WO2019102855A1 - Encre liquide aqueuse et article imprimé - Google Patents

Encre liquide aqueuse et article imprimé Download PDF

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Publication number
WO2019102855A1
WO2019102855A1 PCT/JP2018/041463 JP2018041463W WO2019102855A1 WO 2019102855 A1 WO2019102855 A1 WO 2019102855A1 JP 2018041463 W JP2018041463 W JP 2018041463W WO 2019102855 A1 WO2019102855 A1 WO 2019102855A1
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WIPO (PCT)
Prior art keywords
polyol
mass
less
aqueous liquid
liquid ink
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Application number
PCT/JP2018/041463
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English (en)
Japanese (ja)
Inventor
定 永浜
直人 佐竹
康敬 小代
利桂 佐坂
隆晃 工藤
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 JP2019531357A priority Critical patent/JP6622947B2/ja
Priority to CN201880073255.7A priority patent/CN111344364B/zh
Priority to AU2018373095A priority patent/AU2018373095B2/en
Publication of WO2019102855A1 publication Critical patent/WO2019102855A1/fr

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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
    • C08G18/40—High-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • 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 polyuretan 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).
  • aqueous printing inks are slower to dry compared to solvent-based inks, and in addition to having adhesion to a plastic substrate which is the basic performance, blocking resistance, etc., it is necessary to have pigment dispersibility etc. It is difficult to improve the printing density after combining these.
  • the basic performance as an aqueous liquid ink may not be sufficient.
  • water-based printing ink composition for laminations described in patent document 2 there existed a case where it could not be said that it could especially stand long run printing.
  • the present invention has been made in view of the above-mentioned circumstances, and in addition to having the basic performance as an aqueous liquid ink (adhesion to a substrate, resistance to blocking, high printing density, etc.), further high water resistance (boiling)
  • An object of the present invention is to provide a water-based liquid ink having both retort resistance and solvent resistance.
  • 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 polyol (b1) comprising at least one selected from the group consisting of a polyol (b1-1) having an acid group and a polyester polyol (b1-2) and a polycarbonate polyol (b1-3), and a polyisocyanate (b2)
  • the urethane resin (B1) which is a reaction product with (a), and the content of the alicyclic structure contained in the urethane resin (B1) is 1,000 mmol / m in the total amount of the urethane resin (B1).
  • It relates an aqueous liquid ink, characterized in that those comprising.
  • an aqueous liquid which not only has basic performance (adhesivity, blocking resistance, high printing density, etc.) as an aqueous liquid ink but also has high water resistance (boil retort resistance) and high solvent resistance. It is possible to provide liquid ink.
  • 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 polyol comprising at least one selected from the group consisting of a polyol (b1-1) having an acid group and a polyether polyol (b1-2) and a polycarbonate polyol (b1-3)
  • the urethane resin (B1) which is a reaction product of (b1) and polyisocyanate (b2) is included.
  • 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 30 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 1,200 mmol / kg or more, more preferably 1 in the total amount of the urethane resin (B1). , Preferably 500 mmol / kg or less, more preferably 3,000 mmol / kg or less, still 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 urethane resin (B1) may contain an aromatic ring.
  • the content thereof is preferably 0 mmol / kg or more, more preferably 500 mmol / kg or more, still more preferably 1,000 mmol / kg of the total amount of the urethane resin (B1). It is not less than kg, preferably not more than 4,000 mmol / kg, more preferably not more than 3,000 mmol / kg, still more preferably not more than 2,500 mmol / kg.
  • 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).
  • polyester polyol (b1-2) examples include polyester polyols obtained by subjecting a low molecular weight polyol (for example, a polyol having a molecular weight of 50 to 300) to esterification reaction with a polycarboxylic acid; cyclic esters such as ⁇ -caprolactone Examples thereof include polyester polyols obtained by ring-opening polymerization reaction of the compounds; and copolyester polyols thereof.
  • 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.
  • the number average molecular weight of the polyester polyol (b1-2) is preferably 500 or more, more preferably 1,000 or more, preferably 4,000 or less, more preferably 3 from the viewpoint of compatibility with the pigment etc. Less than 1,000.
  • Examples of the polycarbonate polyol (b1-3) include a reaction product of a carbonate ester and a polyol; a reaction product of phosgene and a polyol and the like.
  • Examples of the carbonic ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.
  • the number average molecular weight of the polycarbonate polyol (b1-3) is preferably 500 or more, more preferably 1,000 or more, preferably 4,000 or less, more preferably 3 from the viewpoint of compatibility with the pigment etc. Less than 1,000.
  • the content of the polycarbonate polyol (b1-3) in the total of the polyester polyol (b1-2) and the polycarbonate polyol (b1-3) in the polyol (b1) is preferably 0% by mass or more, more preferably It is 10% by mass or more, more preferably 20% by mass or more, preferably 100% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less.
  • the polyol (b1) preferably contains at least a polycarbonate polyol (b1-3).
  • the content of the polycarbonate polyol (b1-3) in the polyol (b1) is preferably 0% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 100% by mass or less More preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less.
  • the total content of the polyol (b1-1) having the acid group, the ester polyol (b1-2) and the polycarbonate polyol (b1-3) is preferably 60% by mass or more in the polyol (b1). Preferably it is 75 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, and may be 95 mass% or less.
  • the polyol (b1) preferably further contains a polyol (b1-4) having an alicyclic structure.
  • a polyol (b1-4) 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 the 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 the acid group, the polyester polyol (b1-2), the polycarbonate polyol (b1-3) and the polyol (b1-4) having the alicyclic structure is as follows:
  • the content is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the polyol (b1).
  • the polyol (b1) may contain other polyols (b1-5).
  • examples of the other polyols include polyether polyols, low molecular weight polyols (for example, having a molecular weight of 50 or more and 300 or less), and polyolefin polyols.
  • 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).
  • 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.
  • polystyrene polyol examples include polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, hydrogenated (hydrogenated) polyisoprene polyol and the like.
  • the content of the other polyol (b1-5) 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.
  • 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 triene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane Fats such as 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 at least one selected from the group consisting of 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.
  • 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.
  • the basic compound (C) preferably contains at least an organic amine (C2).
  • 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 Examples 1 to 10, Comparative Synthesis Examples 1 to 3 Preparation of Binders (1) to (13) Molecular termination by reacting the polyol (b1) shown in Table 1 and the polyisocyanate (b2) shown in Table 1 in methyl ethyl ketone in a thermometer, a nitrogen gas inlet tube, and a nitrogen-substituted container equipped with a stirrer. An organic solvent solution of a urethane prepolymer (a binder having an acid group) having an isocyanate group is obtained.
  • a basic compound (C) shown in Table 1 or an aqueous solution thereof is added to neutralize part or all of the carboxy groups possessed by the urethane prepolymer, and further an aqueous solution of water and a chain extender shown in Table 1
  • the aqueous dispersion of the urethane resin was obtained by sufficiently stirring, and then aging and solvent removal to obtain binders (1) to (13) having a nonvolatile content of 40% by mass.
  • the content of the alicyclic structure in the urethane resin, the content of the aromatic ring and the acid value of the obtained binders (1) to (13) are shown in Table 1.
  • polyester polyol 1 represents aliphatic polyester polyol ("L 212 AL” manufactured by Daicel Corporation, number average molecular weight 1, 250), and polyester polyol 2 is aromatic polyester polyol (ethylene glycol 13.1 parts by mass, neopentyl) An aromatic polyester polyol in which 22.0 parts by mass of glycol, 18.5 parts by mass of terephthalic acid, 18.5 parts by mass of isophthalic acid and 7.9 parts by mass of acrylic acid are reacted in the presence of 0.03 parts by mass of monobutyl tin oxide
  • the polycarbonate polyol 1 represents a number average molecular weight of 1,000), and the polycarbonate polyol 2 represents a polycarbonate polyol (Ube Industries, Ltd., a number average molecular weight of 2,000). Company Ltd.
  • "ETERNACOLL UH-100" represents the number average molecular weight of 1,000
  • polyether polyol 1 represents a polytetramethylene glycol (number average molecular weight of 2,000
  • 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 10 and Comparative Examples 1 to 3 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
  • OPP biaxially oriented polypropylene
  • the resulting printed matter was evaluated for boil retort resistance, solvent resistance, blocking resistance and substrate adhesion when using each film, and the ink transferability was confirmed by the printing density.
  • 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 four 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.
  • the aqueous liquid ink of the present invention By using the aqueous liquid ink of the present invention, the basic performance as the aqueous liquid ink (adhesion to a substrate, resistance to blocking, high printing density, etc.) is obtained, and further high water resistance (boil retort resistance) and It is possible to provide a water-based liquid ink that combines solvent resistance. By combining the above-mentioned performances, it is possible to provide a printed matter that can withstand boiling retort.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention aborde le problème de fourniture d'une encre liquide aqueuse qui présente des caractéristiques fondamentales en tant qu'encre liquide aqueuse (adhérence à un matériau de base, résistance à l'adhérence, densité d'impression élevée, etc.), et qui présente également une résistance élevée à l'eau (propriétés d'autoclavage) et une résistance élevée aux solvants. Cette encre liquide aqueuse comprend un agent colorant (A), un liant (B) possédant des groupes acides, un composé basique (C) et un milieu aqueux (D). Le liant (B) possédant des groupes acides comprend une résine d'uréthane (B1) qui est un produit de réaction d'un polyisocyanate (b2) et d'un polyol (b1) comprenant au moins l'un parmi un polyol (b1-1) possédant des groupes acides, un polyester-polyol (b1-2) et un polycarbonate-polyol (b1-3). La teneur en structures alicycliques dans la résine d'uréthane (B1) est d'au moins 1000 mmoles/kg. Le composé basique (C) comprend au moins l'un parmi un composé métallique basique (C1) et une amine organique (C2).
PCT/JP2018/041463 2017-11-22 2018-11-08 Encre liquide aqueuse et article imprimé WO2019102855A1 (fr)

Priority Applications (3)

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JP2019531357A JP6622947B2 (ja) 2017-11-22 2018-11-08 水性リキッドインキ及び印刷物
CN201880073255.7A CN111344364B (zh) 2017-11-22 2018-11-08 水性液体墨及印刷物
AU2018373095A AU2018373095B2 (en) 2017-11-22 2018-11-08 Aqueous liquid ink and printed article

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JP2017-224633 2017-11-22

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WO2011004675A1 (fr) * 2009-07-09 2011-01-13 Dic株式会社 Liant pour encre d’impression par jet d’encre, encre pour impression par jet d’encre le contenant, et matière imprimée
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JP2013527267A (ja) * 2010-03-31 2013-06-27 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 水性インクジェット用インク組成物
JP2013234214A (ja) * 2012-05-07 2013-11-21 Toyo Ink Sc Holdings Co Ltd 水性ポリウレタン樹脂およびその利用
JP2015067818A (ja) * 2013-10-01 2015-04-13 東洋インキＳｃホールディングス株式会社 ラミネート用水性グラビア印刷インキ組成物
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JP2005272587A (ja) * 2004-03-24 2005-10-06 Toyo Ink Mfg Co Ltd ポリウレタン樹脂組成物、およびそれを含有する水性印刷インキ組成物、さらにそれを用いてなるプラスチックシート被覆物とそのラミネート積層物
WO2011004675A1 (fr) * 2009-07-09 2011-01-13 Dic株式会社 Liant pour encre d’impression par jet d’encre, encre pour impression par jet d’encre le contenant, et matière imprimée
JP2013527267A (ja) * 2010-03-31 2013-06-27 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 水性インクジェット用インク組成物
JP2012246486A (ja) * 2010-11-30 2012-12-13 Dic Corp インクジェット印刷インク用バインダー、インクジェット印刷用インク、印刷物、及び、バインダーの製造方法
JP2013234214A (ja) * 2012-05-07 2013-11-21 Toyo Ink Sc Holdings Co Ltd 水性ポリウレタン樹脂およびその利用
JP2015067818A (ja) * 2013-10-01 2015-04-13 東洋インキＳｃホールディングス株式会社 ラミネート用水性グラビア印刷インキ組成物
JP2017088840A (ja) * 2015-11-06 2017-05-25 株式会社リコー インク、インク収容容器、インクジェット記録方法、インクジェット記録装置、及び記録物

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JPWO2019102855A1 (ja) 2019-11-21
CN111344364A (zh) 2020-06-26
JP6622947B2 (ja) 2019-12-18
CN111344364B (zh) 2021-06-18
AU2018373095A1 (en) 2020-06-11
TW201925375A (zh) 2019-07-01
TWI766124B (zh) 2022-06-01

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