WO2023145181A1 - Jeu d'encres et matière imprimée - Google Patents

Jeu d'encres et matière imprimée Download PDF

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Publication number
WO2023145181A1
WO2023145181A1 PCT/JP2022/040720 JP2022040720W WO2023145181A1 WO 2023145181 A1 WO2023145181 A1 WO 2023145181A1 JP 2022040720 W JP2022040720 W JP 2022040720W WO 2023145181 A1 WO2023145181 A1 WO 2023145181A1
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WIPO (PCT)
Prior art keywords
water
mass
pigment
resin emulsion
ink composition
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PCT/JP2022/040720
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English (en)
Japanese (ja)
Inventor
孝明 佐野
恵理 植田
員揮 森安
寛仁 前田
Original Assignee
サカタインクス株式会社
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Publication of WO2023145181A1 publication Critical patent/WO2023145181A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink

Definitions

  • the present invention relates to ink sets and printed matter.
  • Patent References 1-7 A printing method using an ink set comprising an aqueous inkjet ink composition containing a pigment or the like and a primer composition containing an aggregation accelerator for promoting aggregation of the aqueous inkjet ink composition is known (Patent References 1-7).
  • Patent References 1-7 when fine line printing is performed on a primer layer formed from the primer composition using a water-based inkjet ink composition, it is possible to form a good print image quality (print layer) without bleeding. disclosed.
  • metal salts are often used as flocculants contained in primer compositions.
  • metal salts lowers the water resistance of the primer layer itself.
  • a cationic polymer can be used as such a flocculant, as in Patent Documents 4 to 7 above.
  • printed materials such as packaging containers for retort pouches are formed by forming a printed layer (printing ink) on a plastic film (base film) such as PET, and then printing on the surface of the printed layer and on the inside of the packaging container. It is produced by using a laminated film obtained by laminating two sealant films with an adhesive, sealing the sealant film with heat, and processing it into a bag shape.
  • Plastic films such as PET films as described above have higher heat resistance than polypropylene films such as OPP films, but the substrate is hard, and there is a problem that it is difficult to ensure adhesion to the coating film (printing layer). .
  • the present invention has been made in view of the above-mentioned circumstances, and a primer composition capable of forming a primer layer having excellent water resistance, and a primer composition that has improved adhesion, solid image printability, and bleeding resistance on the primer layer.
  • An object of the present invention is to provide an ink set having a water-based inkjet ink composition capable of forming an excellent ink layer.
  • Another object of the present invention is to provide a printed matter obtained by printing the ink set.
  • the present invention includes a water-based inkjet ink composition containing a pigment, a dispersant for the pigment, a water-soluble solvent, and water, a flocculating agent for aggregating the water-based inkjet ink composition, a resin emulsion, and water.
  • the ink set has a primer composition, wherein the dispersant is a polyurethane resin, and the flocculant is a compound having a polyethyleneimine skeleton.
  • the present invention also relates to a printed matter obtained by printing the ink set.
  • the ink set of the present invention comprises an aqueous inkjet ink composition containing a pigment, a dispersant for the pigment, a water-soluble solvent, and water; a flocculant for aggregating the aqueous inkjet ink composition; a resin emulsion; and water.
  • the dispersant is a polyurethane resin
  • the flocculant is a compound having a polyethyleneimine skeleton.
  • at least a polyurethane resin is used as a dispersant for the pigment contained in the water-based inkjet ink composition, and an ink set using a compound having a polyethyleneimine skeleton as a flocculant contained in the primer composition. is not specifically shown.
  • the polyurethane resin used as the pigment dispersant has high adhesion
  • the compound having a polyethyleneimine skeleton used as the coagulant is a polymer compound with excellent water resistance.
  • an aqueous inkjet ink composition capable of forming an ink layer having excellent adhesion, solid image printability, and bleeding resistance on the primer layer.
  • the water-based inkjet ink composition of the present invention contains a pigment, a dispersant for the pigment, a water-soluble solvent, and water.
  • organic pigments and inorganic pigments used in aqueous inkjet ink compositions can be used.
  • the organic pigment include dye lake pigments, azo pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindico pigments, perylene pigments, Perinone pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, nitro pigments, nitroso pigments, anthraquinone pigments, flavanthrone pigments, quinophthalone pigments, pyranthrone pigments, indanthrone pigments, etc.
  • examples of the inorganic pigments include carbon black, titanium oxide, zinc white, red iron oxide, graphite, iron black, chromium oxide green, and aluminum hydroxide.
  • the pigment may be surface-treated with a known surface-treating agent.
  • the pigments may be used alone or in combination of two or more.
  • yellow pigment for example, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 42, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 108, 109, 114, 120, 128, 129, 138, 139, 150, 151, 155, 166, 180, 184, 185, 213 and the like.
  • magenta pigment for example, C.I. I. Pigment Red 5, 7, 12, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1, 57, 57:1, 63:1, 101, 102, 112, 122, 123, 144, 146, 149, 150, 168, 176, 177, 178, 179, 180, 184, 185, 190, 202, 209, 224, 242, 254, 255, 270, C.I. I. Pigment Violet 19 and the like.
  • cyan pigment for example, C.I. I. Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 22, 27, 29, 60 and the like.
  • Black pigments include, for example, carbon black (C.I. Pigment Black 7).
  • white pigments include titanium oxide and aluminum oxide, which may be surface-treated with various materials such as alumina and silica.
  • the proportion of the pigment in the water-based inkjet ink composition is preferably 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of improving the printing density of printed matter, and is stable in ejection. From the viewpoint of improving properties, the content is preferably 10% by mass or less, more preferably 8% by mass or less. That is, the proportion of the pigment in the water-based inkjet ink composition is preferably 1% by mass or more and 10% by mass or less from the viewpoint of improving the printing density of the printed matter and improving the ejection stability. It is more preferable that it is more than mass % and less than 8 mass %.
  • the proportion of the white pigment in the aqueous inkjet ink composition is preferably 4% by mass or more, more preferably 8% by mass or more, and It is preferably 30% by mass or less, more preferably 20% by mass or less. That is, the proportion of the white pigment in the aqueous inkjet ink composition is preferably 4% by mass or more and 30% by mass or less, more preferably 8% by mass or more and 20% by mass or less.
  • the pigment dispersant is a polyurethane resin.
  • the polyurethane resin include polyurethane resins obtained by reacting a diisocyanate compound and a diol compound, optionally with a chain extender or a reaction terminator.
  • the polyurethane resins may be used alone or in combination of two or more.
  • diisocyanate compounds examples include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as isophorone diisocyanate and hydrogenated xylylene diisocyanate; xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate, toluylene diisocyanate, diphenylmethane diisocyanate and other aromatic diisocyanate compounds.
  • the diisocyanate compounds may be used alone or in combination of two or more.
  • diol compound examples include low molecular weight diols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol and triethylene glycol; high molecular weight diols such as polyester diol compounds, polyether diol compounds, polycarbonate diol compounds and polybutadiene glycol compounds types are mentioned.
  • the diol compounds may be used alone or in combination of two or more.
  • the polyurethane resin preferably has one or more skeletons selected from the group consisting of a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, and a polybutadiene skeleton, from the viewpoint of adhesion to plastic films, lamination suitability, and the like. preferable.
  • the polyurethane resin preferably has an ionic group in the molecule in order to easily disperse the pigment in water. preferably.
  • a diol compound having a carboxyl group, a sulfonic acid group, or the like may be used as the diol compound, and the general formula (1):
  • R 1 represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.
  • succinic acid, adipine Aliphatic carboxylic acid-containing polyols obtained by reacting an acid or the like with a polyol, aromatic carboxylic acid-containing polyols obtained by reacting a polyol with phthalic acid, trimellitic acid, pyromellitic acid or anhydride thereof, etc. is mentioned.
  • the polyurethane resin When the polyurethane resin has an anionic group, it preferably has an acid value of 5 to 100 mgKOH/g. If the acid value of the polyurethane resin is less than 5 mgKOH/g, the dispersibility in an aqueous medium described later may decrease, and if it is greater than 100 mgKOH/g, the drying property during printing and the water resistance of the resulting printed matter etc. may decrease.
  • the acid value is more preferably 5 to 50 mgKOH/g from the viewpoint of suitably imparting lamination strength (peel strength between the base film and the sealant film).
  • the acid value is a theoretical acid value, and it depends on the molecular weight of the anionic group-containing compound of the carboxyl group used as a synthetic component of the polyurethane resin, the compounding ratio, and the number of anionic groups of the carboxyl group contained in the molecule of the compound.
  • the number of mg of potassium hydroxide theoretically required to neutralize 1 g of polyurethane resin calculated arithmetically based on the above.
  • a compound having two or more functional groups capable of reacting with an isocyanate group in the molecule
  • Compounds containing two or more amino groups in the molecule include, for example, diamines having two primary amino groups (ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, hexamethylenediamine, isophoronediamine, etc. ), diamines having one primary amino group and one secondary amino group (2-ethylaminoethylamine, etc.), polyamines having two primary amino groups and one or more secondary amino groups (diethylenetriamine, triethylene tetramine, etc.).
  • hydroxyl group-containing compounds containing two or more hydroxyl groups in the molecule include low-molecular-weight diols (ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc.).
  • compounds having two amino groups and one hydroxyl group in the molecule include, for example, aminoethylethanolamine, aminopropylethanolamine, and the like, and 1 mol of ethylene oxide is added to the diamines having two primary amino groups. things, etc.
  • At least one chain extender may be used, and two or more thereof may be used in combination.
  • chain extender for example, from the viewpoint of introducing functional groups such as hydroxyl groups and amino groups into the molecule of the polyurethane resin, compounds having three or more functional groups such as amino groups and hydroxyl groups can be used.
  • compounds having three or more functional groups such as amino groups and hydroxyl groups include glycerin and aminoethylethanolamine.
  • the reaction terminator can be, for example, a compound having one or more functional groups (amino group, hydroxyl group, etc.) capable of reacting with an isocyanate group in the molecule.
  • monoalcohols methanol, ethanol, etc.
  • monoamines n-butylamine, di-n-butylamine, etc.
  • alkanolamines having one amino group and one hydroxyl group in the molecule (monoethanolamine, ethylethanolamine, diethanolamine), and the like.
  • the compounds exemplified as the chain elongation agent can also be used.
  • the reaction terminator is exemplified as alkanolamines having one amino group and one hydroxyl group in the molecule, or the chain extender. , diamines having two primary amino groups, and low-molecular-weight diols can be used. At least one type of the reaction terminator may be used, and two or more types may be used in combination.
  • reaction terminator examples include polyaminohydrazide, hydrazine (hydrazine hydrate), and the following general formula (2): H 2 N—NH—X—NH—NH 2
  • X is an alkylene dihydrazine or a saturated aliphatic diacid, represented by an alkylene group having 1 to 8 carbon atoms, or the residue of a saturated or unsaturated diacid having 1 to 10 carbon atoms
  • Dihydrazide compounds of unsaturated dibasic acids and the like can also be used.
  • alkylene dihydrazine include methylene dihydrazine, ethylene dihydrazine, butylene dihydrazine and the like.
  • dihydrazide compounds of saturated aliphatic dibasic acids include dihydrazide oxalate, dihydrazide malonate, dihydrazide glutarate, dihydrazide adipic acid, dihydrazide sebacate, and dihydrazide compounds of unsaturated dibasic acids.
  • dihydrazide phthalate, dihydrazide fumarate, and dihydrazide itaconate include dihydrazide phthalate, dihydrazide fumarate, and dihydrazide itaconate.
  • the polyurethane resin may be used as a water-based resin varnish using a basic compound or the like.
  • the basic compound is not particularly limited, and commonly used basic compounds can be used. Examples include alkylamines such as butylamine and triethylamine, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, morpholine, Ammonia water, sodium hydroxide, etc. can be mentioned.
  • the amount of the basic compound to be blended is appropriately set according to the physical properties of the polyurethane resin to be used, the amount used, etc., and may be used singly or in combination of two or more.
  • the content of the polyurethane resin is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the pigment.
  • the content of the polyurethane resin is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, relative to 100 parts by mass of the pigment, from the viewpoint of reducing the viscosity of the aqueous inkjet composition. , 50 parts by mass or less. That is, the content of the polyurethane resin is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the pigment, from the viewpoint of enhancing the dispersibility of the pigment and reducing the viscosity of the aqueous inkjet composition. more preferably 10 parts by mass or more and 60 parts by mass or less, and even more preferably 10 parts by mass or more and 50 parts by mass or less.
  • water-soluble solvent known water-soluble solvents used in aqueous inkjet ink compositions can be used. Examples include monoalcohols, polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, nitrogen-containing compounds, Ketones, ethers, esters and the like can be mentioned. The water-soluble solvents can be used alone or in combination of two or more.
  • Examples of the monoalcohols include methanol, ethanol, 1-propanol, 1-butanol, 3-methoxy-3-methyl-1-butanol and the like.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, glycerin, diethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, 1 ,2-hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, heptanediol, 1,8-octanediol and the like.
  • Examples of the lower alkyl ethers of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, Ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -n-butyl ether and the like.
  • nitrogen-containing compounds examples include pyrrolidone and N-methyl-2-pyrrolidone.
  • ketones examples include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, cyclohexanone and the like.
  • ethers examples include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like.
  • esters examples include propylene carbonate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethyl butyrate, dibutyl phthalate, dioctyl phthalate; ⁇ -caprolactone, ⁇ . - Cyclic esters such as caprolactam and the like.
  • the water-soluble solvent includes monoalcohols, polyhydric alcohols, and polyhydric alcohols, from the viewpoint of suppressing drying of the ink composition in the inkjet nozzle and facilitating the formation of an ink layer (film) on the substrate. It preferably contains at least one selected from the group consisting of lower alkyl ethers of alcohol and nitrogen-containing compounds, propylene glycol, glycerin, diethylene glycol, ethylene glycol monobutyl ether and diethylene glycol monobutyl ether, 3-methoxy-3- More preferably, it contains at least one selected from the group consisting of methyl-1-butanol.
  • the proportion of the water-soluble solvent in the water-based inkjet ink composition is preferably 15% by mass or more, more preferably 20% by mass or more, from the viewpoint of improving ejection stability.
  • the content is preferably 60% by mass or less, more preferably 50% by mass or less. That is, the proportion of the water-soluble solvent in the water-based inkjet ink composition is preferably 15% by mass or more and 60% by mass or less from the viewpoint of improving ejection stability and improving coating film drying properties. , more preferably 20% by mass or more and 50% by mass or less.
  • the water of the present invention includes water as an aqueous medium contained in the pigment dispersion described below and water added for adjusting the concentration of the water-based inkjet ink composition of the present invention.
  • Examples of the water include ion-exchanged water, pure water, distilled water, and industrial water.
  • the water may be used alone or in combination of two or more.
  • the proportion of the water (including the water contained in each component) in the water-based inkjet ink composition is preferably 40% by mass or more, and 50% by mass or more, from the viewpoint of improving the drying property of the coating film.
  • the content is preferably 70% by mass or less, and more preferably 60% by mass or less. That is, the proportion of the water (including the water contained in each component) in the water-based inkjet ink composition is 40% by mass or more and 70% by mass from the viewpoint of improving the drying property of the coating film and improving the ejection stability. % or less, more preferably 50% by mass or more and 60% by mass or less.
  • a resin emulsion may be used in the water-based inkjet ink composition from the viewpoint of improving bleeding resistance.
  • resin emulsion known resin emulsions used in aqueous inkjet ink compositions can be used. Examples include acrylic resin emulsion, styrene-acrylic resin emulsion, polyester resin emulsion, polyurethane resin emulsion, and polyvinyl acetate. system resin emulsion, polyvinyl chloride system resin emulsion, polybutadiene system resin emulsion, polyolefin system resin emulsion, and the like.
  • the resin emulsion preferably has a glass transition temperature of 20° C.
  • the glass transition temperature is obtained by differential scanning calorimetry (DSC), and is usually calculated from the midpoint of the temperature range where glass transition occurs.
  • the resin emulsions may be used alone or in combination of two or more.
  • the resin solid content of the resin emulsion is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of improving print quality and scratch resistance in the water-based inkjet ink composition. From the viewpoint of improving print image quality and storage stability, the content is preferably 10% by mass or less, more preferably 8% by mass or less. That is, the proportion of resin solids in the resin emulsion is preferably 1% by mass or more and 10% by mass or less from the viewpoint of improving print image quality, print image quality, and storage stability in the water-based inkjet ink composition. It is more preferably 3% by mass or more and 8% by mass or less.
  • the water-based inkjet ink composition may contain optional components depending on the purpose.
  • optional components include known resins, wax emulsions, pigment dispersants other than the pigment dispersants, surfactants, Additives such as antifungal agents, antirust agents, thickeners, antioxidants, ultraviolet absorbers, preservability improvers, antifoaming agents, and pH adjusters may also be added.
  • the method for preparing (manufacturing) the aqueous inkjet ink composition is not particularly limited, and the above components may be added in order or at the same time and mixed.
  • the polyurethane resin may be dissolved in water.
  • a pigment dispersant, etc. a pigment dispersion (ink base) is prepared using various dispersing machines such as ball mills, attritors, roll mills, sand mills, agitator mills, etc. and then adding the remaining materials to prepare a water-based inkjet ink composition.
  • the aqueous inkjet ink composition has an initial viscosity after production of 2.0 to 15.0 mPa ⁇ s, preferably 3.0 to 12.0 mPa ⁇ s.
  • the viscosity can be measured, for example, with an E-type viscometer (trade name “RE100L type viscometer”, manufactured by Toki Sangyo Co., Ltd.).
  • the primer composition of the present invention contains an aggregating agent for aggregating the aqueous inkjet ink composition, a resin emulsion, and water.
  • the flocculant is a compound having a polyethyleneimine skeleton.
  • the compound having a polyethyleneimine skeleton may have repeating units of ethyleneimine ( --CH.sub.2CH.sub.2NH-- ).
  • a branched polyethyleneimine in which an imine unit is polymerized in a branched chain is exemplified.
  • Polyethyleneimine may also be modified with a known modifier such as cycloalkyl.
  • the compounds having a polyethyleneimine skeleton can be used alone or in combination of two or more.
  • Examples of commercially available compounds having a polyethyleneimine skeleton include A-131-X (trade name) (manufactured by Mica Corporation), Epomin (trade name) (manufactured by Nippon Shokubai), and Lupasol series (trade name) (manufactured by BASF). .
  • the content of the aggregating agent is preferably 0.01% by mass or more, preferably 0.05% by mass or more, in the primer composition from the viewpoint of improving the clarity and bleeding resistance of printed matter. , more preferably 0.1% by mass or more, and from the viewpoint of improving bleeding resistance, it is preferably 10% by mass or less, more preferably 8% by mass or less in the primer composition. , 6% by mass or less. That is, the content of the flocculant is preferably 0.01% by mass or more and 10% by mass or less in the primer composition from the viewpoint of improving the clarity and bleeding resistance of the printed matter, and 0.05% by mass. It is preferably at least 8% by mass, more preferably at least 0.1% by mass and not more than 6% by mass.
  • the resin emulsion As the resin emulsion, a known one contained in the primer composition used in the aqueous inkjet ink composition can be used. For example, acrylic resin emulsion, polyester resin emulsion, polyurethane resin emulsion, and polyvinyl acetate resin emulsion can be used. , polyvinyl chloride resin emulsion, polybutadiene resin emulsion, polyolefin resin emulsion, and the like. Among these, polyurethane-based resin emulsions and polyolefin-based resin emulsions are preferable from the viewpoint of improving the printability of solid images. The resin emulsions may be used alone or in combination of two or more.
  • the polyurethane-based resin emulsion is an emulsion in which polyurethane resin is dispersed in water, and can be anionic, cationic, or nonionic.
  • the polyurethane resins include polyether-based polyurethane resins, polyester-based polyurethane resins, polyester/polyether-based polyurethane resins, and polycarbonate-based polyurethane resins.
  • the polyolefin resin emulsion is an emulsion in which polyolefin resin is dispersed in water.
  • the polyolefin resins include polyethylene resins, polypropylene resins, polybutylene resins, and polyolefin resins obtained by copolymerizing two or more of ethylene, propylene, and butylene.
  • the polyolefin resin includes a modified polyolefin resin obtained by introducing an amino group, a carboxyl group, a hydroxyl group, an acryloyl group, and other polymer chains into the polyolefin chain; an oxidized polyolefin resin obtained by oxidizing a part of the polyolefin chain; A halogenated polyolefin resin partially treated with halogen may also be used.
  • the resin solid content of the resin emulsion is preferably 0.5% by mass or more, more preferably 1% by mass or more, in the primer composition. And, from the viewpoint of improving bleeding resistance, it is preferably 10% by mass or less, more preferably 5% by mass or less, in the primer composition. That is, the resin solid content of the resin emulsion is 0.5% by mass or more and 10% by mass or less in the primer composition from the viewpoint of improving the printability of a solid image and the viewpoint of improving the bleeding resistance. is preferred, and more preferably 1% by mass or more and 5% by mass or less.
  • the water includes water contained in the resin emulsion, water added to adjust the concentration of the primer composition of the present invention, and the like.
  • Examples of the water include ion-exchanged water, pure water, distilled water, and industrial water.
  • the water may be used alone or in combination of two or more.
  • the proportion of the water (including the water contained in each component) is preferably 70% by mass or more, more preferably 80% by mass or more, from the viewpoint of improving the drying property of the coating film. From the viewpoint of improving stability, the content is preferably 98% by mass or less, more preferably 95% by mass or less. That is, the proportion of the water (including water contained in each component) is preferably 70% by mass or more and 98% by mass or less from the viewpoint of improving the drying property of the coating film and improving the ejection stability. It is more preferably 80% by mass or more and 95% by mass or less.
  • the primer composition of the present invention may contain optional components in addition to the components described above, if necessary.
  • optional components include water-soluble organic solvents and various additives.
  • additives include surfactants such as silicone-based surfactants, acetylene-based surfactants, and fluorine-based surfactants; preservability improvers, antifoaming agents, adhesion-imparting agents, fillers, thickeners, and the like. be done.
  • the primer composition is not particularly limited.
  • the resin emulsion, the flocculant, and, if necessary, the water-soluble organic solvent, the above various additives, etc. are added to water, and the mixture is stirred and mixed with a disper or the like. It can be manufactured by
  • the ink set of the present invention comprises the aqueous inkjet ink composition and the primer composition.
  • the printed matter of the present invention is obtained by printing an ink set comprising the aqueous inkjet ink composition and the primer composition.
  • the primer composition is applied to a substrate and dried to form a primer layer, and then the aqueous inkjet ink composition is printed on the primer layer using an inkjet printer to form an image ( forming a printed layer) method.
  • the coating method of the primer composition includes coating methods using various coating devices such as a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater, a lip coater, a curtain coater, a die coater, and an inkjet. mentioned.
  • a method of ink-jet printing can be mentioned by installing a recording device and ejecting from a nozzle onto a base material.
  • the substrate examples include non-absorbent print media such as art paper, inkjet paper, coated paper such as inkjet glossy paper, and plastic substrates such as polyolefin film, polyester film, nylon film, and polyvinyl chloride sheet.
  • uncoated paper such as plain paper and offset paper; fabrics such as cotton; among these, non-absorbent printing media are preferred from the viewpoint of good adhesion of the primer layer, and plastic-based substrates are more preferred. preferable.
  • food packaging containers such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, nylon-6, nylon-6,6, polyvinyl chloride, polyvinylidene chloride, etc.
  • a laminate film in which a sealant film is laminated on a print layer provided on a base film used in the field is mentioned.
  • the printed layer and the sealant film are usually laminated using a laminating adhesive.
  • the application of the adhesive for lamination and the lamination of the sealant film can be performed using a known dry lamination processing apparatus equipped with various coating apparatuses such as a roll coater, bar coater, and gravure coater.
  • the laminate film preferably has a laminate strength (peel strength between the base film and the sealant film) of 50 g/15 mm or more, more preferably 100 g/15 mm or more.
  • the lamination strength is measured by cutting the laminate film to a width of 15 mm after 3 days at 40° C., creating a sample piece, and performing T-type peeling with a peel tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). (dry laminate strength) is measured.
  • the sealant film side is center-folded toward the inside of the container, or the composite films are superimposed and the ends are thermally melted and crimped using a heat sealer or the like.
  • a heat sealer or the like can be used, and can be applied to packaging containers in the form of various heat seals such as three-side seal, four-side seal, envelope pasting, palm-to-palm pasting, and gusset pasting.
  • the mixture was cooled to 100° C., charged with 1128 parts by mass of water and 20.2 parts by mass of triethylamine to make it aqueous, and furthermore, 34.8 parts by mass of adipic acid dihydrazide was added to stop the reaction. to obtain an aqueous polyurethane resin varnish having a solid content of 30% and a resin acid value of 24 mgKOH/g.
  • Black pigment PBk7 (PRINTEX90, manufactured by Degussa) Yellow pigment: PY17 (Graphtol Yellow GG, manufactured by Clariant) Magenta pigment: PR146 (SYMULER Fast Red 4580, manufactured by DIC) Cyan pigment: PB15:3 (HELIOGEN BLUE D 7088, manufactured by BASF)
  • a resin varnish for pigment dispersion To this varnish, 40 parts by mass of titanium oxide (trade name: R-960, manufactured by DuPont) is further added, and after stirring and mixing, kneading is performed with a wet circulation mill to obtain a water-based white ink base (BASE-UR-W). was prepared.
  • ⁇ Comparative manufacturing example> ⁇ Production of water-based (meth)acrylate copolymer resin varnish> 20 parts by mass of an acrylic acid/n-butyl acrylate/benzyl methacrylate/styrene copolymer having a glass transition temperature of 40°C, a weight average molecular weight of 30,000, and an acid value of 185 mgKOH/g; A water-based (meth)acrylate copolymer resin varnish having a solid content of 20% was obtained by dissolving in a mixed solution of 77.5 parts by mass.
  • Neocryl A-1092 is a styrene-acrylic emulsion (solid content 48.5% by mass, manufactured by DSM, glass transition temperature 6 ° C.); Olfine E1010 is an acetylenic surfactant (solid content: 100% by mass, HLB: 13, manufactured by Nissin Kagaku Kogyo Co., Ltd.);
  • Each primer composition obtained above was printed on an OPP film (P2161, 25 ⁇ m, manufactured by Toyobo Co., Ltd.) using a 0.1 mm bar coater. After rubbing the printed primer coating film five times with a cotton swab moistened with water, the state of the coating film was visually observed. 0 was set as a pass. [Evaluation criteria] ⁇ : No peeling of coating film. ⁇ : The coating film was slightly peeled off. x: The coating film was largely peeled off, and the base material was exposed at the rubbed portion.
  • Each primer obtained above was applied to the treated surface of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., E-5102, thickness 12 ⁇ m, hereinafter referred to as PET film) that had been subjected to corona discharge treatment on one side.
  • PET film polyethylene terephthalate film
  • Each water-based inkjet ink composition thus prepared is packed in a cartridge of Epson's printer PX105 and printed, and then an isocyanate-based adhesive (Takeda Pharmaceutical Co., Ltd., Takenate A-385/Takelac A-50 ethyl acetate solution) is applied. Then, a CPP film was laminated using a dry laminator to obtain a laminated product.
  • Lupasol G20 is polyethyleneimine (solid content 50% by mass, molecular weight 1,300, manufactured by BASF); Lupasol G35 is polyethyleneimine (solid content 50% by mass, molecular weight 2,000, manufactured by BASF); Lupasol G100 is polyethyleneimine (solid content 50% by mass, molecular weight 5,000, manufactured by BASF);
  • Polyurethane-based resin is a polycarbonate-based polyurethane emulsion (Superflex 650, solid content 26% by mass, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.);
  • the polyolefin resin is a chlorinated polypropylene emulsion (Superchron E-604, solid content 40% by mass, manufactured by Nippon Paper Industries Co., Ltd.); Olfine E1010 is an acetylenic surfactant (solid content 100% by mass, HLB: 13, manufactured by Nissin Chemical Industry Co., Ltd.); BYK-331 indicates a silicone surfactant (active ingredient 98%,

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne un jeu d'encres qui comprend une composition d'encre pour jet d'encre à base d'eau comprenant un pigment, un dispersant pour le pigment, un solvant soluble dans l'eau et de l'eau et une composition d'apprêt comprenant un coagulant pour agglutiner la composition d'encre pour jet d'encre à base d'eau, une émulsion de résine et de l'eau, le dispersant étant une résine de polyuréthane, et le coagulant étant un composé ayant un squelette de polyéthylèneimine. Le jeu d'encres comprend : une composition d'apprêt apte à former une couche d'apprêt ayant une excellente résistance à l'eau ; et une composition d'encre pour jet d'encre à base d'eau apte à former une couche d'encre ayant d'excellentes propriétés d'adhérence, une excellente imprimabilité d'image solide et une excellente résistance au déteintage sur la couche d'apprêt.
PCT/JP2022/040720 2022-01-28 2022-10-31 Jeu d'encres et matière imprimée WO2023145181A1 (fr)

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JP2022011618A JP2023110271A (ja) 2022-01-28 2022-01-28 インクセット、及び印刷物
JP2022-011618 2022-01-28

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WO2023145181A1 true WO2023145181A1 (fr) 2023-08-03

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004512987A (ja) * 2000-10-30 2004-04-30 ヒューレット・パッカード・カンパニー インクジェット印刷画像の色及び安定性を改良したインクと下刷り液の組み合わせ
JP2004149806A (ja) * 2002-10-31 2004-05-27 Eastman Kodak Co インクジェットインク組成物
JP2010155442A (ja) * 2009-01-05 2010-07-15 Ricoh Co Ltd 前処理液を用いた画像形成方法、前処理液、インクジェット記録用インクとのセット、カートリッジ、インクジェット記録装置、画像形成物
JP2013510929A (ja) * 2009-11-10 2013-03-28 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 耐スミア性インクジェットインク
JP2017088839A (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
JP2019111770A (ja) * 2017-12-25 2019-07-11 東洋インキＳｃホールディングス株式会社 水性前処理液、水性記録液セット、及び印刷物の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004512987A (ja) * 2000-10-30 2004-04-30 ヒューレット・パッカード・カンパニー インクジェット印刷画像の色及び安定性を改良したインクと下刷り液の組み合わせ
JP2004149806A (ja) * 2002-10-31 2004-05-27 Eastman Kodak Co インクジェットインク組成物
JP2010155442A (ja) * 2009-01-05 2010-07-15 Ricoh Co Ltd 前処理液を用いた画像形成方法、前処理液、インクジェット記録用インクとのセット、カートリッジ、インクジェット記録装置、画像形成物
JP2013510929A (ja) * 2009-11-10 2013-03-28 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 耐スミア性インクジェットインク
JP2017088839A (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
JP2019111770A (ja) * 2017-12-25 2019-07-11 東洋インキＳｃホールディングス株式会社 水性前処理液、水性記録液セット、及び印刷物の製造方法

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