtained by pre-kneading a pigment, a dispersant, an additive, and the like using a two-roll or a mixer with an aqueous medium using various dispersing devices. Can be manufactured.
  • a binder for ink jet printing ink is often used in recent years from the viewpoint of imparting excellent scratch resistance to a printed image formed using the ink.
  • the ink jet printing ink binder is used separately from the pigment and its dispersant.
  • the binder for ink jet printing ink for example, various urethane resins and acrylic resins can be used. Among these, it is particularly preferable to use the urethane resin composition of the present invention as the binder for inkjet printing ink.
  • the urethane resin (A) having an acid value in the range of 2 to 100 is preferably used for improving the dispersion stability of the urethane resin (A) in the ink. It is more preferable to use within a range.
  • the binder for inkjet printing ink is preferably contained in a range of about 0.2 to 10% by mass with respect to the entire inkjet printing ink.
  • additives that can be used in producing the ink for inkjet printing include, for example, viscosity modifiers, wetting agents, antifoaming agents, surfactants, preservatives, pH adjusters, chelating agents, plasticizers, An ultraviolet absorber, antioxidant, etc. can be used.
  • azo dyes such as monoazo and disazo, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, Nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes, perinone dyes, phthalocyanine dyes, triallylmethane dyes, and the like can be used.
  • the ink for inkjet printing can be specifically prepared by the following manufacturing method.
  • a pigment aqueous dispersion comprising an aqueous dispersion of a pigment or dye is prepared by mixing the pigment, the aqueous medium and, if necessary, the additive using various dispersing devices;
  • a method of preparing an ink by mixing an ink precursor composed of the aqueous pigment dispersion, the binder for inkjet printing ink, and, if necessary, an aqueous medium and an additive using various dispersing devices.
  • Examples of the dispersing device that can be used in the production of the ink for inkjet printing include, for example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, an SC mill, and a nanomizer.
  • an ultrasonic homogenizer a high-pressure homogenizer
  • a paint shaker a ball mill, a roll mill
  • a sand mill a sand grinder
  • a dyno mill a disperse mat
  • SC mill and a nanomizer.
  • two or more types can be used in combination.
  • the coarse particles having a particle diameter of approximately 250 nm or more may be present.
  • the coarse particles may cause clogging of printer nozzles and the like, and may deteriorate ink discharge characteristics. Therefore, the coarse particles may be coarsened by a method such as centrifugation or filtration after the preparation of the aqueous dispersion of the pigment or after the preparation of the ink. It is preferred to remove the particles.
  • the ink for ink jet printing obtained above preferably has a volume average particle diameter of 200 nm or less, and particularly in the case of forming a higher gloss image such as photographic image quality, the range is from 80 nm to 120 nm. It is more preferable that
  • the ink for ink jet printing contains 0.2% by mass to 10% by mass of the urethane resin (A), 50% by mass to 95% by mass of an aqueous medium, and a pigment or dye based on the whole ink for ink jet printing. It is preferable to contain 0.5% by mass to 15% by mass.
  • the ink for ink jet printing of the present invention obtained by the above method can be used exclusively for ink jet printing using an ink jet printer, for example, ink jet printing on a substrate such as paper, plastic film, metal film or sheet. be able to.
  • the ink jet method is not particularly limited, but a known method such as a continuous jet type (charge control type, spray type, etc.) or an on-demand type (piezo type, thermal type, electrostatic suction type, etc.) should be applied. Can do.
  • the printed matter printed using the ink for ink jet printing of the present invention has excellent scratch resistance, it is difficult to cause deterioration of a printed image due to lack of pigments and the like, and has excellent alkali resistance. Since it has a high color density image, it can be prevented by bleed or the like due to adhesion of alkaline detergent to the printed image surface, and can be obtained, for example, by photographic printing by inkjet printing or high-speed printing by inkjet printing. It can be used for various purposes such as printed materials.
  • the aqueous urethane resin composition of the present invention can also be used as a molding material that can be used for the production of various cured products such as films in addition to the various uses described above.
  • the aqueous urethane resin composition is applied to the surface of a release paper or release film, cured by the same method as described above, and then the release paper or the like is removed to form a transparent film. A cured product can be obtained.
  • Cured products such as films include optical films such as retardation films and polarizing plate protective films, mobile phones, home appliances, OA equipment, automobile parts such as automobile interior and exterior materials, parts of various household appliances, electronic It can be used for manufacturing materials, building materials, medical materials such as artificial bones and artificial teeth.
  • Example 1 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 65.3 parts by mass of the polyol (a1-2-1) having a tertiary amino group obtained in Synthesis Example 1 and polycarbonate Diol (Nippon Polyurethane Industry Co., Ltd., Nipponporan 981, number average molecular weight 1,000) 105.6 parts by mass, 2,2-dimethylolpropionic acid 12.9 parts by mass, 1,4-cyclohexanedimethanol 19.3 parts by mass And 97.0 parts by mass of isophorone diisocyanate were reacted at 80 ° C.
  • polycarbonate Diol Nippon Polyurethane Industry Co., Ltd., Nipponporan 981, number average molecular weight 1,000
  • the aqueous dispersion of the urethane resin of the present invention was obtained by removing the solvent from the aqueous dispersion of the urethane resin and adjusting the non-volatile content by adding water to 30% by mass.
  • Example 2 Vinyl having two hydroxyl groups at one end and a tertiary amino group in the molecule obtained in Synthesis Example 2 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer 308.6 parts by mass of polymer (a1-3-1), 55.5 parts by mass of polycarbonate diol (manufactured by Nippon Polyurethane Industry Co., Ltd., Nipponran 981, number average molecular weight 1,000), 2,2-dimethylolpropionic acid 12.9 parts by mass, 10.4 parts by mass of 1,4-cyclohexanedimethanol and 67.2 parts by mass of isophorone diisocyanate were reacted at 80 ° C.
  • polycarbonate diol manufactured by Nippon Polyurethane Industry Co., Ltd., Nipponran 981, number average molecular weight 1,000
  • 2,2-dimethylolpropionic acid 12.9 parts by mass
  • the aqueous dispersion of the urethane resin of the present invention was obtained by removing the solvent from the aqueous dispersion of the urethane resin and adjusting the non-volatile content by adding water to 30% by mass.
  • Example 3 Vinyl having two hydroxyl groups at one end and a tertiary amino group in the molecule obtained in Synthesis Example 2 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer 24.7 parts by mass of polymer (a1-3-1), 148.8 parts by mass of polycarbonate diol (manufactured by Nippon Polyurethane Industry Co., Ltd., Nipponran 981, number average molecular weight 1,000), 2,2-dimethylolpropionic acid 12.9 parts by mass, 17.2 parts by mass of 1,4-cyclohexanedimethanol and 98.8 parts by mass of isophorone diisocyanate were reacted at 80 ° C.
  • polycarbonate diol manufactured by Nippon Polyurethane Industry Co., Ltd., Nipponran 981, number average molecular weight 1,000
  • 2,2-dimethylolpropionic acid 12.9 parts by mass
  • Example 4 Vinyl having two hydroxyl groups at one end and having a tertiary amino group in the molecule obtained in Synthesis Example 3 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer 476.2 parts by mass of polymer (a1-3-2), 7.6 parts by mass of polycarbonate diol (Nippon Polyurethane Industry Co., Ltd., Nipponporan 981, number average molecular weight 1,000), 2,2-dimethylolpropionic acid 9.7 parts by mass and 44.6 parts by mass of isophorone diisocyanate were reacted at 80 ° C.
  • aqueous dispersion of the urethane resin was desolvated, and water was added to adjust the nonvolatile content to 30% by mass to obtain an aqueous urethane resin composition.
  • aqueous dispersion of the urethane resin was desolvated, and water was added to adjust the nonvolatile content to 30% by mass to obtain an aqueous urethane resin composition.
  • aqueous dispersion of the urethane resin was desolvated, and water was added to adjust the nonvolatile content to 30% by mass to obtain an aqueous urethane resin composition.
  • the weight average molecular weight of the urethane resin was measured by a gel permeation chromatography (GPC) method.
  • Measurement device GPC measurement device (HLC-8220 type, detector is RI detector) manufactured by Tosoh Corporation.
  • Measurement sample The urethane resin composition was coated on a glass plate with a 3 mil applicator and dried at room temperature for 1 hour to prepare a semi-dry coating film made of urethane resin. The obtained coating film was peeled from the glass plate, and 0.4 g of the coating film dissolved in 100 g of tetrahydrofuran was used as a measurement sample (concentration: 0.4 mass%).
  • Standard sample A calibration curve was prepared using the following monodisperse polystyrene. “A-500”, “A-1000”, “A-2500”, “A-5000”, “F-1”, “F-2”, “F-4”, “F-10”, “F -20 “,” F-40 “,” F-80 “,” F-128 “,” F-288 “and” F-550 "(all manufactured by Tosoh Corporation)
  • aqueous urethane resin composition obtained above was applied to the surfaces of the six types of substrates shown in [1] to [6] below using a bar coater so that the dry film thickness was 2 ⁇ m.
  • the test plate 1 was obtained by laminating and drying at 80 ° C. for 180 seconds using a hot air dryer to obtain a coating film laminated on the surface of each substrate.
  • PP base material polypropylene
  • PET substrate polyethylene terephthalate
  • PC substrate Polycarbonate
  • SUS base material JIS G4305 SUS304
  • AL base material Aluminum, JIS H4000 A1050P, 0.8 mm ⁇ 70 mm ⁇ 150 mm
  • Glass substrate JIS R3202, 2.0 mm x 70 mm x 150 mm
  • the adhesion between the coating film constituting the test plate obtained above and the substrate was measured based on the JIS K5600 cross cut test method and evaluated according to the following evaluation criteria.
  • Table 1 and Table 2 below show the evaluation results of the base material adhesion and blending stability of the aqueous urethane resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3.
  • PC Polycarbonate diol (Nippon Polyurethane Industry Co., Ltd., Nipponporan 981, number average molecular weight 1,000) “DMPA”; 2,2-dimethylolpropionic acid “a1-2-1”; polyol having tertiary amino group obtained in Synthesis Example 1 (a1-2-1) “A1-3-1”; vinyl polymer obtained in Synthesis Example 2 (a1-3-1) “A1-3-2”; vinyl polymer obtained in Synthesis Example 3 (a1-3-2) “NMDEA”; N-methyldiethanolamine “CHDM”; 1,4-cyclohexanedimethanol “IPDI”; isophorone diisocyanate
  • PP substrate polypropylene, 1.0 mm ⁇ 70 mm ⁇ 150 mm PET substrate: Polyethylene terephthalate, 1.0 mm x 70 mm x 150 mm
  • PC substrate Polycarbonate, 1.0 mm x 70 mm x 150 mm SUS base
  • aqueous urethane resin compositions obtained in Examples 1 and 2 were excellent in blending stability and capable of forming a film excellent in adhesion to various substrates.
  • the amount of tertiary amino groups present in the urethane resin is slightly smaller than that described in Example 1. Further, in the aqueous urethane resin composition described in Example 4, the amount of tertiary amino groups present in the urethane resin is slightly larger than that described in Example 1.
  • These water-based urethane resin compositions were slightly lowered in terms of adhesion to some base materials such as SUS base materials and glass base materials, but were at a level causing no practical problems.
  • the aqueous urethane resin composition obtained in Comparative Example 1 does not have a tertiary amino group. For this reason, the adhesiveness to the PP base material or the SUS base material is significantly reduced.
  • the aqueous urethane resin composition obtained in Comparative Example 2 contains a urethane resin obtained by using the vinyl polymer (a1-3-1) obtained in Synthesis Example 2. However, all of the tertiary amino groups introduced by the vinyl polymer (a1-3-1) are neutralized by phosphoric acid, and the unneutralized tertiary amino groups are not present in the urethane resin. It is. Therefore, the water-based urethane resin composition sometimes causes a significant decrease in adhesion to the PP substrate and a significant decrease in blending stability.
  • the aqueous urethane resin composition obtained in Comparative Example 3 has a tertiary amino group, a nitrogen atom constituting a tertiary amino group is present in the main chain skeleton constituting the urethane resin. Therefore, in the said water-based urethane resin composition, the adhesiveness with respect to PP base material or SUS base material fell remarkably.
  • binder for inkjet printing ink comprising the urethane resin composition of the present invention will be described more specifically with reference to Examples and Comparative Examples.
  • Example 5 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 29.1 parts by mass of the polyol (a1-2-1) having a tertiary amino group obtained in Synthesis Example 1 and Oxytetramethylene glycol (number average molecular weight 1,000) 82.9 parts by mass, 2,2-dimethylolpropionic acid 23.0 parts by mass, 1,4-cyclohexanedimethanol 15.2 parts by mass and isophorone diisocyanate 90.3 A mass part was reacted at 80 ° C.
  • the aqueous dispersion of the urethane resin was desolvated, and further adjusted by adding water so that the non-volatile content was 25% by mass, thereby obtaining the ink jet printing ink binder of the present invention.
  • Example 6 Vinyl having two hydroxyl groups at one end and a tertiary amino group in the molecule obtained in Synthesis Example 2 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer Polymer (a1-3-1) 137.4 polyoxytetramethylene glycol (number average molecular weight 1,000) 60.6 parts by mass, 2,2-dimethylolpropionic acid 23.0 parts by mass, 1,4-cyclohexane After reacting 11.1 parts by mass of dimethanol and 77.1 parts by mass of isophorone diisocyanate in the presence of 89.4 parts by mass of methyl ethyl ketone as an organic solvent at 80 ° C. for 10 hours, 2.2 parts by mass of methanol are added. Then, the reaction was terminated, and an organic solvent solution of urethane resin (acid value 40) having a weight average molecular weight of 40,000 was obtained.
  • acid value 40 having a weight
  • Example 7 Vinyl having two hydroxyl groups at one end and a tertiary amino group in the molecule obtained in Synthesis Example 2 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer Polymer (a1-3-2) 391.6 polyoxytetramethylene glycol (number average molecular weight 1,000) 6.2 parts by mass, 2,2-dimethylolpropionic acid 8.0 parts by mass and isophorone diisocyanate 36.7 After the reaction with 10 parts by mass of methyl ethyl ketone as an organic solvent in the presence of 59.9 parts by mass at 80 ° C. for 10 hours, the reaction was terminated by adding 1.1 parts by mass of methanol, and urethane having a weight average molecular weight of 33,000. An organic solvent solution of resin (acid value 13.5) was obtained.
  • the aqueous dispersion of the urethane resin was desolvated, and further adjusted by adding water so that the non-volatile content was 25% by mass, thereby obtaining the ink jet printing ink binder of the present invention.
  • the aqueous dispersion of the urethane resin was desolvated, and further adjusted by adding water so that the non-volatile content was 25% by mass, thereby obtaining the ink jet printing ink binder of the present invention.
  • the ion-exchanged water heated to 60 ° C. with a total amount of 8000 g was added to the kneaded material in 2 hours to obtain a colored resin composition having a nonvolatile content of 37.9% by mass.
  • aqueous pigment dispersion precursor 18 kg was added to a bead mill (Nanomill NM-G2L manufactured by Asada Tekko Co., Ltd., bead diameter: 0.3 mm zirconia beads, bead filling amount: 85 vol%, cooling water temperature: 10 ° C., Rotating speed: 2660 rev / min), the bead mill passing liquid is centrifuged at 13000 G ⁇ 10 minutes, and then filtered through a filter having an effective pore size of 0.5 ⁇ m to thereby obtain a water-based quinacridone pigment. A dispersion was obtained. The concentration of the quinacridone pigment in this aqueous pigment dispersion was 14.9% by mass.
  • Example 1 the binder for inkjet printing ink obtained in Examples 5 to 7 and Comparative Examples 4 to 5 was adjusted so that the concentration of quinacridone pigment was 4% by mass and the concentration of polyurethane was 1% by mass.
  • the obtained water-based pigment dispersion of quinacridone pigment, 2-pyrrolidinone, triethylene glycol monobutyl ether, glycerin, surfactant (Surfinol 440, manufactured by Air Products) and ion-exchanged water are blended in the following proportions:
  • Ink jet printing ink was prepared by mixing and stirring according to the following.
  • the viscosity of the ink and the particle diameter of the dispersed particles in the ink are as follows: It measured by the method similar to the above.
  • Viscosity change rate is less than 2% ⁇ : Viscosity change rate is 2% or more and less than 5% ⁇ : Viscosity change rate is 5% or more
  • PTMG polyoxytetramethylene glycol
  • DMPA 2,2-dimethylolpropionic acid
  • a1-2-1 polyol having tertiary amino group obtained in Synthesis Example 1 (a1-2-1) “A1-3-1”; vinyl polymer obtained in Synthesis Example 2 (a1-3-1) “A1-3-2”; vinyl polymer obtained in Synthesis Example 3 (a1-3-2) “CHDM”; 1,4-cyclohexanedimethanol “IPDI”; isophorone diisocyanate
  • the inkjet printing ink containing the binder for inkjet printing ink obtained in Example 5 was excellent in storage stability and ejection stability, and was able to form a printed matter excellent in scratch resistance and alkali resistance.
  • the inkjet printing ink containing the inkjet printing ink binder described in Example 6 contains a urethane resin obtained using the vinyl polymer (a1-3-1) obtained in Synthesis Example 2. With such an ink for ink jet printing, compared with the ink described in Example 5, it was possible to form a printed matter having further excellent alkali resistance.
  • the ink for inkjet printing containing the binder for inkjet printing ink described in Example 7 has a slightly larger amount of tertiary amino groups present in the urethane resin than that described in Example 5. Even this ink for ink-jet printing can form a printed matter having excellent storage stability and good dischargeability at a practically usable level, and having good scratch resistance and alkali resistance. did it.
  • the ink for inkjet printing containing the binder for inkjet printing ink obtained in Comparative Example 4 does not have a tertiary amino group. For this reason, the printed matter obtained using the ink for ink jet printing has caused a remarkable decrease in scratch resistance and alkali resistance.
  • the aqueous urethane resin composition obtained in Comparative Example 2 contains a urethane resin obtained by using the vinyl polymer (a1-3-1) obtained in Synthesis Example 2. However, all of the tertiary amino groups introduced by the vinyl polymer (a1-3-1) are neutralized by phosphoric acid, and the unneutralized tertiary amino groups are not present in the urethane resin. It is. Since the ink for inkjet printing caused a significant decrease in storage stability and ejection stability, it was not possible to form a printed matter using the ink.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Cette invention a pour objet de pourvoir à une composition de résine uréthanne aqueuse capable d'une excellente adhérence à diverses bases telles qu'une base en métal et une base en plastique. Pour ce faire, la composition de résine uréthanne aqueuse selon l'invention contient : une résine uréthanne (A) qui contient un groupe anionique [X] et un groupe amine tertiaire [Y]; et un milieu aqueux (B). La composition de résine uréthanne aqueuse selon l'invention est caractérisée en ce que la résine uréthanne (A) a un groupe amine tertiaire [Y] dans une chaîne latérale.
PCT/JP2012/050261 2011-02-16 2012-01-10 Composition de résine uréthanne aqueuse, et matériau de revêtement, adhésif, liant pour encre d'impression par jet d'encre, encre pour impression par jet d'encre et matière imprimée contenant chacun la composition de résine uréthanne aqueuse WO2012111360A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012524035A JP5062502B2 (ja) 2011-02-16 2012-01-10 水性ウレタン樹脂組成物、それを含むコーティング剤、接着剤、インクジェット印刷インク用バインダー、インクジェット印刷用インク及び印刷物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011030793 2011-02-16
JP2011-030793 2011-02-16
JP2011030794 2011-02-16
JP2011-030794 2011-02-16

Publications (1)

Publication Number Publication Date
WO2012111360A1 true WO2012111360A1 (fr) 2012-08-23

Family

ID=46672303

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/050261 WO2012111360A1 (fr) 2011-02-16 2012-01-10 Composition de résine uréthanne aqueuse, et matériau de revêtement, adhésif, liant pour encre d'impression par jet d'encre, encre pour impression par jet d'encre et matière imprimée contenant chacun la composition de résine uréthanne aqueuse

Country Status (3)

Country Link
JP (1) JP5062502B2 (fr)
TW (1) TW201239031A (fr)
WO (1) WO2012111360A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3002319A1 (fr) * 2014-09-30 2016-04-06 Fujifilm Corporation Composition d'encre, procédé de production d'une telle composition et procédé de formation d'image
WO2017169840A1 (fr) * 2016-03-29 2017-10-05 Dic株式会社 Agent de dispersion de pigment, dispersion aqueuse de pigment et procédé de production d'une dispersion aqueuse de pigment
JP2017531054A (ja) * 2014-07-31 2017-10-19 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 両性ポリウレタンをバインダーとして含有する水性インクジェットインク
KR20180078958A (ko) * 2016-12-30 2018-07-10 나방주 수성 퍼티의 제조방법
WO2018142892A1 (fr) * 2017-02-02 2018-08-09 セイコーエプソン株式会社 Composition d'encre pour jet d'encre, procédé d'enregistrement et matière enregistrée
JP2019183100A (ja) * 2018-03-30 2019-10-24 株式会社日本触媒 易接着性基材
CN111372965A (zh) * 2017-11-28 2020-07-03 爱克发有限公司 用于喷墨记录的液体套装
CN112969760A (zh) * 2018-08-30 2021-06-15 Dic株式会社 氨基甲酸酯树脂组合物及层叠体

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5594451B1 (ja) * 2013-03-13 2014-09-24 Ｄｉｃ株式会社 受容層形成用樹脂組成物ならびにそれを用いて得られる受容基材、印刷物、導電性パターン及び電気回路
CN107250193B (zh) 2015-01-30 2021-03-12 惠普发展公司，有限责任合伙企业 基于聚氨酯的粘结剂分散体
US11285735B2 (en) 2018-10-26 2022-03-29 Ricoh Company, Ltd. Medium, medium producing method, and medium producing apparatus

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05295076A (ja) * 1992-04-23 1993-11-09 Dainippon Ink & Chem Inc ポリウレタン水性分散液の製造方法
JPH08100039A (ja) * 1994-09-28 1996-04-16 Dainippon Ink & Chem Inc 水性架橋ポリウレタンの製造法
JPH08127632A (ja) * 1994-10-27 1996-05-21 Nippon Polyurethane Ind Co Ltd ポリウレタン樹脂の製造方法
JPH1036471A (ja) * 1996-07-30 1998-02-10 Kanebo Nsc Ltd 両性ポリウレタン樹脂水分散体の製造方法
JP2001262115A (ja) * 2000-03-21 2001-09-26 Nippon Polyurethane Ind Co Ltd 非水系ラミネート接着剤用ポリウレタン樹脂組成物及びこれを用いた非水系ラミネート接着剤
JP2002060451A (ja) * 2000-08-11 2002-02-26 Toyo Ink Mfg Co Ltd 水性ウレタン樹脂及び水性印刷インキ組成物並びに該組成物を用いた包装材料
JP2007327023A (ja) * 2006-05-10 2007-12-20 Kansai Paint Co Ltd 水性樹脂組成物及びこれを含む水性塗料組成物
JP2009235121A (ja) * 2008-03-25 2009-10-15 Fujifilm Corp 顔料分散物およびそれを用いたインク組成物、硬化性組成物、硬化性インク組成物及びインクジェット記録方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05295076A (ja) * 1992-04-23 1993-11-09 Dainippon Ink & Chem Inc ポリウレタン水性分散液の製造方法
JPH08100039A (ja) * 1994-09-28 1996-04-16 Dainippon Ink & Chem Inc 水性架橋ポリウレタンの製造法
JPH08127632A (ja) * 1994-10-27 1996-05-21 Nippon Polyurethane Ind Co Ltd ポリウレタン樹脂の製造方法
JPH1036471A (ja) * 1996-07-30 1998-02-10 Kanebo Nsc Ltd 両性ポリウレタン樹脂水分散体の製造方法
JP2001262115A (ja) * 2000-03-21 2001-09-26 Nippon Polyurethane Ind Co Ltd 非水系ラミネート接着剤用ポリウレタン樹脂組成物及びこれを用いた非水系ラミネート接着剤
JP2002060451A (ja) * 2000-08-11 2002-02-26 Toyo Ink Mfg Co Ltd 水性ウレタン樹脂及び水性印刷インキ組成物並びに該組成物を用いた包装材料
JP2007327023A (ja) * 2006-05-10 2007-12-20 Kansai Paint Co Ltd 水性樹脂組成物及びこれを含む水性塗料組成物
JP2009235121A (ja) * 2008-03-25 2009-10-15 Fujifilm Corp 顔料分散物およびそれを用いたインク組成物、硬化性組成物、硬化性インク組成物及びインクジェット記録方法

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017531054A (ja) * 2014-07-31 2017-10-19 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 両性ポリウレタンをバインダーとして含有する水性インクジェットインク
JP2016069579A (ja) * 2014-09-30 2016-05-09 富士フイルム株式会社 インク組成物、インク組成物の製造方法、及び画像形成方法
US9683121B2 (en) 2014-09-30 2017-06-20 FUJIFIL Corporation Ink composition, method of producing ink composition, and image forming method
EP3002319A1 (fr) * 2014-09-30 2016-04-06 Fujifilm Corporation Composition d'encre, procédé de production d'une telle composition et procédé de formation d'image
WO2017169840A1 (fr) * 2016-03-29 2017-10-05 Dic株式会社 Agent de dispersion de pigment, dispersion aqueuse de pigment et procédé de production d'une dispersion aqueuse de pigment
JPWO2017169840A1 (ja) * 2016-03-29 2018-11-22 Dic株式会社 顔料分散剤、水性顔料分散体及び水性顔料分散体の製造方法
KR102272088B1 (ko) 2016-12-30 2021-07-01 나방주 수성 퍼티의 제조방법
KR20180078958A (ko) * 2016-12-30 2018-07-10 나방주 수성 퍼티의 제조방법
WO2018142892A1 (fr) * 2017-02-02 2018-08-09 セイコーエプソン株式会社 Composition d'encre pour jet d'encre, procédé d'enregistrement et matière enregistrée
CN110234716A (zh) * 2017-02-02 2019-09-13 精工爱普生株式会社 喷墨油墨组合物、记录方法及记录物
CN111372965A (zh) * 2017-11-28 2020-07-03 爱克发有限公司 用于喷墨记录的液体套装
JP2019183100A (ja) * 2018-03-30 2019-10-24 株式会社日本触媒 易接着性基材
JP7257123B2 (ja) 2018-03-30 2023-04-13 株式会社日本触媒 易接着性基材
CN112969760A (zh) * 2018-08-30 2021-06-15 Dic株式会社 氨基甲酸酯树脂组合物及层叠体
CN112969760B (zh) * 2018-08-30 2023-05-12 Dic株式会社 氨基甲酸酯树脂组合物及层叠体

Also Published As

Publication number Publication date
TW201239031A (en) 2012-10-01
JPWO2012111360A1 (ja) 2014-07-03
JP5062502B2 (ja) 2012-10-31

Similar Documents

Publication Publication Date Title
JP5062502B2 (ja) 水性ウレタン樹脂組成物、それを含むコーティング剤、接着剤、インクジェット印刷インク用バインダー、インクジェット印刷用インク及び印刷物
JP4984196B1 (ja) インクジェット印刷インク用バインダー、それを含むインクジェット印刷用インク及び印刷物
JP5170345B2 (ja) インクジェット印刷インク用バインダー、インクジェット印刷用インク、印刷物、及び、バインダーの製造方法
KR101925353B1 (ko) 잉크젯 인쇄 잉크용 바인더, 그것을 함유하는 잉크젯 인쇄용 잉크 및 인쇄물
JP5760569B2 (ja) ポリウレタンの製造方法
JP5672172B2 (ja) インクジェット印刷インク用バインダー、それを含むインクジェット印刷用インク及び印刷物
JP5316427B2 (ja) 水性ウレタン樹脂組成物、それを含むインク用バインダー、インクジェット印刷インク用バインダー及びインクジェット印刷用インク、ならびに、それを用いて印刷の施された印刷物
WO2011004675A1 (fr) Liant pour encre d’impression par jet d’encre, encre pour impression par jet d’encre le contenant, et matière imprimée
JP5029931B2 (ja) インクジェット印刷用インクの製造方法及び印刷物
JP5939426B2 (ja) インクジェット印刷インク用バインダー、それを含むインクジェット印刷用インク及び印刷物
JP5936043B2 (ja) インクジェット印刷インク用バインダーの製造方法
JP5733591B2 (ja) 顔料分散体、インク、インクジェット印刷用インク及び顔料分散体の製造方法
JP2013199606A (ja) インクジェット印刷インク用バインダーの製造方法、インクジェット印刷用インク及び印刷物
JP6102227B2 (ja) インク用バインダー、インク、インクジェット印刷用インク及び印刷物
JP4993040B2 (ja) インクジェット印刷インク用バインダー、それを含むインクジェット印刷用インク及び印刷物
JP2014024975A (ja) インク及びインクジェット印刷用インク
JP2010195965A (ja) インクジェット顔料インク用バインダー
WO2012042968A1 (fr) Liant pour encre d'impression à jet d'encre, encre d'impression à jet d'encre contenant celui-ci, et matériau imprimé

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2012524035

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12747735

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12747735

Country of ref document: EP

Kind code of ref document: A1