WO2019102854A1 - Aqueous liquid ink and printed article - Google Patents

Aqueous liquid ink and printed article Download PDF

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Publication number
WO2019102854A1
WO2019102854A1 PCT/JP2018/041462 JP2018041462W WO2019102854A1 WO 2019102854 A1 WO2019102854 A1 WO 2019102854A1 JP 2018041462 W JP2018041462 W JP 2018041462W WO 2019102854 A1 WO2019102854 A1 WO 2019102854A1
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WIPO (PCT)
Prior art keywords
mass
parts
polyol
binder
less
Prior art date
Application number
PCT/JP2018/041462
Other languages
French (fr)
Japanese (ja)
Inventor
定 永浜
直人 佐竹
克郎 小田
利桂 佐坂
康敬 小代
Original Assignee
Ｄｉｃグラフィックス株式会社
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グラフィックス株式会社 filed Critical Ｄｉｃグラフィックス株式会社
Priority to AU2018373094A priority Critical patent/AU2018373094B2/en
Priority to CN201880073217.1A priority patent/CN111344363B/en
Priority to JP2019531348A priority patent/JP6588683B1/en
Publication of WO2019102854A1 publication Critical patent/WO2019102854A1/en

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Classifications

    • 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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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

Definitions

  • the present invention relates to an aqueous liquid ink that can be used for aqueous printing and a printed matter printed using the aqueous liquid ink.
  • Gravure printing and flexographic printing are widely used for the purpose of imparting cosmetic properties and functionality to a substrate.
  • problems such as pollution such as air pollution by solvent type printing ink, occupational safety and health such as organic solvent poisoning, and danger such as flammable explosion in printing ink industry, safety and health during work at the same time
  • problems such as pollution such as air pollution by solvent type printing ink, occupational safety and health such as organic solvent poisoning, and danger such as flammable explosion in printing ink industry, safety and health during work at the same time
  • problems such as pollution such as air pollution by solvent type printing ink, occupational safety and health such as organic solvent poisoning, and danger such as flammable explosion in printing ink industry, safety and health during work at the same time
  • water-based printing inks have been widely used for printing general packaging paper and paper containers such as cardboard.
  • an organic solvent solution of a polyurethane resin obtained by reacting an isocyanate group-containing polymer with a polyhydrazide compound and a polyamine compound other than a polyhydrazide compound is neutralized with deionized water containing ammonia water
  • a surface-printing aqueous ink for packaging using an aqueous polyurethane resin which has been made water-soluble by being used as a binder see, for example, Patent Document 1: JP-A-8-53641.
  • an aqueous printing ink composition for lamination using an aqueous polyurethane resin obtained by reacting water and trimethylamine after being obtained by reacting an organic diisocyanate compound, a polymer diol compound containing a specific polycarbonate diol, and a chain extender is proposed (see, for example, Patent Document 2: Japanese Patent Application Laid-Open No. 5-171091).
  • the aqueous printing ink dries more slowly than the solvent-based ink, and in addition to having adhesion to a plastic substrate which is the basic performance and blocking resistance, it is dried on the pigment dispersibility, gravure plate, etc. It is necessary that the ink film has re-solubility which can be dissolved again by the aqueous printing ink, and it is difficult to improve the printing density by combining these.
  • the surface printing aqueous ink for packaging described in Patent Document 1 there are cases where the blocking resistance and the re-dissolution are not sufficient.
  • re-solubility may not be enough, and in particular, it might not be able to be said that it can resist long run printing.
  • the present invention has been made in view of the above circumstances, and it has both adhesion to a substrate, resistance to blocking, re-solubility, high printing density, and compatibility with higher water resistance (boil retort).
  • An object of the present invention is to provide an aqueous liquid ink that can be used. By combining the above-mentioned performances, it is possible to provide a print which can withstand boiling retort when it is used as an aqueous liquid ink (in particular, an aqueous liquid ink for printing for laminating a packaging material).
  • the present invention is an aqueous liquid ink comprising a colorant (A), a binder (B) having an acid group, a basic compound (C) and an aqueous medium (D), wherein the binder (B) has the acid group A urethane resin (B1) which is a reaction product of a polyol (b1) containing an acid group-containing polyol (b1-1) and a polyether polyol (b1-2) and a polyisocyanate (b2)
  • the content of the alicyclic structure contained in the urethane resin (B1) is 1,000 mmol / kg or more and 5,000 mmol / kg or less in the total amount of the urethane resin (B1), and the basic compound It relates to an aqueous liquid ink characterized in that C) contains a basic metal compound (C1) and an organic amine (C2).
  • an aqueous liquid ink not only having adhesiveness, blocking resistance, re-solubility, and high printing density, but also having high water resistance (boil retort).
  • the aqueous liquid ink of the present invention comprises a colorant (A), a binder (B) having an acid group, a basic compound (C) and an aqueous medium (D).
  • the coloring agent (A) one or more kinds can be used, and a pigment such as an organic pigment or an inorganic pigment, a dye and the like can be mentioned, and those used for an ink, a paint, a recording agent and the like are preferable.
  • the organic pigment include azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, diketopyrrolopyrrole pigments, and isoindoline pigments. And other pigments.
  • the inorganic pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, mica (mica) and the like. Further, it is possible to use a bright pigment (Metashine; Nippon Sheet Glass Co., Ltd.) in which a metal flake or a metal oxide is coated on a glass flake or a massive flake as a base material.
  • a bright pigment Metalashine; Nippon Sheet Glass Co., Ltd.
  • Aluminum is in powder or paste form, but it is preferable to use paste form in terms of handleability and safety, and it is preferable to use leafing type aluminum or non-leafing in terms of brightness and density. It is suitably selected from
  • the total content of the pigment is preferably 1% by mass or more, and preferably 50% by mass or less, based on the total amount of the ink, from the viewpoint of securing the concentration and coloring power of the ink.
  • the binder (B) having an acid group is a urethane which is a reaction product of a polyol (b1) containing an acid group-containing polyol (b1-1) and a polyether polyol (b1-2) and a polyisocyanate (b2) It contains a resin (B1).
  • the acid value of the urethane resin (B1) is preferably 3 mg KOH / g or more, more preferably 5 mg KOH / g or more, preferably 40 mg KOH / g or less, more preferably 25 mg KOH / g or less.
  • the acid value means a theoretical value calculated based on the amount of the acid group-containing compound such as the polyol (b1-1) having an acid group used for the production of the urethane resin (B1).
  • the said urethane resin (B1) contains an alicyclic structure.
  • the alicyclic structure includes, for example, 3 to 10 carbon atoms (preferably 4 to 8 carbon atoms) such as cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, cyclooctyl ring and propylcyclohexyl ring.
  • the content of the alicyclic structure contained in the urethane resin (B1) is 1,000 mmol / kg or more, preferably 1,300 mmol / kg or more, more preferably 1 in the total amount of the urethane resin (B1). , 800 mmol / kg or more and 5,000 mmol / kg or less, preferably 3,000 mmol / kg or less, more preferably 2,500 mmol / kg or less.
  • the proportion of the alicyclic structure contained in the urethane resin (B1) is the total mass of all the raw materials such as the polyol (b1) and the polyisocyanate (b2) used in the production of the urethane resin (B1).
  • an alicyclic structure of an alicyclic structure-containing compound (a polyol (b1-3 having an alicyclic structure, polyisocyanate having an alicyclic structure)) used in the production of the urethane resin (A) It is a value calculated based on the amount of substance.
  • the alicyclic structure may be contained in the polyol (b1) or may be contained in the polyisocyanate (b2).
  • the content ratio of the alicyclic structure derived from the polyisocyanate (b2) to the alicyclic structure derived from the polyol (b1) is 0 or more, preferably 0.05 or more, more preferably on a molar basis Is 0.1 or more, more preferably 0.2 or more, preferably 10 or less, more preferably 8 or less, and still more preferably 5 or less.
  • Examples of the acid group of the polyol (b1-1) having an acid group include, for example, a carboxy group or a sulfonic acid group, and as the polyol (b1-1) having an acid group, for example, a polyol having a carboxy group And polyols having a sulfonic acid group.
  • the polyol having a carboxy group one or two or more kinds thereof can be used.
  • the polyester polyol having a carboxy group can be obtained by reacting the hydroxy acid with various polycarboxylic acids.
  • the polyol having a sulfonic acid group one or two or more species can be used.
  • a dicarboxylic acid having a sulfonic acid group or a salt thereof and a low molecular weight polyol for example, a molecular weight of 100 or more and 1000 or less
  • the polyester polyol etc. which are reaction substances are mentioned.
  • the dicarboxylic acid having a sulfonic acid group include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid and the like.
  • low molecular weight polyol examples include alkanediols having 1 to 10 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc .; carbon atoms such as diethylene glycol Polyether polyols having a number of 2 to 10 can be mentioned.
  • the number average molecular weight of the polyol (b1-1) having an acid group is preferably 100 or more, preferably 2000 or less, and more preferably 1000 or less.
  • the number average molecular weight and the weight average molecular weight refer to polystyrene equivalent values obtained by measurement by gel permeation chromatography (GPC).
  • polyether polyol (b1-2) for example, an alkylene oxide is added using one or two or more compounds having two or more groups (—NH— or —OH) having an active hydrogen atom as an initiator. What was polymerized is mentioned.
  • the initiator examples include hydroxyl groups such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and bisphenol A. And compounds having two hydroxyl groups, such as glycerin, trimethylolethane, trimethylolpropane and the like.
  • alkylene oxide examples include epoxide compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin and the like; carbon atoms having 4 or more carbon atoms such as tetrahydrofuran (preferably 4 to 6 carbon atoms, particularly preferably) And cyclic ethers having 4 carbon atoms.
  • the number average molecular weight of the polyether polyol is preferably 500 or more, more preferably 1,000 or more, preferably 4,000 or less, more preferably 3,000 or less from the viewpoint of compatibility with the pigment etc. is there.
  • the number average molecular weight refers to a value obtained by measurement by gel permeation chromatography (GPC).
  • the total content of the polyol (b1-1) having an acid group and the polyether polyol (b1-2) is preferably 60% by mass or more, more preferably 75% by mass or more, in the polyol (b1) Is 80% by mass or more, more preferably 90% by mass or more, and may be 95% by mass or less.
  • the polyol (b1) preferably further contains a polyol (b1-3) having an alicyclic structure.
  • a polyol (b1-3) having an alicyclic structure one or more species can be used, and examples thereof include cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctane Saturated diols having an alicyclic structure such as diol, butylcyclohexanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, dicyclohexanediol, hydrogenated bisphenol A, 1,3-adamantanediol; 1,1'-bicyclohexene Examples thereof include unsaturated diols having an alicyclic structure such as silidenediol; and saturated triols having an alicyclic structure such as
  • the content thereof is preferably 0% by mass or more, more preferably 5% by mass, in the total amount of the polyol (b1) from the viewpoint of suppression of blocking of printed matter
  • it is 40 mass% or less, Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less.
  • the total content of the polyol (b1-1) having an acid group, the polyether polyol (b1-2) and the polyol (b1-3) having an alicyclic structure is preferably 70% of the polyol (b1).
  • the content is preferably at least 80% by mass, more preferably at least 90% by mass.
  • the polyol (b1) may contain other polyols (b1-4).
  • the other polyols include polyester polyols, low molecular weight polyols (for example, having a molecular weight of 50 or more and 300 or less), polycarbonate polyols, and polyolefin polyols.
  • polyester polyol for example, a polyester polyol obtained by esterification reaction of a low molecular weight polyol (for example, a polyol having a molecular weight of 50 to 300) with a polycarboxylic acid; ring-opening polymerization of cyclic ester compounds such as ⁇ -caprolactone Polyester polyols obtained by reaction; copolyester polyols thereof and the like can be mentioned.
  • low molecular weight polyol examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 1,4-butanediol.
  • Relatively low molecular weight such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol etc. (eg, molecular weight 50 to 300) And the like.
  • polycarboxylic acids examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; And ester-forming derivatives of aromatic polycarboxylic acids and aromatic polycarboxylic acids.
  • polyols having a molecular weight of about 50 to about 300 can be used.
  • ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol Aliphatic polyols having 2 to 6 carbon atoms such as 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, etc .; 1,4-cyclohexanediol, cyclohexane Alicyclic structure-containing polyols such as dimethanol; and aromatic structure-containing polyols such as bisphenol compounds such as bisphenol A and bisphenol F and alkylene oxide adducts thereof.
  • polycarbonate polyol examples include a reaction product of a carbonate and a polyol; and a reaction product of phosgene and bisphenol A or the like.
  • Examples of the carbonic ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.
  • polyols examples include polyols exemplified as the above low molecular weight polyols; high molecular weight polyols (weights such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.), polyester polyols (polyhexamethylene adipate, etc.), etc. And the like.
  • polystyrene polyol examples include polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, hydrogenated (hydrogenated) polyisoprene polyol and the like.
  • the content of the other polyol (b1-4) in the polyol (b1) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass
  • the content is particularly preferably 10% by mass or less.
  • the content of the polyester polyol is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less in the polyol (b1).
  • polyisocyanate (b2) 1 type (s) or 2 or more types can be used, For example, 4,4'- diphenylmethane diisocyanate, 2,4'- diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate
  • Aromatic polyisocyanates such as tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl Fats such as methane diisocyanate
  • the polyisocyanate (b2) preferably contains a polyisocyanate having an alicyclic structure.
  • the content of the polyisocyanate having an alicyclic structure is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass in the polyisocyanate (b2). % Or less.
  • the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyisocyanate (b2) to the hydroxyl group contained in the polyol (b1) is preferably 0.8 or more, more preferably 0.9 or more on a molar basis. Preferably it is 2.5 or less, More preferably, it is 2.0 or less, More preferably, it is 1.5 or less.
  • 1 type (s) or 2 or more types can be used,
  • the compound which has a polyamine, a hydrazine compound, and the other active hydrogen atom is mentioned.
  • polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-ethylaminoethylamine, N-methylaminopropylamine, etc .; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N- Diamines having a hydroxy group such as hydroxypropylaminopropylamine; triamines such as diethylenetriamine and dipropylenetriamine; and tetramines such as triethylenetetramine. Among these, ethylenediamine is preferred.
  • hydrazine compound examples include hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, ⁇ -semicarbazide Propionic acid hydrazide, 3-semicarbazide propyl carbazate, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane and the like can be mentioned.
  • Examples of other compounds having active hydrogen include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and sucrose.
  • Glycols such as methylene glycol, glycerin and sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, phenols such as hydrogenated bisphenol A, hydroquinone, water Etc.
  • the equivalent ratio [amino group / isocyanate group] of the amino group to the isocyanate group possessed by the polyamine is preferably 1.2 or less, and 0.3 or more and 1 or less. More preferable.
  • the weight average molecular weight of the urethane resin (A) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, preferably 500,000, from the viewpoint of improving the durability of the printed matter. Or less, more preferably 200,000 or less, still more preferably 100,000 or less.
  • the urethane resin (B1) can be produced by reacting the polyol (b1) with the polyisocyanate (b2) and, if necessary, further reacting the chain extender.
  • the reaction temperature at the time of making the said polyol (b1) and the said polyisocyanate (b2) react is 50 degreeC or more and 150 degrees C or less.
  • organic solvent one or more species can be used.
  • ketone solvents such as acetone and methyl ethyl ketone
  • ether solvents such as tetrahydrofuran and dioxane
  • ester solvents such as ethyl acetate and butyl acetate
  • nitriles such as acetonitrile
  • Amide solvents such as dimethylformamide, N-methylpyrrolidone and the like can be mentioned.
  • the organic solvent may be partially or entirely removed, for example, by distillation under reduced pressure, during or after the production of the urethane resin (B1), in order to reduce the safety and the load on the environment.
  • the content of the urethane resin (B1) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, particularly preferably 100% by mass in the binder (B) having the acid group. %.
  • the binder (B) having an acid group may be dispersed in an aqueous medium (D) described later in advance.
  • the binder (B) having the acid group is prepared (binder (B) preparation step), The binder (B) and at least a part of the basic compound (C) described later are mixed (neutralization step), and the obtained mixture and the aqueous medium (D) are mixed to prepare a dispersion ( Dispersion process) can be mentioned.
  • the chain extender may be added in the binder (B) preparation step or may be added after the dispersion step.
  • the content of the binder (B) having an acid group is preferably 10% by mass in the dispersion from the viewpoint of resolubility of aqueous ink, suppression of blocking of printed matter, improvement of printing density, and adhesion to a substrate. % Or more, more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less.
  • An emulsifier may be used in the above-mentioned method for making water, if necessary.
  • a machine such as a homogenizer may be used as needed.
  • the emulsifier include nonionic emulsifiers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene / polyoxypropylene copolymer, etc.
  • Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, alkyl diphenyl ether sulfonate sodium salts, etc.
  • Anionic emulsifiers; cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzyl ammonium salts It is. Among them, anionic or nonionic emulsifiers are preferable from the viewpoint of storage stability.
  • the basic compound (C) contains a basic metal compound (C1) and an organic amine (C2).
  • Examples of the basic metal compound (C1) include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and magnesium hydroxide; metal chlorides such as sodium chloride and potassium chloride; copper sulfate And other metal sulfates.
  • organic amine (C2) examples include ammonia; primary amines such as monoethanolamine; tertiary amines such as triethylamine and diethylethanolamine; and cyclic amines such as morpholine.
  • the ratio represented by the following formula is preferably 0.001 or more, more preferably 0.01 or more, more preferably 0.05 or more, 0.3 or less, preferably 0.25 or less, more preferably Is 0.2 or less, more preferably 0.15 or less. Boil retortability becomes good because the ratio is in the above range. Number of moles of basic metal compound (C1) ⁇ valent number of basic metal compound (C1) / ⁇ (number of moles of organic amine (C2) ⁇ valent number of organic amine (C2)) + (basic metal compound (C1) Number of moles of) ⁇ valence of basic metal compound (C1)) ⁇
  • the basic metal compound (C1) and the organic amine (C2) may form a salt with the acid group of the binder (B) having the acid group in an aqueous liquid ink. It becomes easy to improve water dispersibility because the basic compound (C1) and the organic amine (C1) neutralize the acid group of the binder having the acid group.
  • the content of the basic compound (C) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 100 parts by mass of the binder (B) having the acid group. It is 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 4 parts by mass or less.
  • aqueous medium (D) examples include water; hydrophilic organic solvents; mixtures of water and hydrophilic organic solvents and the like, and from the viewpoint of safety and addition to the environment, water or a mixture of water and hydrophilic organic solvents is preferable.
  • the hydrophilic organic solvent may be used alone or in combination of two or more, and is preferably miscible with water.
  • alcohol solvents such as methanol, ethanol, n-propanol and 2-propanol
  • acetone Ketone solvents such as methyl ethyl ketone
  • polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, propylene glycol, polyalkylene glycol, and glycerin
  • propylene glycol monomethyl ether propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethyl carbitol And ether solvents such as N-methyl-2-pyrrolidone.
  • the content of water in the aqueous medium (D) is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass. % Or more, for example, 100% by mass or less, or even 95% by mass or less is acceptable.
  • the aqueous liquid ink of the present invention may further contain an auxiliary.
  • the auxiliary include paraffin-based waxes for imparting abrasion resistance, slipperiness, etc., waxes such as polyethylene-based waxes and carnauba waxes; fatty acid amide compounds such as oleic acid amide, stearic acid amide and erucic acid amide; printing It is also possible to appropriately use a silicon-based or non-silicon-based antifoaming agent, a dispersing agent, and the like for suppressing foaming at that time.
  • the acid value of the dispersant is preferably 30 mg KOH / g or less, more preferably 25 mg KOH / g or less, still more preferably 20 mg KOH / g or less, and may be, for example, 1 mg KOH / g or more, further 3 mg KOH / g or more.
  • the acid value of the dispersant is preferably smaller than the acid value of the binder (B) having the acid group.
  • the difference between the acid value of the binder (B) having an acid group and the acid value of the dispersant is, for example, 1 mg KOH / g or more, more preferably 3 mg KOH / g or more, preferably 30 mg KOH / g or less, more preferably It is 20 mg KOH / g or less.
  • the content of the dispersant is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, preferably 100 parts by mass with respect to 100 parts by mass of the colorant (A).
  • the amount is preferably at most 80 parts by mass, more preferably at most 75 parts by mass.
  • the content of the dispersant is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, with respect to 100 parts by mass of the binder (B) having the acid group. Is 100 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less.
  • the viscosity of the aqueous liquid ink is preferably 7 seconds or more, more preferably 10 seconds or more, preferably 25 seconds or less, more preferably 7 seconds or more, more preferably 10 seconds or more, as a numerical value measured at 25 ° C. Is less than 20 seconds.
  • the viscosity in millipascal second is preferably 70 (mPa ⁇ s) or more, more preferably 100 (mPa ⁇ s) or more, preferably 350 (mPa ⁇ s) or less, more preferably 250 (mPa ⁇ s) at 25 ° C. It is less than mPa ⁇ s).
  • the surface tension of the aqueous liquid ink is preferably 25 mN / m or more, more preferably 33 mN / m or more, and preferably 50 mN / m or less, more preferably 43 mN / m or less.
  • the surface tension of the aqueous liquid ink is preferably 25 mN / m or more, more preferably 33 mN / m or more, and preferably 50 mN / m or less, more preferably 43 mN / m or less.
  • the aqueous liquid ink according to the present invention can be produced using an Eiger mill, a sand mill, a gamma mill, an attritor or the like generally used in the production of gravure and flexographic printing inks.
  • the colorant (A), at least a part of the binder (B) having the acid group, and at least the basic compound (C) in advance A pre-composition (mill base ink) may be prepared by mixing a part, the dispersant and at least a part of the aqueous medium (D).
  • the aqueous liquid ink of the present invention has excellent adhesion to various substrates, and can be used for printing on paper, synthetic paper, thermoplastic resin film, plastic products, steel plates, etc. While it is useful as an ink for gravure printing using a gravure printing plate according to the present invention or for flexographic printing using a flexographic printing plate using a resin plate etc., it is suitable for an inkjet system which ejects ink from an inkjet nozzle without using a plate It excludes the ink.
  • ink droplets ejected from the nozzles are in close contact with the substrate directly to form a printed matter, whereas the aqueous liquid ink of the present invention once adheres and transfers the printing ink to the printing plate or printing pattern. After that, only the ink is brought into close contact with the substrate again, and it is dried as required to form a printed matter.
  • the film thickness of the printing ink formed from the gravure printing method or the flexographic printing method using the aqueous liquid ink of the present invention is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • the base material is polyamide resin such as nylon 6, nylon 66, nylon 46, polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc.
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • polytrimethylene terephthalate polytrimethylene naphthalate
  • polybutylene terephthalate polybutylene naphthalate, etc.
  • Biodegradable resins such as polyhydroxycarboxylic acid such as resin, polylactic acid, etc., aliphatic polyester resin such as poly (ethylene succinate), poly (butylene succinate), polyolefin resin such as PP, polyethylene, polyimide resin, poly Films made of thermoplastic resins such as arylate resins or mixtures thereof and laminates thereof are mentioned, and among them, films made of polyester, polyamide, polyethylene and polypropylene can be suitably used. These base films may be unstretched films or stretched films, and the production method is not limited. Also, the thickness of the base film is not particularly limited, but usually, it may be in the range of 1 to 500 ⁇ m.
  • the printed surface of the substrate film is preferably subjected to corona discharge treatment, and silica, alumina or the like may be vapor deposited.
  • Synthesis Example 1 Preparation of Binder (1) 195 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 145 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer
  • the organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal was obtained by reacting the component and 28 parts by mass of 1,4-cyclohexanedimethanol in 203 parts by mass of methyl ethyl ketone.
  • aqueous dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass and 9.2 parts by mass of an aqueous solution of hydrazine, and then a binder (1) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
  • the ratio of the alicyclic structure in the urethane resin in the binder (1) was 2115 mmol / kg, and the acid value was 28 mg KOH / g.
  • aqueous dispersion of a urethane resin is obtained by adding and stirring thoroughly with a mass part and 9.1 mass part of an 80% aqueous hydrazine solution, and then a binder (2) having a nonvolatile content of 40 mass% is obtained by aging and desolvation. Obtained.
  • the proportion of the alicyclic structure in the urethane resin in the binder (2) was 2103 mmol / kg, and the acid value was 28 mg KOH / g.
  • Binder 192 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 142 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer An organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular end (a binder having an acid group) was obtained by reacting the compound and 28 parts by mass of 1,4-cyclohexanedimethanol in 200 parts by mass of methyl ethyl ketone.
  • aqueous dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass of an aqueous 80% hydrazine solution, and then a binder (4) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
  • the proportion of the alicyclic structure in the urethane resin in the binder (4) was 2080 mmol / kg, and the acid value was 28 mg KOH / g.
  • a water dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass of an aqueous 80% hydrazine solution, and then a binder (5) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
  • the proportion of the alicyclic structure in the urethane resin in the binder (5) was 2069 mmol / kg, and the acid value was 28 mg KOH / g.
  • Synthesis Example 6 Preparation of Binder (6) 269 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 102 parts by mass of isophorone diisocyanate, 24 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer
  • the organic solvent solution of the urethane prepolymer (binder having an acid group) having an isocyanate group at the molecular terminal was obtained by reacting the part and 3.5 parts by mass of neopentyl glycol in 204 parts by mass of methyl ethyl ketone.
  • aqueous dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass and 6.4 parts by mass of a 80% aqueous hydrazine solution, and then a binder (6) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
  • the ratio of the alicyclic structure in the urethane resin in the binder (6) was 1142 mmol / kg, and the acid value was 25 mg KOH / g.
  • An aqueous dispersion of a urethane resin is obtained by adding and stirring thoroughly with a mass part and 6.3 mass parts of an 80% aqueous hydrazine solution, and then a binder (7) having a nonvolatile content of 40 mass% is obtained by aging and desolvation. Obtained.
  • the proportion of the alicyclic structure in the urethane resin in the binder (7) was 1222 mmol / kg, and the acid value was 23 mg KOH / g.
  • aqueous dispersion of a urethane resin is obtained by adding 10 parts by mass and 7.0 parts by mass of a 80% aqueous hydrazine solution, and then an aqueous dispersion of urethane resin is obtained. Obtained.
  • the proportion of the alicyclic structure in the urethane resin in the binder (8) was 1683 mmol / kg, and the acid value was 9 mg KOH / g.
  • Binder 9 115 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 181 parts by mass of isophorone diisocyanate, 17 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer
  • the organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal was obtained by reacting part and 85 parts by mass of 1,4-cyclohexanedimethanol in 205 parts by mass of methyl ethyl ketone.
  • aqueous dispersion of a urethane resin is obtained by adding 2 parts by mass and 2.2 parts by mass of an aqueous 80% hydrazine solution, and then an aqueous dispersion of a urethane resin is obtained. Then, a binder (9) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
  • the proportion of the alicyclic structure in the urethane resin in the binder (9) was 3511 mmol / kg, and the acid value was 18 mg KOH / g.
  • Comparative Synthesis Example 1 Preparation of Binder (10) 196 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 145 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer
  • the organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal was obtained by reacting the compound and 28 parts by mass of 1,4-cyclohexanedimethanol in 204 parts by mass of methyl ethyl ketone.
  • aqueous ammonia solution is added to neutralize part or all of the carboxy groups possessed by the urethane prepolymer, and further 725 parts by mass of water and 9.2 parts by mass of 80% aqueous hydrazine solution
  • the aqueous dispersion of the urethane resin was obtained by sufficiently stirring, and then aging and solvent removal to obtain a binder (10) having a nonvolatile content of 40% by mass.
  • the proportion of the alicyclic structure in the urethane resin in the binder (10) was 2120 mmol / kg, and the acid value was 28 mg KOH / g.
  • Comparative Synthesis Example 2 Preparation of Binder (11) 196 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 145 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer The organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal was obtained by reacting the compound and 28 parts by mass of 1,4-cyclohexanedimethanol in 204 parts by mass of methyl ethyl ketone.
  • Comparative Synthesis Example 3 Preparation of Binder (12) 191 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 141 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer By reacting 1 part and 27 parts by mass of 1,4-cyclohexanedimethanol in 198 parts by mass of methyl ethyl ketone, an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular end was obtained.
  • aqueous dispersion of a urethane resin was obtained by adding parts and stirring sufficiently, and then aging and desolvation to obtain a binder (12) having a nonvolatile content of 40% by mass.
  • the proportion of the alicyclic structure in the urethane resin in the binder (12) was 2064 mmol / kg, and the acid value was 28 mg KOH / g.
  • Comparative Synthesis Example 4 Preparation of Binder (13) 296 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 82 parts by mass of isophorone diisocyanate, 17 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer
  • the organic solvent solution of the urethane prepolymer which has an isocyanate group at the molecular terminal was obtained by making the part and 3.6 parts by mass of neopentyl glycol react in 205 parts by mass of methyl ethyl ketone.
  • 1.4 parts by mass of 50% by mass potassium hydroxide aqueous solution and 7.6 parts by mass of 25% by mass ammonia aqueous solution are added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and water 727 is further added.
  • An aqueous dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass and 3.4 parts by mass of a 80% aqueous hydrazine solution, and then a binder (13) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
  • the proportion of the alicyclic structure in the urethane resin in the binder (13) was 917 mmol / kg, and the acid value was 17 mg KOH / g.
  • Examples 1 to 9 and Comparative Examples 1 to 4 The binders (1) to (13) obtained in Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 4 were well stirred and mixed according to the following compositions, respectively, and then milled using a bead mill to prepare a milled base ink . Subsequently, 10 parts by mass of each of the binders (1) to (13) and 4 parts by mass of water were further added to the obtained ground meat base ink to prepare an aqueous blue printing ink.
  • the viscosity of the obtained printing ink is adjusted with water so as to be 16 seconds (25 ° C.) with Zahn cup # 4 (manufactured by Rigosha Co., Ltd.), and the aqueous liquid inks of Examples 1 to 9 and Comparative Examples 1 to 4 respectively. did.
  • the surface tension at 25 ° C. was measured to confirm the surface tension of the obtained aqueous liquid ink.
  • the surface tension was measured based on the Wilhelmy method using an automatic surface tension meter DY-300 manufactured by Kyowa Interface Science Co., Ltd.
  • Total blending amount of water-based liquid ink blue (excluding water for viscosity adjustment)
  • FASTOGEN BLUE LA 5380 mochi pigment 15 parts by mass
  • Binder for aqueous flexographic ink 50 parts by mass nonionic pigment dispersant (manufactured by BYK) 10 parts by mass isopropyl alcohol 3 parts by mass water 12 parts by mass silicone defoamer (BYK Made by company) 0.2 parts by mass
  • the aqueous liquid inks of Examples 1 to 9 and Comparative Examples 1 to 4 were treated with a corona-treated polyethylene terephthalate (PET) film shown in Table 1 (Toyobo ( Co., Ltd. Ester E5102 thickness 12 ⁇ m, Corona-treated biaxially oriented polypropylene (OPP) film (Toyobo Co., Ltd. Pyrene P 2161 thickness 20 ⁇ m), print a solid pattern of 240 mm long ⁇ 80 mm wide, and then dry it with a dryer I got the printed matter.
  • PET polyethylene terephthalate
  • OPP Corona-treated biaxially oriented polypropylene
  • a non-oriented polypropylene film (hereinafter, R-CPP: Toray Synthetic Film ZK-75 50 ⁇ m) is laminated, and subjected to aging at 40 ° C. for 5 days, A three-layer composite laminate 2 was obtained.
  • the obtained laminate 2 was formed into a pouch of 120 mm ⁇ 120 mm and filled with 70 g of simulated food containing vinegar, salad oil and meat sauce at a weight ratio of 1: 1: 1.
  • the resulting pouch was subjected to steam retort sterilization treatment at 135 ° C. for 30 minutes, and the degree of peeling of the ink film was evaluated in three steps.
  • ⁇ There is no peeling at all.
  • ⁇ There is very little blister-like peeling.
  • ⁇ Partially blister-like peeling of medium size.
  • X There is peeling on the entire surface regardless of size.
  • an aqueous liquid ink which has both adhesion to a substrate, resistance to blocking, re-dissolution and high printing density and is compatible with higher water resistance (boil retort)can be provided.
  • oil retort water resistance

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Abstract

The present invention addresses the problem of providing an aqueous liquid ink which exhibits adhesion to a base material, blocking resistance, redissolution properties, and a high printing density, and which is also capable of achieving high water resistance (boil retort properties). This aqueous liquid ink includes a colouring agent (A), a binder (B) having acid groups, a basic compound (C), and an aqueous medium (D). The binder (B) having acid groups includes a urethane resin (B1) which is a reaction product of a polyisocyanate (b2), and a polyol (b1) including a polyol (b1-1) having acid groups and a polyether polyol (b1-2). The content of alicyclic structures included in the urethane resin (B1) is in the range of 1,000-5,000 mmol/kg inclusive. The basic compound (C) includes a basic metal compound (C1) and an organic amine (C2).

Description

水性リキッドインキ及び印刷物Water-based liquid ink and printed matter
　本発明は、水性印刷に使用可能な水性リキッドインキ及び水性リキッドインキを用いて印刷されたものである印刷物に関する。 The present invention relates to an aqueous liquid ink that can be used for aqueous printing and a printed matter printed using the aqueous liquid ink.
　グラビア印刷やフレキソ印刷は、被印刷体に美粧性、機能性を付与させる目的で広く用いられている。近年、印刷インキ業界において溶剤型印刷インキによる大気汚染等の公害、有機溶剤中毒等の労働安全衛生、更に引火爆発等の危険といった問題を解決する一つの手段として、さらには作業時の安全衛生性、環境の保護、包装材の残留溶剤の低減等の見地から水性印刷インキへの転換の要望が高まっている。事実、水性印刷インキは一般包装紙や段ボール等の紙器等の印刷に広く実用されてきている。 Gravure printing and flexographic printing are widely used for the purpose of imparting cosmetic properties and functionality to a substrate. In recent years, as a means to solve problems such as pollution such as air pollution by solvent type printing ink, occupational safety and health such as organic solvent poisoning, and danger such as flammable explosion in printing ink industry, safety and health during work at the same time There is an increasing demand for conversion to water-based printing inks from the standpoint of environmental protection, reduction of residual solvents in packaging materials, and the like. In fact, water-based printing inks have been widely used for printing general packaging paper and paper containers such as cardboard.
　こうした水性印刷インキの一例として、イソシアネート基含有ポリマーに、ポリヒドラジド化合物及びポリヒドラジド化合物以外のポリアミン化合物を反応させて得られたポリウタン樹脂の有機溶剤溶液を、アンモニア水を含む脱イオン水で中和することで水溶化した水性ポリウレタン樹脂をバインダーとする包装用表刷り水性インキが提案されている（例えば、特許文献１：特開平８－５３６４１参照）。 As an example of such an aqueous printing ink, an organic solvent solution of a polyurethane resin obtained by reacting an isocyanate group-containing polymer with a polyhydrazide compound and a polyamine compound other than a polyhydrazide compound is neutralized with deionized water containing ammonia water There has been proposed a surface-printing aqueous ink for packaging using an aqueous polyurethane resin which has been made water-soluble by being used as a binder (see, for example, Patent Document 1: JP-A-8-53641).
　また、有機ジイソシアネート化合物、特定のポリカーボネートジオールを含有する高分子ジオール化合物および鎖伸長剤を反応させて得た後、水及びトリメチルアミンを加えて水性化した水性ポリウレタン樹脂を用いたラミネート用水性印刷インキ組成物が提案されている（例えば、特許文献２：特開平５－１７１０９１参照）。 In addition, an aqueous printing ink composition for lamination using an aqueous polyurethane resin obtained by reacting water and trimethylamine after being obtained by reacting an organic diisocyanate compound, a polymer diol compound containing a specific polycarbonate diol, and a chain extender. An object is proposed (see, for example, Patent Document 2: Japanese Patent Application Laid-Open No. 5-171091).
特開平８－　５３６４１号公報JP-A-8-53641 特開平５－１７１０９１号公報Unexamined-Japanese-Patent No. 5-171091
　しかしながら、水性印刷インキは溶剤型インキと比較すると乾燥が遅く、基本性能であるプラスチック基材への接着性、耐ブロッキング性を有することに加えて、顔料の分散性、グラビア版上などで乾燥したインキ皮膜が再度水性印刷インキによって溶解できる再溶解性を有することが必要であり、これらを兼ね備えた上で印刷濃度を向上することは困難である。例えば、特許文献１に記載の包装用表刷り水性インキでは、耐ブロッキング性、再溶解性が十分でない場合があった。また、特許文献２に記載のラミネート用水性印刷インキ組成物では、再溶解性は十分でない場合があり、特にロングラン印刷に耐えうるものとはいえない場合があった。 However, the aqueous printing ink dries more slowly than the solvent-based ink, and in addition to having adhesion to a plastic substrate which is the basic performance and blocking resistance, it is dried on the pigment dispersibility, gravure plate, etc. It is necessary that the ink film has re-solubility which can be dissolved again by the aqueous printing ink, and it is difficult to improve the printing density by combining these. For example, in the case of the surface printing aqueous ink for packaging described in Patent Document 1, there are cases where the blocking resistance and the re-dissolution are not sufficient. Moreover, in the case of the aqueous | water-based printing ink composition for laminations described in patent document 2, re-solubility may not be enough, and in particular, it might not be able to be said that it can resist long run printing.
　本発明は、前記事情に鑑みてなされたものであり、基材に対する密着性・耐ブロッキング性・再溶解性・高い印刷濃度を兼ね備えた上に、さらに高い耐水性（ボイルレトルト性）とを両立できる水性リキッドインキを提供することを課題とする。上記性能を兼ね備えることで、水性リキッドインキ（特に、包装材料のラミネート用印刷用の水性リキッドインキ）として用いた場合に、ボイルレトルトにも耐えうる印刷物を提供可能である。 The present invention has been made in view of the above circumstances, and it has both adhesion to a substrate, resistance to blocking, re-solubility, high printing density, and compatibility with higher water resistance (boil retort). An object of the present invention is to provide an aqueous liquid ink that can be used. By combining the above-mentioned performances, it is possible to provide a print which can withstand boiling retort when it is used as an aqueous liquid ink (in particular, an aqueous liquid ink for printing for laminating a packaging material).
　本発明者らは、上記の課題を解決すべく鋭意研究した結果、ウレタン樹脂が有する酸基を、塩基性金属化合物と有機アミンとを含む塩基性化合物で中和したウレタン樹脂を含有する水性フレキソインキ用バインダーを用いることによって、前記課題を解決できることを見出し、本発明を完成させた。 MEANS TO SOLVE THE PROBLEM As a result of earnestly researching that the present inventors should solve said subject, as a result of the aqueous | water-based flexo containing the urethane resin which neutralized the acid group which a urethane resin has with the basic compound containing a basic metal compound and organic amine. By using the binder for ink, it discovers that the said subject is solvable and completed this invention.
　すなわち、本発明は、着色剤（Ａ）、酸基を有するバインダー（Ｂ）、塩基性化合物（Ｃ）及び水性媒体（Ｄ）を含む水性リキッドインキであって、前記酸基を有するバインダー（Ｂ）が、酸基を有するポリオール（ｂ１－１）及びポリエーテルポリオール（ｂ１－２）を含むポリオール（ｂ１）と、ポリイソシアネート（ｂ２）との反応物であるウレタン樹脂（Ｂ１）を含むものであり、前記ウレタン樹脂（Ｂ１）に含まれる脂環式構造の含有量が、前記ウレタン樹脂（Ｂ１）の総量中、１，０００ｍｍｏｌ／ｋｇ以上５，０００ｍｍｏｌ／ｋｇ以下であり、前記塩基性化合物（Ｃ）が、塩基性金属化合物（Ｃ１）と有機アミン（Ｃ２）とを含むものであることを特徴とする水性リキッドインキに関するものである。 That is, the present invention is an aqueous liquid ink comprising a colorant (A), a binder (B) having an acid group, a basic compound (C) and an aqueous medium (D), wherein the binder (B) has the acid group A urethane resin (B1) which is a reaction product of a polyol (b1) containing an acid group-containing polyol (b1-1) and a polyether polyol (b1-2) and a polyisocyanate (b2) The content of the alicyclic structure contained in the urethane resin (B1) is 1,000 mmol / kg or more and 5,000 mmol / kg or less in the total amount of the urethane resin (B1), and the basic compound It relates to an aqueous liquid ink characterized in that C) contains a basic metal compound (C1) and an organic amine (C2).
　本発明によれば、接着性・耐ブロッキング性・再溶解性・高い印刷濃度を有するだけでなく、さらに高い耐水性（ボイルレトルト性）を有する水性リキッドインキを提供可能である。 According to the present invention, it is possible to provide an aqueous liquid ink not only having adhesiveness, blocking resistance, re-solubility, and high printing density, but also having high water resistance (boil retort).
　本発明の水性リキッドインキは、着色剤（Ａ）、酸基を有するバインダー（Ｂ）、塩基性化合物（Ｃ）及び水性媒体（Ｄ）を含む。 The aqueous liquid ink of the present invention comprises a colorant (A), a binder (B) having an acid group, a basic compound (C) and an aqueous medium (D).
　前記着色剤（Ａ）としては、１種又は２種以上を用いることができ、有機顔料又は無機顔料等の顔料、染料等が挙げられ、インキ、塗料、記録剤等に用いられるものが好ましい。
　前記有機顔料としては、アゾ系、フタロシアニン系、アントラキノン系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系、アゾメチンアゾ系、ジケトピロロピロール系、イソインドリン系などの顔料が挙げられる。 As the coloring agent (A), one or more kinds can be used, and a pigment such as an organic pigment or an inorganic pigment, a dye and the like can be mentioned, and those used for an ink, a paint, a recording agent and the like are preferable.
Examples of the organic pigment include azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, diketopyrrolopyrrole pigments, and isoindoline pigments. And other pigments.
　記無機顔料としては、カーボンブラック、酸化チタン、酸化亜鉛、硫化亜鉛、硫酸バリウム、炭酸カルシウム、酸化クロム、シリカ、ベンガラ、アルミニウム、マイカ（雲母）などが挙げられる。また、ガラスフレーク又は塊状フレークを母材とした上に金属、又は金属酸化物をコートした光輝性顔料（メタシャイン；日本板硝子株式会社）を使用できる。 Examples of the inorganic pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, mica (mica) and the like. Further, it is possible to use a bright pigment (Metashine; Nippon Sheet Glass Co., Ltd.) in which a metal flake or a metal oxide is coated on a glass flake or a massive flake as a base material.
　カラーインデックス名としては、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１、３、１２、１３、１４、１７、４２、７４、８３；
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　１６；
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　５、２２、３８、４８：１、４８：２、４８：４、４９：１、５３：１、５７：１、６３：１、８１、１０１；
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１９、２３；
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　２３、１５：１、１５：３、１５：４、１７：１、１８、２７、２９
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７、３６、５８、５９；
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　７；
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｗｈｉｔｅ　４、６、１８などが挙げられる。 As a color index name,
C. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 42, 74, 83;
C. I. Pigment Orange 16;
C. I. Pigment Red 5, 22, 38, 48: 1, 48: 2, 48: 4, 49: 1, 53: 1, 57: 1, 63: 1, 81, 101;
C. I. Pigment Violet 19, 23;
C. I. Pigment Blue 23, 15: 1, 15: 3, 15: 4, 17: 1, 18, 27, 29
C. I. Pigment Green 7, 36, 58, 59;
C. I. Pigment Black 7;
C. I. Pigment White 4, 6, 18 and the like.
　藍インキにはＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：３（銅フタロシアニン）、黄インキにはコスト・耐光性の点からＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ８３、紅インキにはＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　５７：１を用いることが好ましい。白インキには酸化チタン、墨インキにはカーボンブラック、金、銀インキにはアルミニウム、パールインキにはマイカ（雲母）を使用することがコストや着色力の点から好ましい。アルミニウムは粉末又はペースト状であるが、取扱い性および安全性の面からペースト状で使用するのが好ましく、リーフィングタイプのアルミニウムを使用するかそれともノンリーフィングを使用するかは、輝度感および濃度の点から適宜選択される。 C.I. I. Pigment Blue 15: 3 (copper phthalocyanine), yellow ink, C.I. I. Pigment Yellow 83, C.I. I. It is preferable to use Pigment Red 57: 1. It is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for gold and silver ink, and mica for pearl ink from the viewpoint of cost and coloring power. Aluminum is in powder or paste form, but it is preferable to use paste form in terms of handleability and safety, and it is preferable to use leafing type aluminum or non-leafing in terms of brightness and density. It is suitably selected from
　前記顔料の合計含有率は、インキの濃度、着色力を確保する観点から、インキの総量中、好ましくは１質量％以上であり、好ましくは５０質量％以下である。 The total content of the pigment is preferably 1% by mass or more, and preferably 50% by mass or less, based on the total amount of the ink, from the viewpoint of securing the concentration and coloring power of the ink.
　前記酸基を有するバインダー（Ｂ）は、酸基を有するポリオール（ｂ１－１）及びポリエーテルポリオール（ｂ１－２）を含むポリオール（ｂ１）と、ポリイソシアネート（ｂ２）との反応物であるウレタン樹脂（Ｂ１）を含む。 The binder (B) having an acid group is a urethane which is a reaction product of a polyol (b1) containing an acid group-containing polyol (b1-1) and a polyether polyol (b1-2) and a polyisocyanate (b2) It contains a resin (B1).
　前記ウレタン樹脂（Ｂ１）の酸価は、好ましくは３ｍｇＫＯＨ／ｇ以上、より好ましくは５ｍｇＫＯＨ／ｇ以上であり、好ましくは４０ｍｇＫＯＨ／ｇ以下、より好ましくは２５ｍｇＫＯＨ／ｇ以下である。本明細書において、酸価は、前記ウレタン樹脂（Ｂ１）の製造に用いる酸基を有するポリオール（ｂ１－１）等の酸基含有化合物等の使用量に基づいて算出した理論値を意味する。 The acid value of the urethane resin (B1) is preferably 3 mg KOH / g or more, more preferably 5 mg KOH / g or more, preferably 40 mg KOH / g or less, more preferably 25 mg KOH / g or less. In the present specification, the acid value means a theoretical value calculated based on the amount of the acid group-containing compound such as the polyol (b1-1) having an acid group used for the production of the urethane resin (B1).
　また、前記ウレタン樹脂（Ｂ１）は、脂環式構造を含む。脂環式構造を含むことで、印刷物のブロッキングを抑制することができる。前記脂環式構造としては、例えば、シクロブチル環、シクロペンチル環、シクロヘキシル環、シクロヘプチル環、シクロオクチル環、プロピルシクロヘキシル環等の炭素原子数３以上１０以下（好ましくは炭素原子数４以上８以下）の飽和の単環構造；トリシクロ［５．２．１．０.　２．６］デシル骨格、ビシクロ［４．３．０］ノニル骨格、トリシクロ［５．３．１．１］ドデシル骨格、プロピルトリシクロ［５．３．１．１］ドデシル骨格、ノルボルニル骨格、イソボルニル骨格、ジシクロペンタニル骨格、アダマンチル骨格等の炭素原子数５以上２０以下（好ましくは炭素原子数７以上１２以下）の飽和の橋掛け環構造などが挙げられる。これらの中でも、飽和の単環構造が好ましく、シクロヘキシル環構造がより好ましい。 Moreover, the said urethane resin (B1) contains an alicyclic structure. By including the alicyclic structure, blocking of the printed matter can be suppressed. The alicyclic structure includes, for example, 3 to 10 carbon atoms (preferably 4 to 8 carbon atoms) such as cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, cyclooctyl ring and propylcyclohexyl ring. Saturated monocyclic ring structure; tricyclo [5.2.1.0.2.6] decyl skeleton, bicyclo [4.3.0] nonyl skeleton, tricyclo [5.3.1.1] dodecyl skeleton, propyl tri Saturated with 5 to 20 carbon atoms (preferably 7 to 12 carbon atoms) such as cyclo [5.3.1.1] dodecyl skeleton, norbornyl skeleton, isobornyl skeleton, dicyclopentanyl skeleton, adamantyl skeleton, etc. A bridged ring structure etc. are mentioned. Among these, a saturated single ring structure is preferable, and a cyclohexyl ring structure is more preferable.
　前記ウレタン樹脂（Ｂ１）に含まれる脂環式構造の含有量は、前記ウレタン樹脂（Ｂ１）の総量中、１，０００ｍｍｏｌ／ｋｇ以上であり、好ましくは１，３００ｍｍｏｌ／ｋｇ以上、より好ましくは１，８００ｍｍｏｌ／ｋｇ以上であり、５，０００ｍｍｏｌ／ｋｇ以下であり、好ましくは３，０００ｍｍｏｌ／ｋｇ以下、より好ましくは２，５００ｍｍｏｌ／ｋｇ以下である。
　本明細書において、前記ウレタン樹脂（Ｂ１）に含まれる脂環式構造の割合は、前記ウレタン樹脂（Ｂ１）の製造に使用するポリオール（ｂ１）やポリイソシアネート（ｂ２）等の全原料の合計質量と、前記ウレタン樹脂（Ａ）の製造に使用される脂環式構造含有化合物（脂環式構造を有するポリオール（ｂ１－３）、脂環式構造を有するポリイソシアネート）の有する脂環式構造の物質量に基づいて算出した値である。 The content of the alicyclic structure contained in the urethane resin (B1) is 1,000 mmol / kg or more, preferably 1,300 mmol / kg or more, more preferably 1 in the total amount of the urethane resin (B1). , 800 mmol / kg or more and 5,000 mmol / kg or less, preferably 3,000 mmol / kg or less, more preferably 2,500 mmol / kg or less.
In the present specification, the proportion of the alicyclic structure contained in the urethane resin (B1) is the total mass of all the raw materials such as the polyol (b1) and the polyisocyanate (b2) used in the production of the urethane resin (B1). And an alicyclic structure of an alicyclic structure-containing compound (a polyol (b1-3 having an alicyclic structure, polyisocyanate having an alicyclic structure)) used in the production of the urethane resin (A) It is a value calculated based on the amount of substance.
　前記脂環式構造は、前記ポリオール（ｂ１）に含まれていてもよく、前記ポリイソシアネート（ｂ２）に含まれていてもよい。前記ポリイソシアネート（ｂ２）由来の脂環式構造と、前記ポリオール（ｂ１）由来の脂環式構造との含有量比は、モル基準で、０以上であり、好ましくは０．０５以上、より好ましくは０．１以上、さらに好ましくは０．２以上であり、好ましくは１０以下、より好ましくは８以下、さらに好ましくは５以下である。 The alicyclic structure may be contained in the polyol (b1) or may be contained in the polyisocyanate (b2). The content ratio of the alicyclic structure derived from the polyisocyanate (b2) to the alicyclic structure derived from the polyol (b1) is 0 or more, preferably 0.05 or more, more preferably on a molar basis Is 0.1 or more, more preferably 0.2 or more, preferably 10 or less, more preferably 8 or less, and still more preferably 5 or less.
　前記酸基を有するポリオール（ｂ１－１）の酸基としては、例えば、カルボキシ基又はスルホン酸基が挙げられ、前記酸基を有するポリオール（ｂ１－１）としては、例えば、カルボキシ基を有するポリオール、スルホン酸基を有するポリオール等が挙げられる。 Examples of the acid group of the polyol (b1-1) having an acid group include, for example, a carboxy group or a sulfonic acid group, and as the polyol (b1-1) having an acid group, for example, a polyol having a carboxy group And polyols having a sulfonic acid group.
　前記カルボキシ基を有するポリオールとしては、１種又は２種以上を用いることができ、例えば、２，２－ジメチロールプロピオン酸、２，２－ジメチロールブタン酸、２，２－ジメチロール吉草酸等のヒドロキシ酸；カルボキシ基を有するポリエステルポリオールなどが挙げられる。前記カルボキシ基を有するポリエステルポリオールは、前記ヒドロキシ酸と各種ポリカルボン酸とを反応させることで得ることができる。 As the polyol having a carboxy group, one or two or more kinds thereof can be used. For example, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid, etc. Hydroxy acid; polyester polyol having a carboxy group and the like can be mentioned. The polyester polyol having a carboxy group can be obtained by reacting the hydroxy acid with various polycarboxylic acids.
　前記スルホン酸基を有するポリオールとしては、１種又は２種以上を用いることができ、例えば、スルホン酸基を有するジカルボン酸又はその塩と、低分子量ポリオール（例えば、分子量１００以上１０００以下）との反応物であるポリエステルポリオール等が挙げられる。前記スルホン酸基を有するジカルボン酸としては、例えば、５－スルホイソフタル酸、スルホテレフタル酸、４－スルホフタル酸、５－（４－スルホフェノキシ）イソフタル酸等が挙げられる。前記低分子量ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール等の炭素原子数が１～１０のアルカンジオール；ジエチレングリコール等の炭素原子数が２～１０のポリエーテルポリオールなどが挙げられる。 As the polyol having a sulfonic acid group, one or two or more species can be used. For example, a dicarboxylic acid having a sulfonic acid group or a salt thereof and a low molecular weight polyol (for example, a molecular weight of 100 or more and 1000 or less) The polyester polyol etc. which are reaction substances are mentioned. Examples of the dicarboxylic acid having a sulfonic acid group include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid and the like. Examples of the low molecular weight polyol include alkanediols having 1 to 10 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc .; carbon atoms such as diethylene glycol Polyether polyols having a number of 2 to 10 can be mentioned.
　前記酸基を有するポリオール（ｂ１－１）の数平均分子量は、好ましくは１００以上であり、好ましくは２０００以下、より好ましくは１０００以下である。
　本明細書において、数平均分子量及び重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定して得られたポリスチレン換算値を表すものとする。 The number average molecular weight of the polyol (b1-1) having an acid group is preferably 100 or more, preferably 2000 or less, and more preferably 1000 or less.
In the present specification, the number average molecular weight and the weight average molecular weight refer to polystyrene equivalent values obtained by measurement by gel permeation chromatography (GPC).
　前記ポリエーテルポリオール（ｂ１－２）としては、例えば、活性水素原子を有する基（－ＮＨ－又は－ＯＨ）を２個以上有する化合物の１種又は２種以上を開始剤として、アルキレンオキサイドを付加重合させたものが挙げられる。 As the polyether polyol (b1-2), for example, an alkylene oxide is added using one or two or more compounds having two or more groups (—NH— or —OH) having an active hydrogen atom as an initiator. What was polymerized is mentioned.
　前記開始剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、トリメチレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、ビスフェノールＡ等の水酸基を２個有する化合物；グリセリン、トリメチロールエタン、トリメチロールプロパン等の水酸基を３個有する化合物などが挙げられる。 Examples of the initiator include hydroxyl groups such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and bisphenol A. And compounds having two hydroxyl groups, such as glycerin, trimethylolethane, trimethylolpropane and the like.
　前記アルキレンオキサイドとしては、例えば、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド、エピクロロヒドリン等のエポキシド化合物；テトラヒドロフラン等の炭素原子数４以上（好ましくは炭素原子数４～６、特に好ましくは炭素原子数４）の環状エーテルなどが挙げられる。 Examples of the alkylene oxide include epoxide compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin and the like; carbon atoms having 4 or more carbon atoms such as tetrahydrofuran (preferably 4 to 6 carbon atoms, particularly preferably) And cyclic ethers having 4 carbon atoms.
　前記ポリエーテルポリオールの数平均分子量は、顔料等との相溶性の観点から、好ましくは５００以上、より好ましくは１，０００以上であり、好ましくは４，０００以下、より好ましくは３，０００以下である。
　本明細書において、数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定して得られる値を表すものとする。 The number average molecular weight of the polyether polyol is preferably 500 or more, more preferably 1,000 or more, preferably 4,000 or less, more preferably 3,000 or less from the viewpoint of compatibility with the pigment etc. is there.
In the present specification, the number average molecular weight refers to a value obtained by measurement by gel permeation chromatography (GPC).
　酸基を有するポリオール（ｂ１－１）及び前記ポリエーテルポリオール（ｂ１－２）の合計の含有率は、ポリオール（ｂ１）中、好ましくは６０質量％以上、より好ましくは７５質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、９５質量％以下であってもよい。 The total content of the polyol (b1-1) having an acid group and the polyether polyol (b1-2) is preferably 60% by mass or more, more preferably 75% by mass or more, in the polyol (b1) Is 80% by mass or more, more preferably 90% by mass or more, and may be 95% by mass or less.
　前記ポリオール（ｂ１）は、さらに、脂環式構造を有するポリオール（ｂ１－３）を含むことが好ましい。
　前記脂環式構造を有するポリオール（ｂ１－３）としては、１種又は２種以上を用いることができ、例えば、シクロブタンジオール、シクロペンタンジオール、１，４－シクロヘキサンジオール、シクロヘプタンジオール、シクロオクタンジオール、ブチルシクロヘキサンジオール、シクロヘキサンジメタノール、ヒドロキシプロピルシクロヘキサノール、ジシクロヘキサンジオール、水素添加ビスフェノ－ルＡ、１，３－アダマンタンジオール等の脂環式構造を有する飽和ジオール；１，１’－ビシクロヘキシリデンジオール等の脂環式構造を有する不飽和ジオール；シクロヘキサントリオール等の脂環式構造を有する飽和トリオールなどが挙げられる。前記脂環式構造を有するポリオール（ｂ１－３）の数平均分子量は、好ましくは１００以上５００以下である。 The polyol (b1) preferably further contains a polyol (b1-3) having an alicyclic structure.
As the polyol (b1-3) having an alicyclic structure, one or more species can be used, and examples thereof include cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctane Saturated diols having an alicyclic structure such as diol, butylcyclohexanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, dicyclohexanediol, hydrogenated bisphenol A, 1,3-adamantanediol; 1,1'-bicyclohexene Examples thereof include unsaturated diols having an alicyclic structure such as silidenediol; and saturated triols having an alicyclic structure such as cyclohexanetriol. The number average molecular weight of the polyol (b1-3) having an alicyclic structure is preferably 100 or more and 500 or less.
　前記脂環式構造を有するポリオール（ｂ１－３）を用いる場合、その含有率は、印刷物のブロッキング抑制の観点から、ポリオール（ｂ１）全量中、好ましくは０質量％以上、より好ましくは５質量％以上であり、好ましくは４０質量％以下、好ましくは２５質量％以下、より好ましくは２０質量％以下、さらに好ましくは１０質量％以下である。 When the polyol (b1-3) having an alicyclic structure is used, the content thereof is preferably 0% by mass or more, more preferably 5% by mass, in the total amount of the polyol (b1) from the viewpoint of suppression of blocking of printed matter It is the above, Preferably it is 40 mass% or less, Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less.
　酸基を有するポリオール（ｂ１－１）、前記ポリエーテルポリオール（ｂ１－２）及び前記脂環式構造を有するポリオール（ｂ１－３）の合計の含有率は、ポリオール（ｂ１）中、好ましくは７０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上である。 The total content of the polyol (b1-1) having an acid group, the polyether polyol (b1-2) and the polyol (b1-3) having an alicyclic structure is preferably 70% of the polyol (b1). The content is preferably at least 80% by mass, more preferably at least 90% by mass.
　前記ポリオール（ｂ１）としては、他のポリオール（ｂ１－４）を含んでいてもよい。前記他のポリオールとしては、ポリエステルポリオール、低分子量ポリオール（例えば、分子量５０以上３００以下）、ポリカーボネートポリオール、ポリオレフィンポリオール等が挙げられる。 The polyol (b1) may contain other polyols (b1-4). Examples of the other polyols include polyester polyols, low molecular weight polyols (for example, having a molecular weight of 50 or more and 300 or less), polycarbonate polyols, and polyolefin polyols.
　前記ポリエステルポリオールとしては、例えば、低分子量ポリオール（例えば、分子量５０以上３００以下のポリオール）とポリカルボン酸とをエステル化反応して得られるポリエステルポリオール；ε－カプロラクトン等の環状エステル化合物を開環重合反応して得られるポリエステルポリオール；これらの共重合ポリエステルポリオールなどが挙げられる。 As the polyester polyol, for example, a polyester polyol obtained by esterification reaction of a low molecular weight polyol (for example, a polyol having a molecular weight of 50 to 300) with a polycarboxylic acid; ring-opening polymerization of cyclic ester compounds such as ε-caprolactone Polyester polyols obtained by reaction; copolyester polyols thereof and the like can be mentioned.
　前記低分子量ポリオールとしては、例えば、エチレングリコール、ジエチレングリコール、１，２－プロピレングリコール、ジプロピレングリコール、ネオペンチルグリコール、２－ブチル－２－エチル－１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，４－シクロヘキサンジオール、１，６－ヘキサンジオール、シクロヘキサンジメタノール等の比較的低分子量（例えば、分子量５０以上３００以下）のポリオールなどが挙げられる。 Examples of the low molecular weight polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 1,4-butanediol. Relatively low molecular weight such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol etc. (eg, molecular weight 50 to 300) And the like.
　前記ポリカルボン酸としては、コハク酸、アジピン酸、セバシン酸、ドデカンジカルボン酸等の脂肪族ポリカルボン酸；テレフタル酸、イソフタル酸、フタル酸、ナフタレンジカルボン酸等の芳香族ポリカルボン酸；並びに前記脂肪族ポリカルボン酸及び芳香族ポリカルボン酸の無水物又はエステル形成性誘導体などが挙げられる。 Examples of the polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; And ester-forming derivatives of aromatic polycarboxylic acids and aromatic polycarboxylic acids.
　前記低分子量ポリオールとしては、分子量が５０以上３００以下程度のポリオールを用いることができ、例えば、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、１，３－ブタンジオール等の炭素原子数２以上６以下の脂肪族ポリオール；１，４－シクロヘキサンジオール、シクロヘキサンジメタノール等の脂環式構造含有ポリオール；ビスフェノールＡ、ビスフェノールＦ等のビスフェノール化合物及びそれらのアルキレンオキシド付加物等の芳香族構造含有ポリオールなどが挙げられる。 As the low molecular weight polyol, polyols having a molecular weight of about 50 to about 300 can be used. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol Aliphatic polyols having 2 to 6 carbon atoms such as 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, etc .; 1,4-cyclohexanediol, cyclohexane Alicyclic structure-containing polyols such as dimethanol; and aromatic structure-containing polyols such as bisphenol compounds such as bisphenol A and bisphenol F and alkylene oxide adducts thereof.
　前記ポリカーボネートポリオールとしては、例えば、炭酸エステルとポリオールとの反応物；ホスゲンとビスフェノールＡ等との反応物などが挙げられる。 Examples of the polycarbonate polyol include a reaction product of a carbonate and a polyol; and a reaction product of phosgene and bisphenol A or the like.
　前記炭酸エステルとしては、例えば、メチルカーボネート、ジメチルカーボネート、エチルカーボネート、ジエチルカーボネート、シクロカーボネート、ジフェニルカーボネート等が挙げられる。 Examples of the carbonic ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.
　前記炭酸エステルと反応しうるポリオールとしては、例えば、上記低分子量ポリオールとして例示したポリオール；ポリエーテルポリオール（ポリエチレングリコール、ポリプロピレングリコール等）、ポリエステルポリオール（ポリヘキサメチレンアジペート等）等の高分子量ポリオール（重量平均分子量５００以上５，０００以下）などが挙げられる。 Examples of the polyol that can react with the carbonic ester include polyols exemplified as the above low molecular weight polyols; high molecular weight polyols (weights such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.), polyester polyols (polyhexamethylene adipate, etc.), etc. And the like.
　前記ポリオレフィンポリオールとしては、例えば、ポリイソブテンポリオール、水素添加（水添）ポリブタジエンポリオール、水素添加（水添）ポリイソプレンポリオール等が挙げられる。 Examples of the polyolefin polyol include polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, hydrogenated (hydrogenated) polyisoprene polyol and the like.
　前記他のポリオール（ｂ１－４）の含有率は、ポリオール（ｂ１）中、好ましくは５０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３０質量％以下、よりいっそう好ましくは２０質量％以下、特に好ましくは１０質量％以下である。
　特に、前記ポリエステルポリオールの含有率は、ポリオール（ｂ１）中、好ましくは１０質量％以下、より好ましくは５質量％以下、さらに好ましくは３質量％以下、特に好ましくは１質量％以下である。 The content of the other polyol (b1-4) in the polyol (b1) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass The content is particularly preferably 10% by mass or less.
In particular, the content of the polyester polyol is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less in the polyol (b1).
　前記ポリイソシアネート（ｂ２）としては、１種又は２種以上を用いることができ、例えば、４，４’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネート、クルードジフェニルメタンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ポリイソシアネート；シクロヘキサンジイソシアネート、水添キシリレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート等の脂環式構造を有するポリイソシアネートなどが挙げられる。 As said polyisocyanate (b2), 1 type (s) or 2 or more types can be used, For example, 4,4'- diphenylmethane diisocyanate, 2,4'- diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate Aromatic polyisocyanates such as tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl Fats such as methane diisocyanate Such polyisocyanates having the formula structure.
　前記ポリイソシアネート（ｂ２）としては、脂環式構造を有するポリイソシアネートを含むことが好ましい。脂環式構造を有するポリイソシアネートの含有率は、前記ポリイソシアネート（ｂ２）中、好ましくは５０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、好ましくは１００質量％以下である。 The polyisocyanate (b2) preferably contains a polyisocyanate having an alicyclic structure. The content of the polyisocyanate having an alicyclic structure is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass in the polyisocyanate (b2). % Or less.
　前記ポリオール（ｂ１）に含まれる水酸基に対する前記ポリイソシアネート（ｂ２）のイソシアネート基の当量割合［イソシアネート基／水酸基］は、モル基準で、好ましくは０．８以上、より好ましくは０．９以上であり、好ましくは２．５以下、より好ましくは２．０以下、さらに好ましくは１．５以下である。 The equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyisocyanate (b2) to the hydroxyl group contained in the polyol (b1) is preferably 0.8 or more, more preferably 0.9 or more on a molar basis. Preferably it is 2.5 or less, More preferably, it is 2.0 or less, More preferably, it is 1.5 or less.
　前記ウレタン樹脂（Ｂ１）を製造する際、必要に応じて鎖伸長剤を用いてもよい。 When manufacturing the said urethane resin (B1), you may use a chain extender as needed.
　前記鎖伸長剤としては、１種又は２種以上を用いることができ、例えば、ポリアミン、ヒドラジン化合物、その他活性水素原子を有する化合物が挙げられる。 As said chain extender, 1 type (s) or 2 or more types can be used, For example, the compound which has a polyamine, a hydrazine compound, and the other active hydrogen atom is mentioned.
　前記ポリアミンとしては、例えば、エチレンジアミン、１，２－プロパンジアミン、１，６－ヘキサメチレンジアミン、ピペラジン、２，５－ジメチルピペラジン、イソホロンジアミン、４，４’－ジシクロヘキシルメタンジアミン、３，３’－ジメチル－４，４’－ジシクロヘキシルメタンジアミン、１，４－シクロヘキサンジアミン、Ｎ－エチルアミノエチルアミン、Ｎ－メチルアミノプロピルアミン等のジアミン；Ｎ－ヒドロキシメチルアミノエチルアミン、Ｎ－ヒドロキシエチルアミノエチルアミン、Ｎ－ヒドロキシプロピルアミノプロピルアミン等のヒドロキシ基を有するジアミン；ジエチレントリアミン、ジプロピレントリアミン等のトリアミン；トリエチレンテトラミン等テトラミンなどが挙げられる。これらの中でも、エチレンジアミンが好ましい。 Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-ethylaminoethylamine, N-methylaminopropylamine, etc .; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N- Diamines having a hydroxy group such as hydroxypropylaminopropylamine; triamines such as diethylenetriamine and dipropylenetriamine; and tetramines such as triethylenetetramine. Among these, ethylenediamine is preferred.
　前記ヒドラジン化合物としては、例えば、ヒドラジン、Ｎ，Ｎ’－ジメチルヒドラジン、１，６－ヘキサメチレンビスヒドラジン、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、グルタル酸ジヒドラジド、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド、β－セミカルバジドプロピオン酸ヒドラジド、３セミカルバジッドプロピルカルバジン酸エステル、セミカルバジド－３－セミカルバジドメチル－３，５，５－トリメチルシクロヘキサン等が挙げられる。 Examples of the hydrazine compound include hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide Propionic acid hydrazide, 3-semicarbazide propyl carbazate, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane and the like can be mentioned.
　前記その他活性水素を有する化合物としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ヘキサメチレングリコール、サッカロース、メチレングリコール、グリセリン、ソルビトール等のグリコール；ビスフェノールＡ、４，４’－ジヒドロキシジフェニル、４，４’－ジヒドロキシジフェニルエーテル、４，４’－ジヒドロキシジフェニルスルホン、水添ビスフェノールＡ、ハイドロキノン等のフェノール、水等が挙げられる。 Examples of other compounds having active hydrogen include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and sucrose. , Glycols such as methylene glycol, glycerin and sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, phenols such as hydrogenated bisphenol A, hydroquinone, water Etc.
　前記鎖伸長剤として、例えば、ポリアミンを用いる場合、ポリアミンが有するアミノ基とイソシアネート基との当量比［アミノ基／イソシアネート基］は、１．２以下が好ましく、０．３以上１以下の範囲がより好ましい。 When, for example, a polyamine is used as the chain extender, the equivalent ratio [amino group / isocyanate group] of the amino group to the isocyanate group possessed by the polyamine is preferably 1.2 or less, and 0.3 or more and 1 or less. More preferable.
　ウレタン樹脂（Ａ）の重量平均分子量は、印刷物の耐久性向上の観点から、好ましくは５，０００以上、より好ましくは１０，０００以上、さらに好ましくは２０，０００以上であり、好ましくは５００，０００以下、より好ましくは２００，０００以下、さらに好ましくは１００，０００以下である。重量平均分子量を大きくすることで、印刷物の耐久性を向上できるだけでなく、乾燥不良によるブロッキング等を抑制することができ、重量平均分子量を適度に小さくすることで、インキの転移不良や再溶解性等を抑制することができる。 The weight average molecular weight of the urethane resin (A) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, preferably 500,000, from the viewpoint of improving the durability of the printed matter. Or less, more preferably 200,000 or less, still more preferably 100,000 or less. By increasing the weight average molecular weight, not only the durability of the printed matter can be improved, but also blocking due to drying defects can be suppressed, and by appropriately reducing the weight average molecular weight, ink transfer failure and resolubility Etc. can be suppressed.
　前記ウレタン樹脂（Ｂ１）は、前記ポリオール（ｂ１）と前記ポリイソシアネート（ｂ２）とを反応させ、必要に応じて、さらに鎖伸長剤を反応させることで製造することができる。前記ポリオール（ｂ１）と前記ポリイソシアネート（ｂ２）とを反応させる際には、有機溶剤を共存させてもよい。前記ポリオール（ｂ１）と前記ポリイソシアネート（ｂ２）とを反応させる際の反応温度は、５０℃以上１５０℃以下であることが好ましい。 The urethane resin (B1) can be produced by reacting the polyol (b1) with the polyisocyanate (b2) and, if necessary, further reacting the chain extender. When making the said polyol (b1) and the said polyisocyanate (b2) react, you may coexist an organic solvent. It is preferable that the reaction temperature at the time of making the said polyol (b1) and the said polyisocyanate (b2) react is 50 degreeC or more and 150 degrees C or less.
　前記有機溶剤としては、１種又は２種以上を用いることができ、例えば、アセトン、メチルエチルケトン等のケトン溶剤；テトラヒドロフラン、ジオキサン等のエーテル溶剤；酢酸エチル、酢酸ブチル等のエステル溶剤；アセトニトリル等のニトリル溶剤；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド溶剤などが挙げられる。 As the organic solvent, one or more species can be used. For example, ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butyl acetate; nitriles such as acetonitrile Solvents: Amide solvents such as dimethylformamide, N-methylpyrrolidone and the like can be mentioned.
　また、前記有機溶剤は、安全性や環境に対する負荷低減を図るため、前記ウレタン樹脂（Ｂ１）の製造途中又は製造後に、例えば、減圧留去等により一部又は全部を除去してもよい。 The organic solvent may be partially or entirely removed, for example, by distillation under reduced pressure, during or after the production of the urethane resin (B1), in order to reduce the safety and the load on the environment.
　前記ウレタン樹脂（Ｂ１）の含有率は、前記酸基を有するバインダー（Ｂ）中、好ましくは９０質量％以上、より好ましくは９５質量％以上、さらに好ましくは９９質量％以上、特に好ましくは１００質量％である。 The content of the urethane resin (B1) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, particularly preferably 100% by mass in the binder (B) having the acid group. %.
　前記酸基を有するバインダー（Ｂ）は、予め後述する水性媒体（Ｄ）に分散させておいてもよい。ウレタン樹脂（Ｂ１）を水性媒体（Ｄ）に分散させる方法（水性化方法）としては、前記酸基を有するバインダー（Ｂ）を調製し（バインダー（Ｂ）調製工程）、得られた酸基を有するバインダー（Ｂ）と後述する塩基性化合物（Ｃ）の少なくとも一部とを混合し（中和工程）、得られた混合物と前記水性媒体（Ｄ）とを混合して分散液を調製する（分散工程）方法が挙げられる。
　鎖伸長剤を用いる場合、鎖伸長剤は、前記バインダー（Ｂ）調製工程で添加してもよいし、前記分散工程の後に添加してもよい。 The binder (B) having an acid group may be dispersed in an aqueous medium (D) described later in advance. As a method of dispersing the urethane resin (B1) in the aqueous medium (D) (water-making method), the binder (B) having the acid group is prepared (binder (B) preparation step), The binder (B) and at least a part of the basic compound (C) described later are mixed (neutralization step), and the obtained mixture and the aqueous medium (D) are mixed to prepare a dispersion ( Dispersion process) can be mentioned.
When a chain extender is used, the chain extender may be added in the binder (B) preparation step or may be added after the dispersion step.
　酸基を有するバインダー（Ｂ）の含有率は、水性インキの再溶解性、印刷物のブロッキングの抑制、印刷濃度の向上、及び基材への密着性観点から、前記分散液中、好ましくは１０質量％以上、より好ましくは２０質量％以上であり、好ましくは５０質量％以下、より好ましくは４０質量％以下である。 The content of the binder (B) having an acid group is preferably 10% by mass in the dispersion from the viewpoint of resolubility of aqueous ink, suppression of blocking of printed matter, improvement of printing density, and adhesion to a substrate. % Or more, more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less.
　前記水性化方法では、必要に応じて乳化剤を使用してもよい。また、水溶解や水分散の際には、必要に応じてホモジナイザー等の機械を使用してもよい。
　前記乳化剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビトールテトラオレエート、ポリオキシエチレン・ポリオキシプロピレン共重合体等のノニオン系乳化剤；オレイン酸ナトリウム等の脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、ナフタレンスルホン酸塩、ポリオキシエチレンアルキル硫酸塩、アルカンスルフォネートナトリウム塩、アルキルジフェニルエーテルスルホン酸ナトリウム塩等のアニオン系乳化剤；アルキルアミン塩、アルキルトリメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩等のカチオン系乳化剤などが挙げられる。中でも、保存安定性の観点から、アニオン性又はノニオン性の乳化剤が好ましい。 An emulsifier may be used in the above-mentioned method for making water, if necessary. In addition, in the case of water dissolution or water dispersion, a machine such as a homogenizer may be used as needed.
Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene / polyoxypropylene copolymer, etc. Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, alkyl diphenyl ether sulfonate sodium salts, etc. Anionic emulsifiers; cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzyl ammonium salts It is. Among them, anionic or nonionic emulsifiers are preferable from the viewpoint of storage stability.
　前記塩基性化合物（Ｃ）は、塩基性金属化合物（Ｃ１）と有機アミン（Ｃ２）とを含む。
　前記塩基性金属化合物（Ｃ１）としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化カルシウム、水酸化マグネシウム等の金属水酸化物；塩化ナトリウム、塩化カリウム等の金属塩化物；硫酸銅等の金属硫酸塩などが挙げられる。 The basic compound (C) contains a basic metal compound (C1) and an organic amine (C2).
Examples of the basic metal compound (C1) include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and magnesium hydroxide; metal chlorides such as sodium chloride and potassium chloride; copper sulfate And other metal sulfates.
　前記有機アミン（Ｃ２）としては、アンモニア；モノエタノールアミン等の第１級アミン；トリエチルアミン、ジエチルエタノールアミン等の第３級アミン；モルホリン等の環状アミンなどが挙げられる。 Examples of the organic amine (C2) include ammonia; primary amines such as monoethanolamine; tertiary amines such as triethylamine and diethylethanolamine; and cyclic amines such as morpholine.
　以下の式で表される比率は、好ましくは０．００１以上、より好ましくは０．０１以上、さらに好ましくは０．０５以上であり、０．３以下あり、好ましくは０．２５以下、より好ましくは０．２以下、さらに好ましくは０．１５以下である。前記比率が前記範囲にあることで、ボイルレトルト性が良好となる。
　塩基性金属化合物（Ｃ１）のモル数×塩基性金属化合物（Ｃ１）の価数／｛（有機アミン（Ｃ２）のモル数×有機アミン（Ｃ２）の価数）＋（塩基性金属化合物（Ｃ１）のモル数×塩基性金属化合物（Ｃ１）の価数）｝ The ratio represented by the following formula is preferably 0.001 or more, more preferably 0.01 or more, more preferably 0.05 or more, 0.3 or less, preferably 0.25 or less, more preferably Is 0.2 or less, more preferably 0.15 or less. Boil retortability becomes good because the ratio is in the above range.
Number of moles of basic metal compound (C1) × valent number of basic metal compound (C1) / {(number of moles of organic amine (C2) × valent number of organic amine (C2)) + (basic metal compound (C1) Number of moles of) × valence of basic metal compound (C1))}
　前記塩基性金属化合物（Ｃ１）及び前記有機アミン（Ｃ２）は、水性リキッドインキ中で、前記酸基を有するバインダー（Ｂ）の酸基と塩を形成していてもよい。前記塩基性化合物（Ｃ１）及び前記有機アミン（Ｃ１）が前記酸基を有するバインダーの酸基を中和することで、水分散性を向上しやすくなる。 The basic metal compound (C1) and the organic amine (C2) may form a salt with the acid group of the binder (B) having the acid group in an aqueous liquid ink. It becomes easy to improve water dispersibility because the basic compound (C1) and the organic amine (C1) neutralize the acid group of the binder having the acid group.
　前記塩基性化合物（Ｃ）の含有量は、前記酸基を有するバインダー（Ｂ）１００質量部に対して、好ましくは０．０１質量部以上、より好ましくは０．０５質量部以上、さらに好ましくは０．１質量部以上であり、好ましくは１０質量部以下、より好ましくは７質量部以下、さらに好ましくは４質量部以下である。 The content of the basic compound (C) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 100 parts by mass of the binder (B) having the acid group. It is 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 4 parts by mass or less.
　前記水性媒体（Ｄ）としては、水；親水性有機溶剤；水及び親水性有機溶剤の混合物等が挙げられ、安全性や環境に対する付加の観点から、水又は水及び親水性有機溶剤の混合物が好ましい。
　前記親水性有機溶剤としては、１種又は２種以上を用いることができ、水と混和するものであることが好ましく、例えば、メタノール、エタノール、ｎ－プロパノール及び２－プロパノール等のアルコール溶剤；アセトン、メチルエチルケトン等のケトン溶剤；エチレングリコール、ジエチレングリコール、プロピレングリコール、ポリアルキレングリコール、グリセリン等の多価アルコール溶剤；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－プロピルエーテル、エチルカルビトール等のエーテル溶剤；Ｎ－メチル－２－ピロリドン等のアミド溶剤などが挙げられる。 Examples of the aqueous medium (D) include water; hydrophilic organic solvents; mixtures of water and hydrophilic organic solvents and the like, and from the viewpoint of safety and addition to the environment, water or a mixture of water and hydrophilic organic solvents is preferable.
The hydrophilic organic solvent may be used alone or in combination of two or more, and is preferably miscible with water. For example, alcohol solvents such as methanol, ethanol, n-propanol and 2-propanol; acetone Ketone solvents such as methyl ethyl ketone; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, propylene glycol, polyalkylene glycol, and glycerin; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethyl carbitol And ether solvents such as N-methyl-2-pyrrolidone.
　前記水性媒体（Ｄ）が水及び親水性有機溶剤を含む場合、水の含有率は、水性媒体（Ｄ）中、好ましくは８０質量％以上、より好ましくは８５質量％以上、さらに好ましくは９０質量％以上であり、例えば１００質量％以下、さらには９５質量％以下であることも許容される。 When the aqueous medium (D) contains water and a hydrophilic organic solvent, the content of water in the aqueous medium (D) is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass. % Or more, for example, 100% by mass or less, or even 95% by mass or less is acceptable.
　本発明の水性リキッドインキは、さらに助剤を含んでいてもよい。前記助剤としては、耐摩擦性、滑り性等を付与するためのパラフィン系ワックス、ポリエチレン系ワックス、カルナバワックス等のワックス；オレイン酸アミド、ステアリン酸アミド、エルカ酸アミド等の脂肪酸アミド化合物；印刷時の発泡を抑制するためのシリコン系、非シリコン系消泡剤；分散剤等を適宜使用することもできる。 The aqueous liquid ink of the present invention may further contain an auxiliary. Examples of the auxiliary include paraffin-based waxes for imparting abrasion resistance, slipperiness, etc., waxes such as polyethylene-based waxes and carnauba waxes; fatty acid amide compounds such as oleic acid amide, stearic acid amide and erucic acid amide; printing It is also possible to appropriately use a silicon-based or non-silicon-based antifoaming agent, a dispersing agent, and the like for suppressing foaming at that time.
　前記分散剤としては、ノニオン系分散剤が好ましい。
　前記分散剤の酸価は、好ましくは３０ｍｇＫＯＨ／ｇ以下、より好ましくは２５ｍｇＫＯＨ／ｇ以下、さらに好ましくは２０ｍｇＫＯＨ／ｇ以下であり、例えば１ｍｇＫＯＨ／ｇ以上、さらには３ｍｇＫＯＨ／ｇ以上であってもよい。
　前記分散剤の酸価は、前記酸基を有するバインダー（Ｂ）の酸価よりも小さいことが好ましい。前記酸基を有するバインダー（Ｂ）の酸価と前記分散剤の酸価との差は、例えば１ｍｇＫＯＨ／ｇ以上、より好ましくは３ｍｇＫＯＨ／ｇ以上であり、好ましくは３０ｍｇＫＯＨ／ｇ以下、より好ましくは２０ｍｇＫＯＨ／ｇ以下である。 As the dispersing agent, nonionic dispersing agents are preferable.
The acid value of the dispersant is preferably 30 mg KOH / g or less, more preferably 25 mg KOH / g or less, still more preferably 20 mg KOH / g or less, and may be, for example, 1 mg KOH / g or more, further 3 mg KOH / g or more. .
The acid value of the dispersant is preferably smaller than the acid value of the binder (B) having the acid group. The difference between the acid value of the binder (B) having an acid group and the acid value of the dispersant is, for example, 1 mg KOH / g or more, more preferably 3 mg KOH / g or more, preferably 30 mg KOH / g or less, more preferably It is 20 mg KOH / g or less.
　前記分散剤の含有量は、前記着色剤（Ａ）１００質量部に対して、好ましくは４０質量部以上、より好ましくは５０質量部以上、さらに好ましくは６０質量部以上であり、好ましくは１００質量部以下、より好ましくは８０質量部以下、さらに好ましくは７５質量部以下である。
　前記分散剤の含有量は、前記酸基を有するバインダー（Ｂ）１００質量部に対して、好ましくは１０質量部以上、より好ましくは２０質量部以上、さらに好ましくは３０質量部以上であり、好ましくは１００質量部以下、より好ましくは８０質量部以下、さらに好ましくは６０質量部以下である。 The content of the dispersant is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, preferably 100 parts by mass with respect to 100 parts by mass of the colorant (A). The amount is preferably at most 80 parts by mass, more preferably at most 75 parts by mass.
The content of the dispersant is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, with respect to 100 parts by mass of the binder (B) having the acid group. Is 100 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less.
　前記水性リキッドインキの粘度は、離合社製ザーンカップ＃４を使用して２５℃において測定した数値として、好ましくは７秒以上、より好ましくは１０秒以上であり、好ましくは２５秒以下、より好ましくは２０秒以下である。
　ミリパスカル秒で粘度を示すと、２５℃において好ましくは７０（ｍＰａ・ｓ）以上、より好ましくは１００（ｍＰａ・ｓ）以上であり、好ましくは３５０（ｍＰａ・ｓ）以下、より好ましくは２５０（ｍＰａ・ｓ）以下である。 The viscosity of the aqueous liquid ink is preferably 7 seconds or more, more preferably 10 seconds or more, preferably 25 seconds or less, more preferably 7 seconds or more, more preferably 10 seconds or more, as a numerical value measured at 25 ° C. Is less than 20 seconds.
The viscosity in millipascal second is preferably 70 (mPa · s) or more, more preferably 100 (mPa · s) or more, preferably 350 (mPa · s) or less, more preferably 250 (mPa · s) at 25 ° C. It is less than mPa · s).
　前記水性リキッドインキの表面張力は、好ましくは２５ｍＮ／ｍ以上、より好ましくは３３ｍＮ／ｍ以上であり、好ましくは５０ｍＮ／ｍ以下、より好ましくは４３ｍＮ／以下である。インキの表面張力を適度に高めることで、基材へのインキの濡れ性を維持しつつ、ドットブリッジ（中間調の網点部分で隣り合う網点同士が繋がった印刷面の汚れ）を抑制することができ、インキの表面張力を適度に低くすることで、基材へのインキの濡れ性を高め、ハジキを抑制することができる。 The surface tension of the aqueous liquid ink is preferably 25 mN / m or more, more preferably 33 mN / m or more, and preferably 50 mN / m or less, more preferably 43 mN / m or less. By appropriately increasing the surface tension of the ink, it is possible to suppress the dot bridge (dirt of the printing surface in which adjacent halftone dots are connected in halftone halftone dots) while maintaining the wettability of the ink to the substrate By appropriately lowering the surface tension of the ink, the wettability of the ink to the substrate can be enhanced, and repelling can be suppressed.
　本発明に係る水性リキッドインキは、グラビア、フレキソ印刷インキの製造に一般的に使用されているアイガーミル、サンドミル、ガンマミル、アトライター等を用いて製造することができる。 The aqueous liquid ink according to the present invention can be produced using an Eiger mill, a sand mill, a gamma mill, an attritor or the like generally used in the production of gravure and flexographic printing inks.
　本発明の水性リキッドインキを調製する際、均一性の観点から、予め前記着色剤（Ａ）と、前記酸基を有するバインダー（Ｂ）の少なくとも一部と、前記塩基性化合物（Ｃ）の少なくとも一部と、前記分散剤と、前記水性媒体（Ｄ）の少なくとも一部を混合して、予備組成物（練肉ベースインキ）を調製してもよい。 When preparing the aqueous liquid ink of the present invention, from the viewpoint of uniformity, the colorant (A), at least a part of the binder (B) having the acid group, and at least the basic compound (C) in advance A pre-composition (mill base ink) may be prepared by mixing a part, the dispersant and at least a part of the aqueous medium (D).
　本発明の水性リキッドインキは、各種の基材と密着性に優れ、紙、合成紙、熱可塑性樹脂フィルム、プラスチック製品、鋼板等への印刷に使用することができるものであり、電子彫刻凹版等によるグラビア印刷版を用いたグラビア印刷用、又は樹脂版等によるフレキソ印刷版を用いたフレキソ印刷用のインキとして有用である一方で、版を使用せずインクジェットノズルからインキを吐出するインクジェット方式向けのインキを除くものである。即ち、インクジェットインキの場合、ノズルから吐出したインク滴が、直接基材に密着し印刷物を形成するのに対し、本発明の水性リキッドインキは、印刷インキを一旦印刷版又は印刷パターンに密着・転写した後、インキのみを再度基材に密着させ、必要に応じて乾燥させ印刷物とするものである。
　本発明の水性リキッドインキを用いてグラビア印刷方式やフレキソ印刷方式から形成される印刷インキの膜厚は、例えば１０μｍ以下、好ましくは５μｍ以下である。 The aqueous liquid ink of the present invention has excellent adhesion to various substrates, and can be used for printing on paper, synthetic paper, thermoplastic resin film, plastic products, steel plates, etc. While it is useful as an ink for gravure printing using a gravure printing plate according to the present invention or for flexographic printing using a flexographic printing plate using a resin plate etc., it is suitable for an inkjet system which ejects ink from an inkjet nozzle without using a plate It excludes the ink. That is, in the case of ink jet ink, ink droplets ejected from the nozzles are in close contact with the substrate directly to form a printed matter, whereas the aqueous liquid ink of the present invention once adheres and transfers the printing ink to the printing plate or printing pattern. After that, only the ink is brought into close contact with the substrate again, and it is dried as required to form a printed matter.
The film thickness of the printing ink formed from the gravure printing method or the flexographic printing method using the aqueous liquid ink of the present invention is, for example, 10 μm or less, preferably 5 μm or less.
　基材は、ナイロン６、ナイロン６６、ナイロン４６等のポリアミド樹脂、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、ポリトリメチレンテレフタレート、ポリトリメチレンナフタレート、ポリブチレンテレフタレート、ポリブチレンナフタレート等のポリエステル系樹脂、ポリ乳酸等のポリヒドロキシカルボン酸、ポリ（エチレンサクシネート）、ポリ（ブチレンサクシネート）等の脂肪族ポリエステル系樹脂などの生分解性樹脂、ＰＰ、ポリエチレン等のポリオレフィン樹脂、ポリイミド樹脂、ポリアリレート樹脂又はそれらの混合物等の熱可塑性樹脂よりなるフィルムやこれらの積層体が挙げられるが、中でも、ポリエステル、ポリアミド、ポリエチレン、ポリプロピレンからなるフィルムが好適に使用できる。これらの基材フィルムは、未延伸フィルムでも延伸フィルムでもよく、その製法も限定されるものではない。また、基材フィルムの厚さも特に限定されるものではないが、通常は１～５００μｍの範囲であればよい。
　基材フィルムの印刷面には、コロナ放電処理がされていることが好ましく、シリカ、アルミナ等が蒸着されていてもよい。 The base material is polyamide resin such as nylon 6, nylon 66, nylon 46, polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc. Biodegradable resins such as polyhydroxycarboxylic acid such as resin, polylactic acid, etc., aliphatic polyester resin such as poly (ethylene succinate), poly (butylene succinate), polyolefin resin such as PP, polyethylene, polyimide resin, poly Films made of thermoplastic resins such as arylate resins or mixtures thereof and laminates thereof are mentioned, and among them, films made of polyester, polyamide, polyethylene and polypropylene can be suitably used. These base films may be unstretched films or stretched films, and the production method is not limited. Also, the thickness of the base film is not particularly limited, but usually, it may be in the range of 1 to 500 μm.
The printed surface of the substrate film is preferably subjected to corona discharge treatment, and silica, alumina or the like may be vapor deposited.
　以下、実施例と比較例とにより、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described by examples and comparative examples.
（合成例１：バインダー（１）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１９５質量部、イソホロンジイソシアネート１４５質量部、２，２－ジメチロールプロピオン酸２６質量部及び１，４－シクロヘキサンジメタノール２８質量部を、メチルエチルケトン２０３質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液２．２質量部及び２５質量％アンモニア水溶液１２．０質量部を加えることで前記ウレタンプレポリマーが有するカルボキシ基の一部又は全部を中和し、さらに水７２６質量部と８０％ヒドラジン水溶液９．２質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（１）を得た。
　このバインダー（１）における前記ウレタン樹脂中の脂環式構造の割合は、２１１５ｍｍｏｌ／ｋｇであり、酸価は２８ｍｇＫＯＨ／ｇであった。 Synthesis Example 1: Preparation of Binder (1)
195 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 145 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer The organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal (binder having an acid group) was obtained by reacting the component and 28 parts by mass of 1,4-cyclohexanedimethanol in 203 parts by mass of methyl ethyl ketone.
Next, 2.2 parts by mass of a 50% by mass aqueous solution of potassium hydroxide and 12.0 parts by mass of a 25% by mass aqueous solution of ammonia are added to neutralize part or all of the carboxy groups possessed by the urethane prepolymer. An aqueous dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass and 9.2 parts by mass of an aqueous solution of hydrazine, and then a binder (1) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
The ratio of the alicyclic structure in the urethane resin in the binder (1) was 2115 mmol / kg, and the acid value was 28 mg KOH / g.
（合成例２：バインダー（２）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１９４質量部、イソホロンジイソシアネート１４４質量部、２，２－ジメチロールプロピオン酸２６質量部及び１，４－シクロヘキサンジメタノール２８質量部を、メチルエチルケトン２０２質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液６．５質量部及び２５質量％アンモニア水溶液９．３質量部を加えることで前記ウレタンプレポリマーが有するカルボキシ基の一部又は全部を中和し、さらに水７２７質量部と８０％ヒドラジン水溶液９．１質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（２）を得た。
　このバインダー（２）における前記ウレタン樹脂中の脂環式構造の割合は、２１０３ｍｍｏｌ／ｋｇであり、酸価は２８ｍｇＫＯＨ／ｇであった。 Synthesis Example 2 Preparation of Binder (2)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 194 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 144 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid The organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal (binder having an acid group) was obtained by reacting the component and 28 parts by mass of 1,4-cyclohexanedimethanol in 202 parts by mass of methyl ethyl ketone.
Next, 6.5 parts by mass of 50% by mass potassium hydroxide aqueous solution and 9.3 parts by mass of 25% by mass ammonia aqueous solution are added to neutralize a part or all of the carboxy groups possessed by the urethane prepolymer, and further water 727 An aqueous dispersion of a urethane resin is obtained by adding and stirring thoroughly with a mass part and 9.1 mass part of an 80% aqueous hydrazine solution, and then a binder (2) having a nonvolatile content of 40 mass% is obtained by aging and desolvation. Obtained.
The proportion of the alicyclic structure in the urethane resin in the binder (2) was 2103 mmol / kg, and the acid value was 28 mg KOH / g.
（合成例３：バインダー（３）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１９３質量部、イソホロンジイソシアネート１４３質量部、２，２－ジメチロールプロピオン酸２６質量部及び１，４－シクロヘキサンジメタノール２８質量部を、メチルエチルケトン２０１質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液１０．８質量部及び２５質量％アンモニア水溶液６．６質量部を加えることで前記ウレタンプレポリマーが有するカルボキシ基の一部又は全部を中和し、さらに水７２８質量部と８０％ヒドラジン水溶液９．１質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（３）を得た。
　このバインダー（３）における前記ウレタン樹脂中の脂環式構造の割合は、２０９２ｍｍｏｌ／ｋｇであり、酸価は２８ｍｇＫＯＨ／ｇであった。 Synthesis Example 3 Preparation of Binder (3)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 193 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 143 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid The organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal (binder having an acid group) was obtained by reacting the component and 28 parts by mass of 1,4-cyclohexanedimethanol in 201 parts by mass of methyl ethyl ketone.
Then, 10.8 parts by mass of a 50% by mass aqueous solution of potassium hydroxide and 6.6 parts by mass of a 25% by mass aqueous ammonia solution are added to neutralize part or all of the carboxy groups possessed by the urethane prepolymer. An aqueous dispersion of a urethane resin is obtained by adding and stirring thoroughly with a mass part and 9.1 mass part of an 80% aqueous hydrazine solution, and then a binder (3) having a nonvolatile content of 40 mass% is obtained by aging and desolvation. Obtained.
The proportion of the alicyclic structure in the urethane resin in this binder (3) was 2092 mmol / kg, and the acid value was 28 mg KOH / g.
（合成例４：バインダー（４）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１９２質量部、イソホロンジイソシアネート１４２質量部、２，２－ジメチロールプロピオン酸２６質量部及び１，４－シクロヘキサンジメタノール２８質量部を、メチルエチルケトン２００質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液１５．１質量部及び２５質量％アンモニア水溶液３．９質量部を加えることで前記ウレタンプレポリマーが有するカルボキシ基の一部又は全部を中和し、さらに水７２９質量部と８０％ヒドラジン水溶液９．０質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（４）を得た。
　このバインダー（４）における前記ウレタン樹脂中の脂環式構造の割合は、２０８０ｍｍｏｌ／ｋｇであり、酸価は２８ｍｇＫＯＨ／ｇであった。 Synthesis Example 4 Preparation of Binder (4)
192 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 142 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer An organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular end (a binder having an acid group) was obtained by reacting the compound and 28 parts by mass of 1,4-cyclohexanedimethanol in 200 parts by mass of methyl ethyl ketone.
Next, 15.1 parts by mass of 50% by mass aqueous potassium hydroxide solution and 3.9 parts by mass of 25% by mass aqueous ammonia solution are added to neutralize part or all of the carboxy groups of the urethane prepolymer, and water 729 is further added. An aqueous dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass of an aqueous 80% hydrazine solution, and then a binder (4) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
The proportion of the alicyclic structure in the urethane resin in the binder (4) was 2080 mmol / kg, and the acid value was 28 mg KOH / g.
（合成例５：バインダー（５）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１９１質量部、イソホロンジイソシアネート１４２質量部、２，２－ジメチロールプロピオン酸２６質量部及び１，４－シクロヘキサンジメタノール２８質量部を、メチルエチルケトン１９９質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液１９．２質量部及び２５質量％アンモニア水溶液１．３質量部を加えることで前記ウレタンプレポリマーが有するカルボキシ基の一部又は全部を中和し、さらに水７３０質量部と８０％ヒドラジン水溶液９．０質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（５）を得た。
　このバインダー（５）における前記ウレタン樹脂中の脂環式構造の割合は、２０６９ｍｍｏｌ／ｋｇであり、酸価は２８ｍｇＫＯＨ／ｇであった。 Synthesis Example 5 Preparation of Binder (5)
191 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 142 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer An organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular end (a binder having an acid group) was obtained by reacting 1 part and 28 parts by mass of 1,4-cyclohexanedimethanol in 199 parts by mass of methyl ethyl ketone.
Then, 19.2 parts by mass of a 50% by mass aqueous solution of potassium hydroxide and 1.3 parts by mass of a 25% by mass aqueous ammonia solution are added to neutralize part or all of the carboxy groups possessed by the urethane prepolymer. A water dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass of an aqueous 80% hydrazine solution, and then a binder (5) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
The proportion of the alicyclic structure in the urethane resin in the binder (5) was 2069 mmol / kg, and the acid value was 28 mg KOH / g.
（合成例６：バインダー（６）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）２６９質量部、イソホロンジイソシアネート１０２質量部、２，２－ジメチロールプロピオン酸２４質量部及びネオペンチルグリコール３．５質量部を、メチルエチルケトン２０４質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液２．０質量部及び２５質量％アンモニア水溶液１０．８質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部又は全部を中和し、さらに水７２６質量部と８０％ヒドラジン水溶液６．４質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（６）を得た。
　このバインダー（６）における前記ウレタン樹脂中の脂環式構造の割合は、１１４２ｍｍｏｌ／ｋｇであり、酸価は２５ｍｇＫＯＨ／ｇであった。 Synthesis Example 6: Preparation of Binder (6)
269 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 102 parts by mass of isophorone diisocyanate, 24 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer The organic solvent solution of the urethane prepolymer (binder having an acid group) having an isocyanate group at the molecular terminal was obtained by reacting the part and 3.5 parts by mass of neopentyl glycol in 204 parts by mass of methyl ethyl ketone.
Next, 2.0 parts by mass of 50% by mass potassium hydroxide aqueous solution and 10.8 parts by mass of 25% by mass ammonia aqueous solution are added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and water 726 is further added. An aqueous dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass and 6.4 parts by mass of a 80% aqueous hydrazine solution, and then a binder (6) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
The ratio of the alicyclic structure in the urethane resin in the binder (6) was 1142 mmol / kg, and the acid value was 25 mg KOH / g.
（合成例７：バインダー（７）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）２６８質量部、イソホロンジイソシアネート１００質量部、２，２－ジメチロールプロピオン酸２２質量部及び１，４－シクロヘキサンジメタノール５．６質量部を、メチルエチルケトン２０４質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液１．８質量部及び２５質量％アンモニア水溶液１０．０質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部又は全部を中和し、さらに水７２６質量部と８０％ヒドラジン水溶液６．３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（７）を得た。
　このバインダー（７）における前記ウレタン樹脂中の脂環式構造の割合は、１２２２ｍｍｏｌ／ｋｇであり、酸価は２３ｍｇＫＯＨ／ｇであった。 Synthesis Example 7 Preparation of Binder (7)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 268 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 100 parts by mass of isophorone diisocyanate, 22 parts by mass of 2,2-dimethylol propionic acid The organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal (binder having an acid group) is obtained by reacting the acid and 5.6 parts by mass of 1,4-cyclohexanedimethanol in 204 parts by mass of methyl ethyl ketone The
Next, 1.8 parts by mass of 50% by mass potassium hydroxide aqueous solution and 10.0 parts by mass of 25% by mass ammonia aqueous solution are added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and water 726 is further added. An aqueous dispersion of a urethane resin is obtained by adding and stirring thoroughly with a mass part and 6.3 mass parts of an 80% aqueous hydrazine solution, and then a binder (7) having a nonvolatile content of 40 mass% is obtained by aging and desolvation. Obtained.
The proportion of the alicyclic structure in the urethane resin in the binder (7) was 1222 mmol / kg, and the acid value was 23 mg KOH / g.
（合成例８：バインダー（８）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）２５２質量部、イソホロンジイソシアネート１１０質量部、２，２－ジメチロールプロピオン酸８．７質量部及び１，４－シクロヘキサンジメタノール２６質量部を、メチルエチルケトン２０４質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液０．７質量部及び２５質量％アンモニア水溶液４．０質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部又は全部を中和し、さらに水７２６質量部と８０％ヒドラジン水溶液７．０質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（８）を得た。
　このバインダー（８）における前記ウレタン樹脂中の脂環式構造の割合は、１６８３ｍｍｏｌ／ｋｇであり、酸価は９ｍｇＫＯＨ／ｇであった。 Synthesis Example 8 Preparation of Binder (8)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 252 parts by mass of polyoxytetramethylene glycol (molecular weight: 2000), 110 parts by mass of isophorone diisocyanate, 2, 2-dimethylol propionic acid 8. By reacting 7 parts by mass and 26 parts by mass of 1,4-cyclohexanedimethanol in 204 parts by mass of methyl ethyl ketone, an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular end (a binder having an acid group) is obtained. The
Next, 0.7 parts by mass of a 50% by mass aqueous solution of potassium hydroxide and 4.0 parts by mass of a 25% by mass aqueous solution of ammonia are added to neutralize part or all of the carboxyl groups of the urethane prepolymer. An aqueous dispersion of a urethane resin is obtained by adding 10 parts by mass and 7.0 parts by mass of a 80% aqueous hydrazine solution, and then an aqueous dispersion of urethane resin is obtained. Obtained.
The proportion of the alicyclic structure in the urethane resin in the binder (8) was 1683 mmol / kg, and the acid value was 9 mg KOH / g.
（合成例９：バインダー（９）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１１５質量部、イソホロンジイソシアネート１８１質量部、２，２－ジメチロールプロピオン酸１７質量部及び１，４－シクロヘキサンジメタノール８５質量部を、メチルエチルケトン２０５質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマー（酸基を有するバインダー）の有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液１．４質量部及び２５質量％アンモニア水溶液７．９質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部又は全部を中和し、さらに水７２７質量部と８０％ヒドラジン水溶液２．２質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（９）を得た。
　このバインダー（９）における前記ウレタン樹脂中の脂環式構造の割合は、３５１１ｍｍｏｌ／ｋｇであり、酸価は１８ｍｇＫＯＨ／ｇであった。 Synthesis Example 9 Preparation of Binder (9)
115 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 181 parts by mass of isophorone diisocyanate, 17 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer The organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal (binder having an acid group) was obtained by reacting part and 85 parts by mass of 1,4-cyclohexanedimethanol in 205 parts by mass of methyl ethyl ketone.
Next, 1.4 parts by mass of 50% by mass aqueous potassium hydroxide solution and 7.9 parts by mass of 25% by mass aqueous ammonia solution are added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and water 727 is further added. An aqueous dispersion of a urethane resin is obtained by adding 2 parts by mass and 2.2 parts by mass of an aqueous 80% hydrazine solution, and then an aqueous dispersion of a urethane resin is obtained. Then, a binder (9) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
The proportion of the alicyclic structure in the urethane resin in the binder (9) was 3511 mmol / kg, and the acid value was 18 mg KOH / g.
（比較合成例１：バインダー（１０）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１９６質量部、イソホロンジイソシアネート１４５質量部、２，２－ジメチロールプロピオン酸２６質量部及び１，４－シクロヘキサンジメタノール２８質量部を、メチルエチルケトン２０４質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
　次いで、２５質量％アンモニア水溶液１３．３質量部を加えることで前記ウレタンプレポリマーが有するカルボキシ基の一部又は全部を中和し、さらに水７２５質量部と８０％ヒドラジン水溶液９．２質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（１０）を得た。
　このバインダー（１０）における前記ウレタン樹脂中の脂環式構造の割合は、２１２０ｍｍｏｌ／ｋｇであり、酸価は２８ｍｇＫＯＨ／ｇであった。 Comparative Synthesis Example 1: Preparation of Binder (10)
196 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 145 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer The organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal was obtained by reacting the compound and 28 parts by mass of 1,4-cyclohexanedimethanol in 204 parts by mass of methyl ethyl ketone.
Next, 13.3 parts by mass of 25% by mass aqueous ammonia solution is added to neutralize part or all of the carboxy groups possessed by the urethane prepolymer, and further 725 parts by mass of water and 9.2 parts by mass of 80% aqueous hydrazine solution In addition, the aqueous dispersion of the urethane resin was obtained by sufficiently stirring, and then aging and solvent removal to obtain a binder (10) having a nonvolatile content of 40% by mass.
The proportion of the alicyclic structure in the urethane resin in the binder (10) was 2120 mmol / kg, and the acid value was 28 mg KOH / g.
（比較合成例２：バインダー（１１）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１９６質量部、イソホロンジイソシアネート１４５質量部、２，２－ジメチロールプロピオン酸２６質量部及び１，４－シクロヘキサンジメタノール２８質量部を、メチルエチルケトン２０４質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
　次いで、トリエチルアミン２０質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部又は全部を中和し、さらに水７２５質量部と８０％ヒドラジン水溶液９．２質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（１１）を得た。
　このバインダー（１１）における前記ウレタン樹脂中の脂環式構造の割合は、２１２０ｍｍｏｌ／ｋｇであり、酸価は２８ｍｇＫＯＨ／ｇであった。 Comparative Synthesis Example 2: Preparation of Binder (11)
196 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 145 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer The organic solvent solution of the urethane prepolymer having an isocyanate group at the molecular terminal was obtained by reacting the compound and 28 parts by mass of 1,4-cyclohexanedimethanol in 204 parts by mass of methyl ethyl ketone.
Next, 20 parts by mass of triethylamine is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and 725 parts by mass of water and 9.2 parts by mass of an 80% aqueous hydrazine solution are further added and sufficiently stirred. Thus, a water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a binder (11) having a nonvolatile content of 40% by mass.
The proportion of the alicyclic structure in the urethane resin in this binder (11) was 2120 mmol / kg, and the acid value was 28 mg KOH / g.
（比較合成例３：バインダー（１２）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）１９１質量部、イソホロンジイソシアネート１４１質量部、２，２－ジメチロールプロピオン酸２６質量部及び１，４－シクロヘキサンジメタノール２７質量部を、メチルエチルケトン１９８質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液２１．３質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部又は全部を中和し、さらに水７３０質量部と８０％ヒドラジン水溶液８．９質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（１２）を得た。
　このバインダー（１２）における前記ウレタン樹脂中の脂環式構造の割合は、２０６４ｍｍｏｌ／ｋｇであり、酸価は２８ｍｇＫＯＨ／ｇであった。 Comparative Synthesis Example 3: Preparation of Binder (12)
191 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 141 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer By reacting 1 part and 27 parts by mass of 1,4-cyclohexanedimethanol in 198 parts by mass of methyl ethyl ketone, an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular end was obtained.
Next, 21.3 parts by mass of a 50% by mass aqueous solution of potassium hydroxide is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further, 730 parts by mass of water and 8.9 parts by mass of 80% aqueous hydrazine solution An aqueous dispersion of a urethane resin was obtained by adding parts and stirring sufficiently, and then aging and desolvation to obtain a binder (12) having a nonvolatile content of 40% by mass.
The proportion of the alicyclic structure in the urethane resin in the binder (12) was 2064 mmol / kg, and the acid value was 28 mg KOH / g.
（比較合成例４：バインダー（１３）の調製）
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリオキシテトラメチレングリコール（分子量２０００）２９６質量部、イソホロンジイソシアネート８２質量部、２，２－ジメチロールプロピオン酸１７質量部、及びネオペンチルグリコール３．６質量部を、メチルエチルケトン２０５質量部中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
　次いで、５０質量％水酸化カリウム水溶液１．４質量部及び２５質量％アンモニア水溶液７．６質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部又は全部を中和し、さらに水７２７質量部と８０％ヒドラジン水溶液３．４質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分４０質量％のバインダー（１３）を得た。
　このバインダー（１３）における前記ウレタン樹脂中の脂環式構造の割合は、９１７ｍｍｏｌ／ｋｇであり、酸価は１７ｍｇＫＯＨ／ｇであった。 Comparative Synthesis Example 4: Preparation of Binder (13)
296 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 82 parts by mass of isophorone diisocyanate, 17 parts by mass of 2,2-dimethylol propionic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer The organic solvent solution of the urethane prepolymer which has an isocyanate group at the molecular terminal was obtained by making the part and 3.6 parts by mass of neopentyl glycol react in 205 parts by mass of methyl ethyl ketone.
Next, 1.4 parts by mass of 50% by mass potassium hydroxide aqueous solution and 7.6 parts by mass of 25% by mass ammonia aqueous solution are added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and water 727 is further added. An aqueous dispersion of a urethane resin is obtained by adding and stirring sufficiently by adding 80 parts by mass and 3.4 parts by mass of a 80% aqueous hydrazine solution, and then a binder (13) having a nonvolatile content of 40% by mass is obtained by aging and desolvation. Obtained.
The proportion of the alicyclic structure in the urethane resin in the binder (13) was 917 mmol / kg, and the acid value was 17 mg KOH / g.
　実施例１～９、比較例１～４
　合成例１～９、及び比較合成例１～４で得たバインダー（１）～（１３）をそれぞれ以下の組成によりよく撹拌混合した後、ビーズミルで練肉して、練肉ベースインキを作製した。次いで、得られた練肉ベースインキにさらにバインダー（１）～（１３）をそれぞれ１０質量部と、水４質量部を追加混合して水性青色印刷インキを作製した。得られた印刷インキの粘度をザーンカップ＃４（離合社製）で１６秒（２５℃）になるように水で調整し、それぞれ実施例１～９、比較例１～４の水性リキッドインキとした。 Examples 1 to 9 and Comparative Examples 1 to 4
The binders (1) to (13) obtained in Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 4 were well stirred and mixed according to the following compositions, respectively, and then milled using a bead mill to prepare a milled base ink . Subsequently, 10 parts by mass of each of the binders (1) to (13) and 4 parts by mass of water were further added to the obtained ground meat base ink to prepare an aqueous blue printing ink. The viscosity of the obtained printing ink is adjusted with water so as to be 16 seconds (25 ° C.) with Zahn cup # 4 (manufactured by Rigosha Co., Ltd.), and the aqueous liquid inks of Examples 1 to 9 and Comparative Examples 1 to 4 respectively. did.
　また、得られた水性リキッドインキの表面張力を確認すべく、２５℃における表面張力を測定した。表面張力はＷｉｌｈｅｌｍｙ法に基づき、協和界面科学（株）製　自動表面張力計ＤＹ－３００を用いて測定した。 In addition, the surface tension at 25 ° C. was measured to confirm the surface tension of the obtained aqueous liquid ink. The surface tension was measured based on the Wilhelmy method using an automatic surface tension meter DY-300 manufactured by Kyowa Interface Science Co., Ltd.
　〔練肉ベースインキ配合〕
　　　ＦＡＳＴＯＧＥＮ　ＢＬＵＥ　ＬＡ５３８０藍顔料（ＤＩＣ社製）　　１５質量部
　　　水性フレキソインキ用バインダー　　４０質量部
　　　ノニオン系顔料分散剤（ＢＹＫ社製）１０質量部
　　　イソプロピルアルコール　　　　　　　３質量部
　　　水　　　　　　　　　　　　　　　　　８質量部
　　　シリコン系消泡剤（ＢＹＫ社製）　０．２質量部 [Mixed meat base ink combination]
FASTOGEN BLUE LA 5380 mochi pigment (made by DIC) 15 parts by mass Binder for aqueous flexographic ink 40 parts by mass nonionic pigment dispersant (manufactured by BYK) 10 parts by mass isopropyl alcohol 3 parts by mass water 8 parts by mass silicone defoaming agent (BYK Made by company) 0.2 parts by mass
　〔水性リキッドインキ（青色）の配合総量（粘度調整用の水を除く）〕
　　　ＦＡＳＴＯＧＥＮ　ＢＬＵＥ　ＬＡ５３８０藍顔料（ＤＩＣ社製）　　１５質量部
　　　水性フレキソインキ用バインダー　　５０質量部
　　　ノニオン系顔料分散剤（ＢＹＫ社製）１０質量部
　　　イソプロピルアルコール　　　　　　　３質量部
　　　水　　　　　　　　　　　　　　　　１２質量部
　　　シリコン系消泡剤（ＢＹＫ社製）　０．２質量部 [Total blending amount of water-based liquid ink (blue) (excluding water for viscosity adjustment)]
FASTOGEN BLUE LA 5380 mochi pigment (manufactured by DIC) 15 parts by mass Binder for aqueous flexographic ink 50 parts by mass nonionic pigment dispersant (manufactured by BYK) 10 parts by mass isopropyl alcohol 3 parts by mass water 12 parts by mass silicone defoamer (BYK Made by company) 0.2 parts by mass
　実施例１～９、及び比較例１～４の水性リキッドインキをＦｌｅｘｉｐｒｏｏｆ１００テスト印刷機（Ｔｅｓｔｉｎｇ　Ｍａｃｈｉｎｅｓ，Ｉｎｃ．社製）を用いて、表１に示すコロナ処理ポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績（株）製　エステルＥ５１０２　厚さ１２μｍ）、コロナ処理二軸延伸ポリプロピレン（ＯＰＰ）フィルム（東洋紡績（株）製　パイレンＰ２１６１　厚さ２０μｍ）に、縦２４０ｍｍ×横８０ｍｍのベタ絵柄を印刷後、ドライヤーで乾燥し印刷物を得た。 Using the Flexiproof 100 test printer (Testing Machines, Inc.), the aqueous liquid inks of Examples 1 to 9 and Comparative Examples 1 to 4 were treated with a corona-treated polyethylene terephthalate (PET) film shown in Table 1 (Toyobo ( Co., Ltd. Ester E5102 thickness 12 μm, Corona-treated biaxially oriented polypropylene (OPP) film (Toyobo Co., Ltd. Pyrene P 2161 thickness 20 μm), print a solid pattern of 240 mm long × 80 mm wide, and then dry it with a dryer I got the printed matter.
　得られた印刷物について、各フィルム使用時の再溶解性、耐ブロッキング性、基材密着性について評価し、インキ転移性については印刷濃度で確認した。 About the obtained printed matter, re-solubility at the time of each film use, blocking resistance, base-material adhesiveness were evaluated, and ink transferability was confirmed by printing density.
　〔評価項目１：ボイルレトルト性（耐熱水性）〕
　前記コロナ処理ポリエチレンテレフタレート（ＰＥＴ）フィルム印刷物のインキ面にウレタン系のドライラミネート接着剤ディックドライＬＸ－５００／ＫＷ－７５（ＤＩＣ製）を塗膜量が３．５ｇ／ｍ２となるように塗布、乾燥後、ドライラミネート機（ＤＩＣエンジニアリング製）によってアルミニウム箔（以下、ＡＬ：東洋アルミニウム工業（株）製　アルミ箔Ｃ、１５μｍ）をラミネートし、２層のラミネート物１を得た。次にラミネート物１のＡＬ上に接着剤を同様に塗布し、無延伸ポリプロピレンフィルム（以下、Ｒ－ＣＰＰ：東レ合成フィルム社製　ＺＫ－７５　５０μｍ）を積層し、４０℃で５日間エージング施し、３層の複合ラミネート物２を得た。
　得られたラミネート物２を１２０ｍｍ×１２０ｍｍの大きさのパウチに製袋し、内容物として、食酢、サラダ油、ミートソースを重量比で１：１：１に配合した疑似食品７０ｇを充填密封した。作成したパウチを１３５℃、３０分間の蒸気レトルト殺菌処理をした後、インキ皮膜の剥離の程度を３段階で評価を行った。
　　　◎：剥離が全くない。
　　　○：小さなブリスター状の剥離が極僅かにある。
　　　△：中間サイズのブリスター状の剥離が部分的にある。
　　　×：大小問わず、全面に剥離がある。 [Evaluation item 1: Boil retort property (hot water resistance)]
The ink surface of the above-mentioned corona-treated polyethylene terephthalate (PET) film printed material is coated with a urethane-based dry lamination adhesive Dick Dry LX-500 / KW-75 (made by DIC) in a coating amount of 3.5 g / m 2 After drying, an aluminum foil (hereinafter, AL: manufactured by Toyo Aluminum Industry Co., Ltd., aluminum foil C, 15 μm) was laminated by a dry laminating machine (manufactured by DIC Engineering) to obtain a laminate 1 of two layers. Next, an adhesive is similarly applied on the AL of the laminate 1, a non-oriented polypropylene film (hereinafter, R-CPP: Toray Synthetic Film ZK-75 50 μm) is laminated, and subjected to aging at 40 ° C. for 5 days, A three-layer composite laminate 2 was obtained.
The obtained laminate 2 was formed into a pouch of 120 mm × 120 mm and filled with 70 g of simulated food containing vinegar, salad oil and meat sauce at a weight ratio of 1: 1: 1. The resulting pouch was subjected to steam retort sterilization treatment at 135 ° C. for 30 minutes, and the degree of peeling of the ink film was evaluated in three steps.
◎: There is no peeling at all.
○: There is very little blister-like peeling.
Δ: Partially blister-like peeling of medium size.
X: There is peeling on the entire surface regardless of size.
　〔評価項目２：再溶解性〕
　印刷物のインキ塗膜面にスポイトで蒸留水を１滴たらし、ガーゼで素早く拭きとった。拭き取り後に、塗膜が溶解してなくなるまでの時間を測定し評価した。
　　　◎：滴下後、３秒未満塗膜が溶解する。
　　　〇：滴下後、３秒以上～５秒未満で溶解する。
　　　△：滴下後、５秒以上～７秒未満で溶解する。
　　　×：塗膜溶解に７秒以上要する。 [Evaluation item 2: Resolubility]
A drop of distilled water was dripped with a dropper on the ink coating surface of the printed matter and quickly wiped off with gauze. After wiping off, the time until the coating film dissolved and disappeared was measured and evaluated.
◎: The film is dissolved for less than 3 seconds after dropping.
Good: Dissolve in 3 seconds or more and less than 5 seconds after dropping.
Δ: Dissolve in 5 seconds or more and less than 7 seconds after dropping.
X: It takes 7 seconds or more to dissolve the coating film.
　〔評価項目３：耐ブロッキング性〕
　印刷物の印刷面と非印刷面が接触するようにフィルムを４ｃｍ×４ｃｍサイズにカットしてから重ねあわせ、５Ｋｇｆ／ｃｍ２の荷重をかけ、４０℃の環境下に１２時間放置した後、フィルムを剥離した際の非印刷面へのインキの転移（裏移り）の状態を、裏移りの部分の面積比率（％）を基準に目視で判定した。
　　　◎：非印刷面への転移は全く見られない。
　　　○：５％未満と僅かであるが、裏移りによる転移が見られる。
　　　△：５％以上～２０％未満の裏移りによる転移が見られる。
　　　×：２０％以上の裏移りによる転移が見られる。 [Evaluation item 3: blocking resistance]
The film is cut into 4 cm × 4 cm size so that the printed surface and the non-printed surface of printed matter are in contact, then stacked, applied with a load of 5 Kgf / cm 2 , and left in a 40 ° C. environment for 12 hours. The state of transfer (offset) of the ink to the non-printing surface upon peeling was visually determined based on the area ratio (%) of the offset portion.
◎: Transfer to the non-printing surface is not observed at all.
○: slight, less than 5%, but transition due to offset is observed.
Δ: Transfer by 5% or more and less than 20% offset is observed.
X: Transfer by 20% or more of offset transfer is observed.
　〔評価項目４：基材密着性〕
　印刷物を１日放置後、印刷面にセロハンテープ（ニチバン製１２ｍｍ幅）を貼り付け、セロハンテープの一端を印刷面に対して直角方向に素早く引き剥がした時の印刷皮膜の残存率を基準に外観を目視判定した。
　　　◎：印刷皮膜が全く剥がれない。
　　　○：印刷皮膜の８０％以上～９０％未満がフィルムに残った。
　　　△：印刷皮膜の５０％以上～８０％未満がフィルムに残った。
　　　×：印刷皮膜の５０％未満しかフィルムに残らなかった。 [Evaluation item 4: Adhesiveness to substrate]
After leaving the printed matter for 1 day, paste the cellophane tape (12 mm width made by Nichiban) on the printing surface, and then take the appearance of the remaining film thickness when the cellophane tape is quickly peeled off in the direction perpendicular to the printing surface. Were visually determined.
◎: The printed film does not peel at all.
○: 80% or more and less than 90% of the printed film remained on the film.
Fair: 50% or more and less than 80% of the printed film remained on the film.
X: Less than 50% of the printed film remained on the film.
　〔評価項目５：インキ転移性〕
　前記印刷物のベタ濃度をＸ－Ｒｉｔｅ社製ＳｐｅｃｔｒｏＥｙｅ濃度計を使用してインキ転移性を評価した。
　　　〇：印刷物の藍濃度は１．９以上であり、インキ転移性は良好である。
　　　△：印刷物の藍濃度は１．６以上１．９未満であり、インキ転移性は中位である。
　　　×：印刷物の藍濃度は１．６未満であり、インキ転移性は不良である。 [Evaluation item 5: Ink transferability]
The solid density of the printed matter was evaluated for ink transferability using a SpectroEye densitometer manufactured by X-Rite.
Good: The haze density of the printed matter is 1.9 or more, and the ink transferability is good.
Δ: The haze density of the printed matter is 1.6 or more and less than 1.9, and the ink transferability is moderate.
X: The haze density of the printed matter is less than 1.6, and the ink transferability is poor.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明の水性リキッドインキを用いることで、基材に対する密着性・耐ブロッキング性・再溶解性・高い印刷濃度を兼ね備えた上に、さらに高い耐水性（ボイルレトルト性）と両立できる水性リキッドインキを提供することができる。上記性能を兼ね備えることで、ボイルレトルトにも耐えうる印刷物を提供可能である。 By using the aqueous liquid ink of the present invention, an aqueous liquid ink which has both adhesion to a substrate, resistance to blocking, re-dissolution and high printing density and is compatible with higher water resistance (boil retort) Can be provided. By combining the above-mentioned performances, it is possible to provide a printed matter that can withstand boiling retort.

Claims (6)

  1. 　着色剤（Ａ）、酸基を有するバインダー（Ｂ）、塩基性化合物（Ｃ）及び水性媒体（Ｄ）を含む水性リキッドインキであって、
    　前記酸基を有するバインダー（Ｂ）が、酸基を有するポリオール（ｂ１－１）及びポリエーテルポリオール（ｂ１－２）を含むポリオール（ｂ１）と、ポリイソシアネート（ｂ２）との反応物であるウレタン樹脂（Ｂ１）を含むものであり、
    　前記ウレタン樹脂（Ｂ１）に含まれる脂環式構造の含有量が、前記ウレタン樹脂（Ｂ１）の総量中、１，０００ｍｍｏｌ／ｋｇ以上５，０００ｍｍｏｌ／ｋｇ以下であり、
    　前記塩基性化合物（Ｃ）が、塩基性金属化合物（Ｃ１）と有機アミン（Ｃ２）とを含むものであることを特徴とする水性リキッドインキ。     An aqueous liquid ink comprising a colorant (A), a binder (B) having an acid group, a basic compound (C) and an aqueous medium (D),
    Urethane which is a reaction product of the polyol (b1) containing the acid group-containing polyol (b1-1) and the polyether polyol (b1-2) and the polyisocyanate (b2). Containing resin (B1),
    The content of the alicyclic structure contained in the urethane resin (B1) is 1,000 mmol / kg or more and 5,000 mmol / kg or less in the total amount of the urethane resin (B1),
    An aqueous liquid ink characterized in that the basic compound (C) contains a basic metal compound (C1) and an organic amine (C2).
  2. 　以下の式で表される比率が、０．３以下である請求項１に記載の水性リキッドインキ。
    　塩基性金属化合物（Ｃ１）のモル数×塩基性金属化合物（Ｃ１）の価数／｛（有機アミン（Ｃ２）のモル数×有機アミン（Ｃ２）の価数）＋（塩基性金属化合物（Ｃ１）のモル数×塩基性金属化合物（Ｃ１）の価数）｝     The water-based liquid ink according to claim 1, wherein a ratio represented by the following formula is 0.3 or less.
    Number of moles of basic metal compound (C1) × valent number of basic metal compound (C1) / {(number of moles of organic amine (C2) × valent number of organic amine (C2)) + (basic metal compound (C1) Number of moles of) × valence of basic metal compound (C1))}
  3. 　前記酸基を有するバインダー（Ｂ）の酸価が、３ｍｇＫＯＨ／ｇ以上４０ｍｇＫＯＨ／ｇ以下である請求項１又は２記載の水性リキッドインキ。 The aqueous liquid ink according to claim 1 or 2, wherein the acid value of the binder (B) having an acid group is 3 mg KOH / g or more and 40 mg KOH / g or less.
  4. 　前記ポリオール（ｂ１）が、さらに脂環式構造を有するポリオール（ｂ１－３）を０～２０質量％含むものである請求項１～３のいずれか一項記載の水性リキッドインキ。 The aqueous liquid ink according to any one of claims 1 to 3, wherein the polyol (b1) further comprises 0 to 20% by mass of a polyol (b1-3) having an alicyclic structure.
  5. 　２５℃における表面張力が２５ｍＮ／ｍ以上５０ｍＮ／ｍ以下である請求項１～４のいずれか一項記載の水性リキッドインキ。 The aqueous liquid ink according to any one of claims 1 to 4, which has a surface tension at 25 ° C of 25 mN / m or more and 50 mN / m or less.
  6. 　請求項１～５のいずれか一項記載の水性リキッドインキを用いて印刷されたものであることを特徴とする印刷物。 A printed matter characterized by being printed using the aqueous liquid ink according to any one of claims 1 to 5.
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