JP2018144493A - Ink composition for aqueous ink reception layer, aqueous ink set, aqueous ink printed matter and manufacturing method of aqueous ink printed matter, packaging bag and packaging container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous ink set capable of manufacturing a printed matter having an aqueous ink reception layer and an aqueous ink layer which are thin and stable on a recording medium simply and continuously.SOLUTION: There is provided an ink composition for aqueous ink reception layer containing a resin, a solvent and an acidic component which is at least one selected from an acid with a pKa value of 1 to 6 and an anhydride thereof or derivatives and salts of these compounds (a) and/or at least one of compounds (b) having an acid value of 1 mgKOH/g or more.SELECTED DRAWING: None

Description

  The present invention relates to an ink composition for a water-based ink receiving layer that enables printing of water-based ink on a recording medium.

  2. Description of the Related Art Conventionally, a recording medium provided with a water-based ink receiving layer that can be recorded on a substrate is known, and a printing medium using the recording medium has been proposed.

  In Patent Document 1, a porous resin stretched film obtained by stretching a thermoplastic resin film containing inorganic fine powders such as charcoal cal and titanium oxide is used as a support, and an ink receiving layer made of a nitrogen-containing cationic resin is formed thereon. An ink jet recording paper provided is described, and a paper that is quick to dry and does not cause transfer (so-called back-out or ghost) on the back side even when stacked is proposed.

  Patent Document 2 describes a water-based inkjet recording paper obtained by stretching a thermoplastic resin film containing an inorganic fine powder such as calcium carbonate. The ink dries quickly and transfers to the back surface even when stacked (so-called back-off). Proposals have been made that do not occur.

  Patent Document 3 describes a porous resin film containing a non-hydrophilic thermoplastic resin and a hydrophilic thermoplastic resin, has good water absorption, and has good ink drying properties even when the amount of ink discharged is large. Some have been proposed.

  The above-mentioned Patent Documents 1 to 3 require a film stretching step or become a white opaque film, so that their use is limited depending on the field where transparency is required.

  Patent Document 4 describes an inkjet recording paper having a PP resin film as a support, a primer coating layer of a nitrogen group-containing acrylic resin, and an ink receiving layer formed of a cationic resin and / or a hydrophilic polymer. It has been proposed to give a highly glossy image with water resistance, and this image has extremely good adhesion to the support.

  Patent Document 5 discloses a highly transparent easy-adhesive film in which an anchor layer containing an oxazoline group-modified resin as a component is provided on a polyolefin film provided with a modified layer by applying an ethylene copolymer coating on the surface and drying. It has been described, and it has been proposed to be excellent in transparency, excellent in gravure printing, letterpress printing, offset printing, flexographic printing, etc., or excellent in adhesion of a coating layer capable of recording information such as inkjet.

  In Patent Document 6, at least an anchor layer mainly composed of a urethane-vinyl chloride polymer and an image receiving layer mainly composed of a hydrophilic polymer and porous fine particles are laminated in this order on a base material. Films are described, and films having excellent dryness, excellent water resistance (dyeing property), and adhesion to film base materials such as PE and PP, which are usually difficult to adhere, have been proposed.

  In Patent Document 7, corona discharge machining is performed on a recording portion of a material, an anchor layer made of a polyamide resin is formed on the corona discharge machining portion, and an ink receiving layer made of a polyurethane resin is formed on the anchor layer. Ink jet recording materials are described, and materials with improved ink jet recording characteristics have been proposed for PE and PP materials.

  In Patent Documents 4 to 7, two layers of an anchor layer (also referred to as a primer layer) and an ink receiving layer are essential on a polyethylene (PE) or polypropylene (PP) substrate. Since it is a process, there are problems in terms of cost and productivity. Further, the ink receiving layer is as thick as 10 μm or more and is very difficult to form by printing. Application on polyethylene terephthalate (PET) substrates is difficult.

  Patent Document 8 includes, on a base material, an anchor coat layer including two types of resins, calcium carbonate, an acrylic resin, and a resin having a SP value difference of 0.5 or less from the base material, and polyvinyl alcohol. An ink jet recording sheet provided with an ink receiving layer is described, and a sheet having excellent adhesion strength between a base material-anchor coat layer and an anchor coat layer-an ink receiving layer has been proposed.

  Patent Document 9 describes an ink jet recording material in which an adhesive layer made of an acrylic-urethane copolymer is provided on a transparent substrate, and an ink receiving layer is provided thereon, and has high transparency and good color developability. Thus, it has been proposed that a clear print image can be obtained, cracks are not generated in the print image portion, the adhesion between the ink receiving layer and the substrate is good, and the ink receiving layer is hardly peeled off.

  While the above Patent Documents 8 to 9 are applicable to PET base materials, they are difficult to apply to PE or PP base materials, and there are two layers of an anchor layer (also referred to as an adhesive layer) and an ink receiving layer. Since the formation of the layers is a separate process for each, there is a problem in cost and productivity. In addition, the ink receiving layer is as thick as 25 μm and is very difficult to form by printing.

Patent Document 10 discloses an ink set for ink jet recording having a recording liquid containing at least a colorant and a polymerizable compound, and a treatment liquid containing at least one polysiloxane compound and substantially not containing a colorant. Even if the amount of the treatment liquid constituting the ink set is small, there is no white spot due to repelling, and there is no image disturbance due to landing interference between ink droplets or enlargement of ink droplets. An image forming apparatus has been proposed.
However, the amount of the processing solution is 6 g / m ² , and the amount less than that is unknown. The effect of repelling is inferior and image formation may be difficult.

  Further, Patent Document 11 discloses an ink jet recording having a recording liquid containing at least a colorant and a polymerizable compound, and a treatment liquid containing at least one glycol ether compound and substantially not containing a colorant. Ink sets have been described, and it has been proposed to form high-definition images with excellent image quality and no color mixing on any recording medium containing hydrophilic materials such as glass and corona-treated plastics. ing.

  Patent Document 12 includes a recording liquid for forming an image containing a polymerizable or crosslinkable material, and a processing liquid having a composition different from that of the recording liquid, and the viscosity of the processing liquid. An ink set for ink jet recording having a viscosity of 100 mPa · s or higher at 25 ° C. is described, and is included in the processing liquid as (I) a polymerizable or crosslinkable material, (II) a high boiling point organic solvent, (III) a polymer It has been proposed that at least one selected from the group consisting of:

In Patent Documents 10 to 12, it is essential to make the surface tension of the processing liquid smaller than the surface tension of the recording liquid, and adjustment is necessary. In addition, the coating amount of the treatment liquid is unknown or at least 6 g / m ^{2, which} is quite thick, and there is no description or suggestion about the formation of a thin film such as printing.

Patent Document 13 includes an ink containing a pigment, a water-soluble solvent, and water, and a liquid composition having an action of aggregating the ink, and one of the ink and the liquid composition is alkaline, and the other Inkjet recording ink sets are described, and those having excellent optical density, bleeding, intercolor bleeding, and drying time have been proposed.
However, the recording medium is not a resin film, and is a means for preventing bleeding on a paper medium and improving the color density, and is not satisfactory from the viewpoints of fixability and color reproduction (especially secondary color reproduction). .

  Patent Document 14 includes a maintenance liquid for inkjet recording containing a surfactant having a specific range of HLB values and a specific structure, and a water-soluble organic solvent having a specific structure having an alkyleneoxy group, an ink set for inkjet recording, Patent Document 15 discloses an image forming method and a maintenance method. Inkjet recording maintenance liquid, ink jet recording ink set, and image formation containing inorganic particles having a certain level of hardness and a compound having an HLB value in a specific range. A method has been proposed.

  Patent Documents 14 to 15 describe that the ink set includes an ink composition and a treatment liquid, and it is preferable to apply the ink composition after applying the treatment liquid on the recording medium. Yes. However, the treatment liquid has a high water-solubility that contains at least one hydrophilic structural unit derived from a sulfonic acid group or a salt thereof and at least one hydrophobic structural unit derived from a (meth) acrylic acid ester. Although a molecular compound is used, such a water-soluble polymer compound is not particularly excellent in performance as a binder such as binding property, adhesion to a recording medium, and film strength. In addition, the proportion of water-soluble polymer compounds in the treatment liquid and its solid content is small, and there is no particular additive to supplement the binder properties, so that it can absorb and retain paper and porous materials. If the material is superior to the above, the drying property, film forming property and durability may be remarkably deteriorated.

  Patent Document 16 discloses a maintenance liquid for inkjet recording having water, a water-soluble organic solvent having an ether bond, a basic compound, and an antioxidant, and having a pH of 6 to 9 at 25 ° C., and the use thereof. Inkjet recording ink set and image forming method, and Patent Document 17 discloses an inkjet recording maintenance liquid containing a predetermined amount of a water-soluble organic solvent having an SP value of a certain level or more, an inkjet recording ink set, and image formation. A method has been proposed.

  In Patent Documents 16 to 17, there are an ink composition and a treatment liquid (aggregation liquid) as an ink set, and it is preferable to apply the ink composition after applying the treatment liquid on the recording medium. Have been described. However, dimethylamine / epichlorohydrin copolymer is used as a cationic polymer in the processing liquid (aggregation liquid), but dimethylamine / epichlorohydrin copolymer has binding properties, adhesion to a recording medium, The binder performance such as film strength is not particularly excellent. In addition, since additives that supplement the binder properties are not included, drying, film-forming properties, and durability are significantly reduced except for materials that have excellent absorbency and retention, such as paper and porous materials. There is a risk that. Furthermore, such a cationic polymer is generally used as an aggregating agent in the form of an aqueous solution, and it is difficult to use it by dissolving it in an organic solvent.

Patent Document 18 describes an inkjet recording material having a base material and an ink receiving layer made of polyvinyl butyral formed on one of the substrates, and a clear printed image with good color developability is obtained. Those that do not crack are proposed.
However, since there is only one ink-receiving layer, layer formation is easy, but the ink-receiving layer is as thick as 25 μm and is very difficult to form by printing.

Patent Document 19 describes a printing ink for forming an ink-receiving layer for ink-jet recording, which contains a magnesium aluminate metasilicate fine powder and a cationic polymer, and has a concealing property, drying property, coloring property, fixing property, and water resistance. Those capable of forming an excellent ink receiving layer have been proposed.
However, since there is only one ink-receiving layer, layer formation is easy as in Patent Document 18, but the ink-receiving layer is as thick as 25 μm and is very difficult to form by printing. Further, since magnesium fine powder is used as a solid component, yellowing may occur in a portion in contact with air.

  Therefore, it is possible to easily and continuously produce an ink composition for a water-based ink receiving layer that can form a stable water-based ink receiving layer with a thin film, and a printed material having the water-based ink layer on the receiving layer, regardless of the recording medium. A water-based ink set was desired.

JP-A-10-181188 JP-A-10-217604 JP 2001-181424 A Japanese Patent Laid-Open No. 10-119428 JP 2001-150612 A Japanese Patent Laid-Open No. 2002-103802 JP 2011-178044 A JP 2004-181859 A JP 2007-130780 A JP 2007-313839 A JP 2007-314734 A JP 2008-137156 A JP 2004-10633 A Japanese Patent No. 5823613 JP 2014-65845 A JP 2011-156818 A JP 2013-10267 A JP 2007-130776 A JP 2008-213345 A

  Accordingly, an object of the present invention is to provide a water-based ink set that allows a printed matter having a thin and stable water-based ink receiving layer and a water-based ink layer to be easily and continuously produced on a recording medium.

  As a result of intensive studies, the present inventors have found that an aqueous ink-receiving layer ink composition containing a resin, a solvent and a specific acidic component, and an aqueous ink recording containing a cation neutralized product of an anionic functional group resin. The present invention has been completed by finding that the above object can be achieved by a water-based ink set containing a material.

That is, the present invention
(1) a resin, a solvent, an acid having a pKa value of 1 to 6 and its anhydride or a derivative of these compounds and a salt (a), and / or a compound having an acid value of 1 mgKOH / g or more An ink composition for a water-based ink receiving layer containing an acidic component which is at least one of (b),
(2) The ink composition for a water-based ink-receiving layer according to (1), wherein the resin is a resin that does not destabilize the acidic component;
(3) the water-based ink receiving layer ink composition;
A water-based ink recording material containing a cation neutralized product of a resin having an anionic functional group;
A water-based ink set characterized by containing
(4) A water-based ink print formed using the water-based ink set according to (3),
(5) A method for producing a water-based ink print using the water-based ink set according to (3),
A water-based ink printed matter comprising: a step of forming a water-based ink receiving layer comprising an ink composition for a water-based ink receptive layer on a recording medium; and a step of forming a water-based ink layer comprising a water-based ink recording material. Manufacturing method,
(6) The step of forming the water-based ink receiving layer and the step of forming the water-based ink layer include a silk screen printing method, a gravure printing method, an offset printing method, a flexographic printing method, a roller coater method, a brush coating method, Spray method, knife jet coater method, ink jet printing method, pad printing method, gravure offset printing method, die coater method, bar coater method, spin coater method, comma coater method, impregnation coater method, dispenser method, metal mask method The method for producing a water-based ink printed material according to (6), comprising at least one;
(7) A packaging bag formed using the water-based ink printed matter according to (4),
(8) A packaging container formed using the water-based ink printed matter according to (4),
It is about.

  ADVANTAGE OF THE INVENTION According to this invention, the ink composition for water-based ink receiving layers which can manufacture easily and continuously the printed matter which has the water-based ink receiving layer and water-based ink layer which were stabilized by the thin film on the recording medium can be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. The present embodiment is merely one form for carrying out the present invention, and the present invention is not limited by the present embodiment, and various modifications and embodiments are possible without departing from the gist of the present invention. Is possible.

  The water-based ink receiving layer ink composition of the present invention (hereinafter also simply referred to as “receiving layer ink”) preferably contains a resin, a solvent, and a specific acidic component.

The acidic component is preferably (a) at least one selected from acids having 1 to 6 pKa values and anhydrides thereof, derivatives of these compounds, and salts, and those having 1 to 5 are more preferable. When the pKa value is smaller than 1, it causes deterioration of the receiving layer ink storage container and coating device. Moreover, since it is highly harmful to living things, it is not preferable in terms of environmental load and safety and health. When the pKa value is larger than 6, it is necessary to add a large amount of an acidic component, which causes a decrease in coating suitability and coating film performance. Even if it is a compound which does not have a general acidic group, the acidic substance whose pKa value is in the said range is also included.
The acidic component is preferably (b) at least one compound having an acid value of 1 mgKOH / g or more, more preferably 1 to 1000 mgKOH / g, and still more preferably 100 to 800 mgKOH / g. . When the acid value is less than 1 mgKOH / g, it is necessary to add a large amount of an acidic component, which causes a decrease in coating suitability and coating film performance. If the acid value is large, it causes deterioration of the receiving layer ink storage container and coating device.
The acidic component only needs to contain at least one of (a) and (b), and (a) and (b) may be used in combination.
The pKa value represents the acid dissociation index pKa in an aqueous solution. The acid dissociation index pKa is a logarithmic value of the reciprocal of the acid dissociation constant, and is a commercially available potentiometric titrator (for example, “COM-980Win” manufactured by Hiranuma Sangyo Co., Ltd. or “AT-510” manufactured by Kyoto Electronics Industry Co., Ltd.). And the like, and acid dissociation constants described in documents such as Chemistry Handbook Fundamentals II (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.) can be used.
The acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the resin, and can be measured according to JIS K0070.

  Specific examples of the acidic component include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hypochlorous acid, chloric acid, perchloric acid, hydroiodic acid, hypoiodic acid, iodic acid, periodic acid, and hydrogen bromide. Acids, hypobromite, bromate, perbromate, sulfurous acid, persulfuric acid, carbonic acid, phosphorous acid, hypophosphorous acid and other inorganic acids, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, malein Acid, glyceric acid, methylmalonic acid, dimethylmalonic acid, propylmalonic acid, succinic acid, mesotartaric acid, glutaric acid, β-methylglutaric acid, β, β-dimethylglutaric acid, β-ethylglutaric acid, β, β- Diethyl glutaric acid, β-propyl glutaric acid, β, β-methylpropyl glutaric acid, pimelic acid, suberic acid, sebacic acid, maleic acid, fumaric acid, glutaconic acid, 1,1-cyclobutanedicarboxylic acid, 1,3 Cyclobutane dicarboxylic acid, 1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4- Cyclohexanedicarboxylic acid, 1,2-cyclohexenedicarboxylic acid, benzoic acid, 2,3-dihydroxybenzoic acid, 3,4-dimethylbenzoic acid, 3,4-dimethoxybenzoic acid, 3,5-dimethoxybenzoic acid, p-toluyl Acid, 2-hydroxy-p-toluic acid, 2-hydroxy-m-toluic acid, 2-hydroxy-o-toluic acid, mandelic acid, gallic acid, phthalic acid, isophthalic acid, terephthalic acid, meldrum acid, ascorbic acid, Uric acid, succinic anhydride, glutaric anhydride, maleic anhydride, cyclohex Dicarboxylic anhydride, cyclohexanedicarboxylic anhydride, phthalic anhydride, citric acid, isocitric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid Examples thereof include acids, coumaric acid, thiophenecarboxylic acid, nicotinic acid, benzylic acid, o-sulfobenzimide or derivatives and salts of these compounds. Further, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl acid phosphate Monomers such as fetus, β-carboxyethyl (meth) acrylate, acid-modified epoxy (meth) acrylate and oligomers or polymers thereof, shellacs, rosin-modified maleic resin, rosin-modified phenol resin, cellulose acetate, cellulose acetylpropionate , Cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, vinyl halide resin (eg, vinyl chloride resin, fluorine-containing vinyl resin, etc.), polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polystyrene resin, acrylic resin, Kurylstyrene copolymer, polyacrylic ester, polyester resin, polyvinylidene chloride resin, ketone resin, ethylene vinyl acetate resin, polyurethane resin, polyamide resin, nitrocellulose resin, chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated ethylene -Vinyl acetate resin, polybutyral resin, rosin resin, styrene maleic acid resin, casein, alkyd resin, acrylic emulsion, urethane emulsion, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, polyester (meth) acrylate resin, epoxy ( (Meth) acrylate resin, urethane (meth) acrylate resin, polyether (meth) acrylate resin, (meth) acryl polyol resin, diallyl phthalate resin, Examples thereof include resins such as phenol resin, melamine resin, epoxy resin, urea resin, unsaturated polyester resin, and silicon resin, fats and oils, fatty acids, various surfactants, and various dispersants. Of these, malonic acid, citric acid, isocitric acid, orthophosphoric acid, benzylic acid, benzoic acid, o-sulfobenzimide and the like are more preferable because they are within the range of the pKa value. Further, β-carboxyethyl (meth) acrylate, acid-modified phenol epoxy (meth) acrylate and the like are more preferable because they are within the range of the acid value. These can be used alone or in admixture of two or more.

  The acidic component is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the resin. When the amount is less than 1 part by mass, the acidity of the water-based ink receiving layer is insufficient, and this causes a decrease in color developability and bleeding due to poor fixing of the water-based ink. When the amount is more than 30 parts by mass, the mechanical strength of the water-based ink receiving layer is lowered, which causes a decrease in stability over time, durability, transportability, and adhesion.

  Examples of the resin include a thermoplastic resin, a thermosetting resin, an active energy ray curable resin, and the like, and a resin that does not destabilize the acidic component is more preferable.

  The thermoplastic resin is a silk screen printing method, gravure printing method, offset printing method, flexographic printing method, roller coater method, brush coating method, spray method, knife jet coater method, inkjet printing method, pad printing method, gravure offset printing. Any resin can be used as long as it is applicable to a known printing method such as a method, a die coater method, a bar coater method, a spin coater method, a comma coater method, an impregnation coater method, a dispenser method, or a metal mask method. Among these, a resin that can be applied to a gravure printing method, an offset printing method, a flexographic printing method, and an inkjet printing method is more preferable, and a resin that can be applied to a gravure printing method and an inkjet printing method is more preferable.

  Specific examples of the thermoplastic resin include shellacs, rosin-modified maleic resin, rosin-modified phenol resin, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, and vinyl halide resin. (For example, vinyl chloride resin, fluorine-containing vinyl resin, etc.), polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polystyrene resin, acrylic resin, acrylic styrene copolymer, polyacrylic ester, polyester resin, poly Vinylidene chloride resin, ketone resin, ethylene vinyl acetate resin, polyurethane resin, polyamide resin, nitrocellulose resin, chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated ethylene-vinyl acetate resin, polybutyral resin, rosin tree , Styrene-maleic acid resins, casein, alkyd resin, acrylic emulsion, urethane emulsion, polyvinyl alcohol resins, ethylene - vinyl alcohol resins. Of these, polyurethane resin, nitrocellulose resin, polyamide resin, chlorinated polypropylene resin, vinyl chloride / vinyl acetate copolymer and the like are more preferable. These can be used alone or in admixture of two or more.

  Specific examples of the thermosetting resin include polyester (meth) acrylate resin, epoxy (meth) acrylate resin, urethane (meth) acrylate resin, polyether (meth) acrylate resin, (meth) acrylic polyol resin, diallyl phthalate resin. , Phenol resin, melamine resin, epoxy resin, urea resin, unsaturated polyester resin, silicon resin, urethane resin and the like. Of these, (meth) acryl polyol resin and the like are more preferable. These can be used alone or in admixture of two or more.

Specific examples of the active energy ray-curable resin preferably include an ethylenically unsaturated compound that is a monomer or oligomer that is polymerized by irradiation with active energy rays, and includes a (meth) acryl group. More preferably, it is a compound (hereinafter also referred to as (meth) acrylate). It may be a monofunctional (meth) acrylate or a polyfunctional (meth) acrylate. Further, urethane (meth) acrylate, polyester (meth) acrylate, and epoxidized vegetable oil (meth) acrylate may be used. Specific examples include phenol EO-modified (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolprohan triacrylate, trimethylolpropane PO-modified triacrylate, trimethylolpropane EO-modified tri Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2- (meth) acryloyloxyethyl succinate Acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- Meth) acryloyloxyethyl acid phosphate, beta-carboxyethyl (meth) acrylate, acid-modified phenol epoxy (meth) acrylate. Of these, β-carboxyethyl (meth) acrylate, acid-modified phenol epoxy (meth) acrylate, and the like are more preferable. These can be used alone or in admixture of two or more.
The active energy ray in the present invention represents energy required for the starting material of the curing reaction to be excited from the ground state to the transition state, and the active energy ray in the present invention refers to ultraviolet rays or electron beams.

  In the case of the thermoplastic resin, the receiving layer ink preferably has a solid content of 1 to 70% by mass, more preferably 2 to 65% by mass, and further preferably 3 to 60% by mass. preferable. When the amount is less than 1% by mass, sufficient adhesion cannot be obtained. When the amount is more than 70% by mass, the solid content is too high, the viscosity becomes high, and the coating is difficult.

  In the case of the thermosetting resin, the solid content in the receiving layer ink is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and 3 to 60% by mass. Further preferred. When the amount is less than 1% by mass, sufficient adhesion cannot be obtained. When the amount is more than 70% by mass, the solid content is too high, the viscosity becomes high, and the coating is difficult.

In the case of the active energy ray-curable resin, it is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and more preferably 10 to 85% by mass in the receiving layer ink. More preferably. When the amount is less than 1% by mass, sufficient adhesion cannot be obtained. When the amount is more than 95% by mass, the acidic component and the polymerization initiator cannot be sufficiently contained, which causes poor fixing of the water-based ink and a decrease in curability.
When making the said active energy ray curable resin into an ultraviolet curable composition, it is preferable to contain a polymerization initiator. In addition, when setting it as an electron beam curable composition, it is not necessary to mix | blend a polymerization initiator.

  The ink composition for a water-based ink receiving layer preferably contains a solvent. Examples of the solvent include various solvents, the polymerizable (meth) acrylate monomer, and water for imparting appropriate fluidity during printing and adjusting the viscosity.

  In the case of the thermoplastic resin, any resin that dissolves or disperses the resin in the solvent may be used, and various organic solvents or water may be used.

  Examples of organic solvents usually used in the gravure printing method include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, methanol, ethanol, and isopropyl alcohol. Alcohol solvents such as normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, tert-butanol, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-acetate Ester solvents such as butyl, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Examples thereof include glycol ether solvents such as ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and esterified products thereof. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene Such as glycol monoethyl ether acetate. These can be used alone or in admixture of two or more.

  Examples of the solvent used in the inkjet printing method include a water-soluble organic solvent or water. Examples of water-soluble organic solvents include glycerin, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 2-butene- 1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 1 , 4-butanediol, 3-methyl-1,3-butanediol, 4-methyl-1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, 1,2,4 -Butanetriol, 2-ethyl-2-methyl 1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2, Polyhydric alcohols such as 4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1,2-diol, glucose, mannose, fructose, ribose, xylose, Sugars such as arabinose, galactose, aldonic acid, glucitol, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, so-called solid wetting agents such as sugar alcohols, hyaluronic acids, ureas, ethanol, methanol, butanol, propanol, 1 to 4 carbon atoms such as isopropanol Kill alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol Monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Lenglycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono Glycol ethers such as isopropyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, sulfolane Etc. These can be used alone or in admixture of two or more.

  Examples of the solvent used in the offset printing method include petroleum solvents and vegetable oils. Petroleum solvents include aroma-free solvents, normal paraffin solvents, isoparaffin solvents, machine oil, cylinder oil, and vegetable oils such as soybean oil, linseed oil, rapeseed oil, coconut oil, olive oil, and tung oil. Processed ones, fatty acid esters derived from these vegetable oils, vinylidene olefins and the like can be mentioned.

  The solvent is preferably 200 to 800 parts by mass and more preferably 30 to 700 parts by mass with respect to 100 parts by mass of the resin. When the amount is less than 200 parts by mass, sufficient printability cannot be obtained. When the amount is more than 800 parts by mass, the solid content decreases and the adhesion to the recording medium is lowered.

  Ink compositions for water-based ink receptive layers include colorants, inorganic fillers, organic fillers, antifoaming agents, for the purpose of improving required physical properties such as design properties, applications, hues, ink stability, and printability. Leveling agent, antiblocking agent, wax, pigment dispersant, antistatic agent, slip agent, plasticizer, tackifier, antioxidant, polymerization initiator, photosensitizer, polymerization inhibitor, surfactant, UV absorber Agents, surface conditioners, antifoaming agents, pH adjusters, charge imparting agents, bactericides, deodorants, wetting agents, antiskinning agents, metal chelating agents, and the like can also be contained. Any known and commonly used ones can be selected as long as the printability and the properties of the receiving layer ink are not impaired.

  The color material can contain a pigment, a dye, or a mixture thereof. Examples of the pigment include titanium oxide, petal, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, pearl, aluminum, carbon black and other inorganic pigments, phthalocyanine-based, insoluble azo-based, condensed azo Organic pigments such as organic, dioxazine, anthraquinone, quinacridone, perylene, perinone, and thioindigo, and various other fluorescent pigments, metal powder pigments, extender pigments, and the like. These pigments may be used alone or in combination of two or more. As the dye, those which are dissolved or dispersed in a solvent are preferable, and one kind or a combination of two or more kinds may be used. Among these, it is preferable to use a pigment from the viewpoint of durability. Since it can contain a coloring material, it is very useful in terms of color variation and design.

  The ink composition for a water-based ink receiving layer is preferably provided on the recording medium so as to form an ink receiving layer having a thickness of 0.01 to 10 μm. When the film thickness is smaller than 0.01 μm, the water-based ink receptive effect is hardly exhibited, and when the film thickness is larger than 10 μm, it is difficult to provide an ink receptive layer, and blocking is caused.

  The water-based ink set of the present invention preferably includes the water-based ink receiving layer ink composition and a water-based ink recording material.

  The water-based ink recording material preferably contains a cation neutralized product of a resin having an anionic functional group. More preferably, the anionic functional group is selected from a phosphoric acid group, a polyphosphoric acid group, a sulfuric acid group, a sulfo group, a nitric acid group, a carbonic acid group, a carboxylic acid group and a derivative thereof, or a salt thereof. A carboxylic acid group is more preferable, and a carboxylic acid group is further preferable. These may be used alone or in combination of two or more.

  Examples of resins having an anionic functional group include styrene / butadiene polymers, acrylonitrile / butadiene polymers, methyl methacrylate / butadiene polymers, polychloroprene, vinylpyridine copolymers, polyisoprene, butyl rubber, polysulfide. Rubber, polyurethane resin, polybutene, acrylic resin, vinyl chloride polymer, vinyl acetate polymer, vinylidene chloride copolymer, polyethylene resin, vinyl acetate / ethylene copolymer emulsion, latex, alkyd resin, acrylic Examples thereof include emulsions or colloidal dispersions such as fluorinated alkyd resins, epoxidized alkyd resins, polyester resins, styrene-acrylic resins, epoxy resins, and fluorine resins. These can be used alone or in admixture of two or more.

  Examples of the cation that neutralizes the resin having an anionic functional group include alkali metal ions such as lithium, sodium and potassium, alkaline earth metal ions such as calcium and magnesium, iron, zinc, manganese, nickel, copper and cobalt. And metal ions such as transition metal ions, and ammonium ions such as ammonium, alkylammonium, dialkylammonium, trialkylammonium, and tetraalkylammonium. Of these, monovalent cations are preferable, and sodium ions, potassium ions, and ammonium ions are more preferable.

  The resin having an anionic functional group is neutralized with the cation to form a salt. By forming the salt, hydrophilicity is improved and an aqueous dispersion is formed.

  The cation neutralized product of the resin having an anionic functional group is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and more preferably 3 to 30% by solid content in the water-based ink recording material. More preferably, it is mass%. If the amount is less than 1% by mass, good adhesion to the ink receiving layer cannot be obtained. If the amount is more than 50% by mass, the solid content is too high, the viscosity becomes high, and coating is difficult.

  The water-based ink recording material preferably contains a water-soluble organic solvent. Any water-soluble organic solvent may be used as long as it is compatible with the cation neutralized product of the resin having an anionic functional group. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1 , 3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2 , 6-hexanetriol, trimethylolpropane, polyethylene glycol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 5-hexene-1 , 2-diol, 1,2-oct Diol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 3,3-dimethyl -1,2-butanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-hexanediol, 1,2-pentanediol, 4- Alkanediols (polyhydric alcohols) such as methyl-1,2-pentanediol, C1-C4 alkyl alcohols such as ethanol, methanol, butanol, propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol monobutyl ether, ethylene glycol Methyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert- Butyl ether, butyl carbitol, diethylene glycol mono-tert-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol No-tert-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether , Glycol ethers such as tripropylene glycol methyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbitol, sorbitan, acetin, diacetin , Triacetin, sulfolane and the like. Of these, pyrrolidones such as 2-pyrrolidone, alkylene glycols such as ethyl carbitol, and alkylene glycol monoalkyl ethers such as tripropylene glycol methyl ether are preferable. The water-soluble organic solvent is preferably 20 to 800 parts by mass and more preferably 30 to 700 parts by mass with respect to 100 parts by mass of the cation neutralized product of the resin having an anionic functional group.

  The water-based ink recording material preferably contains water in addition to the water-soluble organic solvent. Although there is no restriction | limiting in particular in the quantity of water, It is preferable that water is 50-800 mass parts with respect to 100 mass parts of cation neutralization products of resin which has an anionic functional group, and it is 100-700 mass parts. Is more preferable.

  For water-based ink recording materials, coloring materials, inorganic fillers, organic fillers, antifoaming agents, leveling agents, blocking, etc., for the purpose of improving the required physical properties such as design, usage, hue, ink stability, and printability. Inhibitors, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, antioxidants, polymerization initiators, photosensitizers, polymerization inhibitors, surfactants, UV absorbers, surface conditioning Agents, antifoaming agents, pH adjusting agents, charge imparting agents, bactericides, deodorants, wetting agents, antiskinning agents, metal chelating agents, and the like can also be contained. Any known and commonly used one can be appropriately selected within the range that does not impair the printability and the characteristics of the water-based ink.

  The color material can contain a pigment, a dye, or a mixture thereof. Examples of the pigment include titanium oxide, petal, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, pearl, aluminum, carbon black and other inorganic pigments, phthalocyanine-based, insoluble azo-based, condensed azo Organic pigments such as organic, dioxazine, anthraquinone, quinacridone, perylene, perinone, and thioindigo, and various other fluorescent pigments, metal powder pigments, extender pigments, and the like. These pigments may be used alone or in combination of two or more. The dye is preferably dissolved or dispersed in a water-soluble organic solvent, and may be used alone or in combination of two or more. Among these, it is preferable to use a pigment from the viewpoint of durability. Since it can contain a coloring material, it is very useful in terms of color variation and design.

  A commercially available water-based ink recording material can also be used. The type of water-based ink can be selected as appropriate depending on the required physical properties such as design, use, and hue, and the printing environment. For example, gravure water-based ink, flexo water-based ink, water-based inkjet ink, water-based varnish, water-based paint and the like can be mentioned, and those prepared by a known method can be preferably used.

  The water-based ink print of the present invention is preferably formed using the water-based ink set. That is, it is formed by a method including a step of forming a water-based ink receiving layer comprising an ink composition for a water-based ink receiving layer on a recording medium and a step of forming a water-based ink layer comprising a water-based ink recording material.

  The step of forming the water-based ink receiving layer and the step of forming the water-based ink layer include a silk screen printing method, a gravure printing method, an offset printing method, a flexographic printing method, a roller coater method, a brush coating method, a spray method, At least one selected from knife jet coater method, inkjet printing method, pad printing method, gravure offset printing method, die coater method, bar coater method, spin coater method, comma coater method, impregnation coater method, dispenser method, and metal mask method It is preferable to contain.

The step of forming the water-based ink receiving layer and the step of forming the water-based ink layer may be the same printing method or a combination of different printing methods. For example, if the step of forming the water-based ink receiving layer is a gravure printing method, the step of forming the water-based ink layer may be the same gravure printing method or an inkjet printing method. Moreover, if the process of forming a water-based ink receiving layer is an inkjet printing system using an active energy ray-curable inkjet ink, the process of forming a water-based ink receiving layer is also preferably an inkjet printing system.
In this case, since the water-based ink receiving layer is cured, the molecular weight and the crosslinking density are increased, and the acceptability of the water-based ink on the water-based ink receiving layer may be decreased. Although it is preferable to cure after forming the water-based ink layer, the water-based ink layer may be formed after the water-based ink receiving layer is formed and then cured. Accordingly, it is possible to easily and continuously form a water-based ink print having a thin and stable water-based ink receiving layer and a water-based ink layer on a recording medium.
Further, the formed water-based ink receiving layer is stable. This is because, for example, a gravure printing method can form a water-based ink-receiving layer on a film-like recording medium, and then it can be normally wound and stored, and a water-based ink layer can be separately formed by an ink-jet printing method. Therefore, versatility is very high.

  A printing ink layer or an anchor coat layer may be included between the water-based ink receiving layer and the recording medium. The formation of the printing ink layer and the anchor coat layer is more preferably a gravure printing method using a multicolor gravure printing machine. In addition, a heat seal layer or overcoat layer may be provided on the water-based ink layer, and an overcoat film or the like is laminated via an anchor coat layer or an adhesive layer, or a thermoplastic resin is dry laminated or non-solvent laminated. Alternatively, lamination may be performed by extrusion lamination or the like. That is, another layer may be formed between the water-based ink receiving layer and the recording medium or on the water-based ink layer as long as the water-based ink receiving layer and the water-based ink layer can be formed in contact with each other.

  The recording medium used in the water-based ink set of the present invention can be a plastic film, an aluminum foil and a synthetic paper on which a synthetic resin is laminated, or a paper substrate, a material other than paper (metal) , Glass, wood, leather), and at least one selected from molded articles having a thickness other than a film or sheet shape.

  The film base material may be a laminate of thermoplastic resin or the like by a method such as dry lamination, non-solvent lamination or extrusion lamination, or a method of bonding through an adhesive or the like, or an appropriate combination of these It may be. Moreover, the laminated body which provided heat sealability can also be used as a paper base material. Examples of a method for imparting heat sealability include bonding of known sealant films, resin coating by extrusion lamination, and the like. A layer imparted with heat sealability by these methods is also referred to as a heat seal layer. Although there will be no restriction | limiting in particular if the thickness of a film base material is in the range which does not have trouble in printability, winding-up property, etc., 5-300 micrometers is preferable and 6-250 micrometers is more preferable.

  The paper substrate can be used as long as it can be printed. Examples of the paper include non-coated paper, non-coated paper, coated paper, art paper, milk carton paper, cardboard paper, coated cardboard paper, Manila cardboard paper, and kent paper.

  Materials other than the paper can be used as long as they can be applied. A metal base material, a glass base material, wood, a leather material etc. are mentioned. For example, examples of the metal substrate include iron plates, steel plates, plated steel plates, copper-zinc alloys, aluminum, titanium, magnesium alloys, and stainless steel plates.

  A molded product having a thickness other than the film or sheet shape can be used as long as it can be applied. Examples thereof include resin molded products, metal molded products, glass molded products, wood products, and molded leather.

  The water-based ink printed matter of the present invention is for packaging, food preservation, agriculture, civil engineering, fishery, automotive interior and exterior use, marine use, daily necessities, building materials interior and exterior use, housing equipment use, medical / medical equipment use, medicine It can be used for household appliances, furniture, furniture, stationery and office supplies, sales promotion, commercial, electrical and electronics industries, clothing, and decorations.

  The packaging bag of the present invention is preferably formed using the water-based ink printed matter. Packing bag forms include two-side seals, three-side seals, four-side seals, pillow seals, standing pouches, envelope stickers, gussets, fusing seals, tubes, caramel packaging, overholds, fin seals, manju packaging, twists, rockets, etc. It can be preferably used as a form.

  The packaging container of the present invention is preferably formed using the water-based ink printed matter. It can be preferably used in the form of food packaging containers, trays, cups, dishes, bottles, tetra packs, gable tops, bricks, carton cans, cake boxes and the like.

  In addition, as a label, it can be preferably used in the form of a label attached to a glass bottle, a metal can, a plastic bottle, another container, or a body-wound label.

  Moreover, as a lid | cover material, it can use preferably as a form of the lid | cover material used as a sealed container by closely_contact | adhering with bottomed cylindrical containers, such as a plastic container for foodstuffs and daily necessities, a glass container, a metal can, and a paper can. The close contact with the container may be performed through human hand, but a machine such as an automatic sealing device may be used. These may be selected as appropriate according to the type, form, size, quantity, container to be sealed, equipment, environment, etc., and sticking or bonding with heat seal (hot pressure seal), face seal, adhesive, etc. It may be performed by a method using such as. Moreover, it can use preferably as forms, such as a cover body for closing the upper part of a paper container by fitting etc. Moreover, it can be preferably used in the form of wrapping contents such as burger wrap for foods, or in the form of wrapping paper, packaging sheet or packaging film as daily necessities, decorative paper for building materials, and the like.

  The ink composition for a water-based ink receiving layer can be produced by a known method by uniformly dissolving or dispersing a resin, an acidic component, a solvent, a pigment, various additives, and the like. Dissolver or disperser is various agitators or dispersers such as dissolver, roll mill, ball mill, bead mill, sand mill, attritor, paint shaker, agitator, Henschel mixer, colloid mill, pearl mill, ultrasonic homogenizer, wet jet mill, kneader, homomixer, etc. You can use the machine. These devices may be used alone or in combination of two or more. When air bubbles and coarse particles are contained in each composition, it is preferable to remove them using a known filter or centrifuge in order to reduce printability and print quality.

  The viscosity of the ink composition for water-based ink receiving layer is not particularly limited as long as it does not interfere with printing. Considering the production suitability and handling of each composition used in gravure printing and flexographic printing, it is preferably 10 to 1,000 mPa · s at 25 ° C. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone plate viscometer. Considering the production suitability and handling of each composition used in inkjet printing, it is preferably 1 to 20 mPa · s at 25 ° C. In this case, it can be measured using a commercially available viscometer such as a cone plate viscometer.

  The ink composition for water-based ink-receiving layer used in gravure printing and flexographic printing can be applied as it is, but Zaan Cup # 3 (manufactured by Kogai Co., Ltd.) depending on the coating conditions and coating effect. Thus, it can be used by adjusting to a desired viscosity by diluting with a diluent solvent. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C.

  The dilution solvent may be any one as long as it can be used after adjusting the viscosity of the ink composition for a water-based ink receiving layer, and examples thereof include organic solvents, and commercially available ones can also be used. Examples of commercially available products include WA735, TA52, PU515, SL9155, CN104, AC372, PP575, and PA463 (all manufactured by Tokyo Ink Co., Ltd.).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these. In addition, the part in an Example and a comparative example represents a mass part, and% represents the mass%.

[Preparation of ink composition for water-based ink receiving layer]
Receiving layer ink 1 (Example 1)
238 parts of urethane resin varnish (solid content 30%) were charged with 190 parts of titanium oxide, 98 parts of ethyl acetate, 98 parts of n-propyl acetate and 90 parts of isopropyl alcohol, and kneaded with a paint shaker to prepare a mill base. Add 95 parts of chlorinated polyolefin resin varnish (solid content 30%), 95 parts of citric acid solution (mixed solution of citric acid: toluene: ethyl acetate: isopropyl alcohol = 1: 3: 3: 3), 48 parts of polyethylene wax, Mixing was performed to prepare a mixed solution, which was added to the mill base and mixed to prepare a receiving layer ink 1. Similarly, according to the composition of Tables 1 to 3, the receiving layer inks of Examples 2 to 16 and Comparative Examples 1 to 6 were prepared. Examples 1 to 12 and Comparative Examples 1 to 5 are examples of thermoplastic resins, Example 13 is an example of a thermosetting resin, and Examples 14 to 16 and Comparative Example 6 are examples of an active energy ray curable resin.

[Production of water-based ink recording material]
Water-based ink 1 (Production Example 1)
167 parts of an aqueous dispersion of styrene acrylic acid copolymer neutralized ammonia (solid content 30%), 167 parts of quinacridone magenta, DISPERBYK-2012 (dispersant, manufactured by Big Chemie Japan Co., Ltd.), 167 parts, butyl carbitol 330 parts and 330 parts of ion-exchanged water were charged and kneaded with a paint shaker to prepare a mill base. 1. Styrene acrylic acid copolymer neutralized ammonia aqueous dispersion (solid content 30%) 167 parts, butyl carbitol 330 parts, ion-exchanged water 170 parts, BYK-307 (by Big Chemie Japan Co., Ltd.) 5 parts were added and mixed to prepare a mixed solution, which was added to the mill base and mixed to prepare water-based ink 1. Similarly, the water-based ink of Production Example 2 was produced according to the formulation shown in Table 4. The water-based ink 1 is an example of a water-based inkjet ink, and the water-based ink 2 is an example of a water-based gravure ink.

The materials used are as follows.
Urethane resin varnish: TA24-507C (solid content 30%, manufactured by Hitachi Chemical Co., Ltd.)
Nitrocellulose resin varnish: DHX5-10 (solid content 70%) prepared with ethyl acetate (solid content 30%, manufactured by Nobel NC)
Polyamide resin varnish: Rheamide S-8200 prepared with a mixed solvent of methylcyclohexanone / ethyl acetate = 50/50 (solid content 30%, manufactured by Kao Corporation)
Vinyl chloride-vinyl acetate copolymer resin varnish: Kane vinyl HM515 was prepared with a mixed solvent of methylcyclohexanone / ethyl acetate = 50/50 (solid content 30%, manufactured by Kaneka Corporation)
Acrylic polyol resin varnish: Acridick WZU-591 prepared with ethyl acetate (solid content 30%, manufactured by DIC Corporation)
Isocyanate-based curing agent solution: Takenate D-120N (solid content 75%) prepared with ethyl acetate (solid content 30%, manufactured by Mitsui Chemicals, Inc.)
Chlorinated polyolefin resin varnish: Super Clone 803M (solid content 30%, manufactured by Nippon Paper Industries Co., Ltd.)
Ditrimethylolpropane tetraacrylate: Aronix M-408 (manufactured by Toagosei Co., Ltd.)
Irgacure 819: polymerization initiator (manufactured by BASF)
Titanium oxide: TITON R-45M (manufactured by Sakai Chemical Co., Ltd.)
Polyethylene wax: (CERAFLOUR 925, manufactured by Big Chemie Japan)
Aqueous dispersion of styrene acrylic acid copolymer neutralized product: Joncrill HPD-96J, solid content 30%, DISPERBYK-2012 manufactured by BASF Corporation: Wet dispersant, BYK-Japan Co., Ltd. BYK-307: Polyether Modified polydimethylsiloxane, manufactured by Big Chemie Japan Co., Ltd. Kinacridone magenta: FASTOGEN Super Magenta RGT (manufactured by DIC Corporation) Citric acid: pKa ₁ = 2.87
Saccharin: pKa ₁ = 1.60
Benzoic acid: pKa ₁ = 4.20
Isocitric acid: pKa ₁ = 3.40
DL-malic acid: pKa ₁ = 3.24
Malonic acid: pKa ₁ = 2.65
Phosphoric acid: pKa ₁ = 2.15
Phenol: pKa ₁ = 9.82
Ethanethiol: pKa ₁ = 10.61
pKa ₁ was quoted from the following document.
Saccharin: Royal Soc. 197. (1949.), Bell, R .; P. Higginson, W .; C. E. 141.
Isocitric acid: Organic Acids and Food Preservation, (1975), Maria M. et al. Theron; F. Rykers Lues, 24
PKa ₁ other than saccharin and isocitrate is a literature value described in Chemical Handbook Basic Edition II (Revised 3rd Edition, The Chemical Society of Japan, Maruzen).
β-carboxyethyl acrylate: β-CEA (manufactured by Daicel Ornex Co., Ltd.), acid value = 365 mgKOH / g
Acid-modified phenol epoxy acrylate: Kayalad PCR-1169H (manufactured by Nippon Kayaku Co., Ltd.), acid value = 95 to 105 mgKOH / g
Isobornyl acrylate: IBOA-B (manufactured by Daicel Ornex Co., Ltd.), acid value = 0.5 mgKOH / g

  About each receiving layer ink of Examples 1-17 and Comparative Examples 1-6, temporal stability and the adhesiveness of the receiving layer were evaluated. Furthermore, each water-based ink of Production Examples 1 and 2 was applied onto the receiving layer ink to form a water-based ink layer, and the color developability and blur were evaluated. Tables 5 and 6 show the results.

<Stability over time>
Cone plate viscometer TV-22 (manufactured by Toki Sangyo Co., Ltd.) equipped with a standard cone rotor (1 °, 34 ′ × R24) for each of the receiving layer inks of Examples 1 to 17 and Comparative Examples 1 to 6 Was used to measure the viscosity (initial viscosity). The viscosity of 60 mPa · s or less is greater than 60 mPa · s at a shear rate of 192 sec ⁻¹ and a rotation speed of 50 rpm, and the viscosity of 150 mPa · s or less is greater than 150 mPa · s at a shear rate of 77 sec ⁻¹ and a rotation speed of 20 rpm. Was measured at a shear rate of 9.6 sec ⁻¹ and a rotational speed of 2.5 rpm. Then, each ink was put into a 45 degreeC thermostat, left still for 3 days, and the viscosity measurement was performed again. With respect to the initial viscosity and the viscosity after 3 days, the rate of viscosity change was determined by the following formula.
(Viscosity change rate) = (viscosity after 3 days) / (initial viscosity)
If the rate of change in viscosity is large, the dilution rate during printing must be increased, resulting in a decrease in the printed film thickness, resulting in insufficient density of the printed material and a decrease in the physical properties of the coating film.
Viscosity change rate: ◎: less than 1.05, ◯: 1.05 or more, less than 1.1 (can be practically used), △: 1.1 or more, x: solidification, incompatibility, etc. Evaluation was made in four stages.

<Adhesiveness of receiving layer>
The receiving layer inks obtained in Examples 1 to 12 and Comparative Examples 1 to 5 were mixed with Zahn Cup # 3 (manufactured by Kogaisha) in a solvent (mixed solvent of toluene: ethyl acetate: isopropyl alcohol = 1: 1: 1). Dilution adjustment was performed at 18 seconds (25 ° C.). Next, a corona discharge-treated OPP film (thickness: 40 μm, manufactured by Futamura Chemical Co., Ltd., abbreviation: OPP) was obtained using a gravure proofing machine equipped with a screen gravure plate having a plate depth of 30 μm, 175 lines, 150 mm × 110 mm solid image. It was applied and dried with a dryer to form a water-based ink receiving layer, and a test print was produced. Similarly, it is applied to an LLDPE film (thickness 40 μm, Mitsui Chemicals Tosero Co., Ltd., abbreviation: LL), PET film (thickness 40 μm, Toyobo Co., Ltd., abbreviation: PET) to form a water-based ink receiving layer. Then, a test print was produced. At this time, the thickness of the water-based ink receiving layer was 3 μm.
The receiving layer ink 13 (thermosetting type) obtained in Example 13 was applied to an OPP film (thickness: 40 μm, manufactured by Phutamura Chemical Co., Ltd.) using a gravure proofing machine in the same manner as described above, and then applied to a 60 ° C. dryer for 12 hours. A water-based ink receiving layer was formed, and a test print was produced. Similarly, an LLDPE film (thickness 40 μm, manufactured by Mitsui Chemicals Tosero Co., Ltd.) and a PET film (thickness 40 μm, manufactured by Toyobo Co., Ltd.) were formed to form a water-based ink receiving layer, and a test print was prepared. At this time, the thickness of the water-based ink receiving layer was 3 μm.
The receiving layer inks 14 to 16 and 23 (ultraviolet curable type) obtained in Examples 14 to 16 and Comparative Example 6 were applied to an OPP film (thickness 40 μm, manufactured by Phutamura Chemical Co., Ltd.) using a gravure proofing machine in the same manner as described above. The sample was applied and irradiated with ultraviolet rays twice at 80 W / cm, an irradiation distance of 10 cm, and a conveyor speed of 10 m / min using a high-pressure mercury lamp irradiation device to form a water-based ink receiving layer, and a test print was produced. Similarly, an LLDPE film (thickness 40 μm, manufactured by Mitsui Chemicals Tosero Co., Ltd.) and a PET film (thickness 40 μm, manufactured by Toyobo Co., Ltd.) were formed to form a water-based ink receiving layer, and a test print was prepared. At this time, the thickness of the water-based ink receiving layer was 3 μm.
The receiving layer ink 17 (electron beam curable type) obtained in Example 17 was applied to an OPP film (thickness 40 μm, manufactured by Phutamura Chemical Co., Ltd.) using a gravure proofing machine in the same manner as described above, and an electron beam irradiation apparatus was used. Then, electron beam irradiation was performed at an oxygen concentration of 300 ppm or less, an acceleration voltage of 90 kV, and an irradiation dose of 50 kGy to form a water-based ink receiving layer, and a test print was produced. Similarly, an LLDPE film (thickness 40 μm, manufactured by Mitsui Chemicals Tosero Co., Ltd.) and a PET film (thickness 40 μm, manufactured by Toyobo Co., Ltd.) were formed to form a water-based ink receiving layer, and a test print was prepared. At this time, the thickness of the water-based ink receiving layer was 3 μm.
Thereafter, an adhesive tape (28 mm, manufactured by Nichiban Co., Ltd.) was attached to the surface of the water-based ink receiving layer of each test print, peeled rapidly at an angle of 60 degrees, and the area of the peeled ink receiving layer was evaluated. The smaller the peeled area, the better the adhesion of the receiving layer. About peeling area, (circle): It does not peel at all, (triangle | delta): The peeling area is less than 10% (no problem in practical use), x: The peeling area is 10% or more, and evaluated in three steps.

<Color development>
The water-based inkjet ink of Production Example 1 and the water-based gravure ink of Production Example 2 were printed by the following method on each test print having an ink-receiving layer formed in the same manner as in <Adhesion of Receiving Layer>. However, for the receiving layer inks 13 to 17 and 23, after forming the ink receiving layer by each of the above-described <Receptor Layer Adhesiveness> formation methods, the aqueous inkjet ink of Production Example 1 was subsequently prepared by the following method. Printed.
[Water-based inkjet ink]
Each test printed matter in which the ink receiving layer was formed with the receiving layer inks obtained in Examples 1 to 12 and Comparative Examples 1 to 5 was fixed on a stainless steel table heated to 60 ° C., and the surface temperature of the ink receiving layer was 60. It waited until it became ° C. Thereafter, the aqueous ink 1 obtained in Production Example 1 was injected into an inkjet head (Konica Minolta IJ Co., Ltd., KM512MH), and a 20 mm square solid image was printed at a resolution of 720 × 720 dpi. After printing, the water-based ink layer was dried with a drier to produce a water-based ink print. At this time, the thickness of the water-based ink layer was 3 μm.
The receiving layer ink 13 obtained in Example 13 and the aqueous ink 1 obtained in Production Example 1 were injected into an inkjet head (Konica Minolta IJ Co., Ltd., KM512MH), and the receiving layer ink 13 was subjected to a resolution of 720 × 720 dpi. Then, a solid image of 20 mm square was printed, and then the solid image was printed with the water-based ink 1 on the receiving layer ink. Then, it was put into a 60 degreeC dryer for 12 hours, and it was made to harden, and produced the water-based ink printed matter. At this time, the thicknesses of the water-based ink receiving layer and the water-based ink layer were 3 μm and 3 μm, respectively.
The receiving layer ink 14 obtained in Example 14 and the aqueous ink 1 obtained in Production Example 1 were injected into an inkjet head (Konica Minolta IJ Co., Ltd., KM512MH), and the receiving layer ink 14 was subjected to a resolution of 720 × 720 dpi. Then, a solid image of 20 mm square was printed, and then the solid image was printed with the water-based ink 1 on the receiving layer ink. Thereafter, using a high-pressure mercury lamp irradiation device, UV irradiation was performed twice at 80 W / cm, an irradiation distance of 10 cm, and a conveyor speed of 10 m / min, followed by curing to prepare a water-based ink printed matter. At this time, the thicknesses of the water-based ink receiving layer and the water-based ink layer were 3 μm and 3 μm, respectively. Similarly, receiving layer inks 15, 16 and 23 were used to produce water-based ink prints. At this time, the thicknesses of the water-based ink receiving layer and the water-based ink layer were 3 μm, 3 μm, 3 μm, 3 μm, 3 μm, and 3 μm, respectively.
The receiving layer ink 17 obtained in Example 17 and the aqueous ink 1 obtained in Production Example 1 were injected into an inkjet head (Konica Minolta IJ Co., Ltd., KM512MH), and the receiving layer ink 17 was subjected to a resolution of 720 × 720 dpi. Then, a solid image of 20 mm square was printed, and then the solid image was printed with the water-based ink 1 on the receiving layer ink. Thereafter, using an electron beam irradiation apparatus, electron beam irradiation was performed at an oxygen concentration of 300 ppm or less, an acceleration voltage of 90 kV, and an irradiation dose of 50 kGy, and cured to prepare a water-based ink printed matter. At this time, the thicknesses of the water-based ink receiving layer and the water-based ink layer were 3 μm and 3 μm, respectively.
[Water-based gravure ink]
The water-based ink 2 obtained in Production Example 2 was diluted with a solvent (water: isopropyl alcohol = 1: 1 mixed solvent) with Zaan Cup # 3 (manufactured by Hosei Co., Ltd.) for 18 seconds (25 ° C.). Next, the adjusted water-based ink 2 was applied to each test printed matter on which the ink receiving layer was formed by a gravure proofing machine equipped with a screen gravure plate having a plate depth of 30 μm, 175 lines, and a 20 mm × 20 mm solid image, and dried with a dryer. To produce a water-based ink print. At this time, the thickness of the water-based ink layer was 3 μm.
Each water-based ink print was visually observed to evaluate the color developability. The higher the visual density, the better the color developability. The density of the water-based ink printed matter was evaluated in three stages: ○: high density, good color developability, Δ: slightly inferior (no problem in practical use), x: poor.

<Smear>
The degree of bleeding of the water-based ink at the boundary between the solid image portion and the non-image portion of the water-based ink print obtained by the same method as in the above <color development> was visually observed to evaluate the bleeding. It can be judged that the smaller the blur, the better the fixing property to the ink receiving layer and the better the quality and stability of the image. The blur was evaluated in three stages: ○: no blur, Δ: slight blur (no problem in practical use), and x: blur.

  According to Tables 5 and 6, the ink compositions for water-based ink-receiving layers of Examples 1 to 17 are excellent in the temporal stability of the ink, and have good adhesion to the recording medium even if it is a thin film. It is clear. In addition, it is clear that the water-based ink printed matter in which the water-based ink layer is formed on the ink-receiving layer has good color developability and bleeding, and is useful in improving the quality and stability of images. Since the ink composition for the water-based ink receiving layer (receiving layer ink 18) of Comparative Example 1 has few acidic components, the color developability is poor and the water-based ink is blurred. On the other hand, in Comparative Examples 2 and 3, which are examples having too many acidic components, the stability of the receiving layer ink itself is deteriorated (viscosity change rate is large) and the adhesion to the recording medium is inferior (receiving layer ink). 19 and 20). In Comparative Examples 4 and 5, which are examples using an acidic component having a pKa value outside the preferred range, color developability and blurring are inferior, and image quality deterioration occurs (receiving layer inks 21 and 22). Further, in Comparative Example 4, it was clarified that, regardless of whether the water-based ink is a water-based inkjet ink or a water-based gravure ink, color developability and bleeding are inferior and image quality is deteriorated. In Comparative Example 6, which uses an acidic component having a low acid value, color developability and blurring are inferior, and image quality deteriorates (receiving layer ink 23).

Claims (8)

  A resin, a solvent, an acid having a pKa value of 1 to 6 and its anhydride or a derivative of these compounds and a salt (a) or / and a compound (b) having an acid value of 1 mgKOH / g or more An ink composition for a water-based ink receiving layer containing an acidic component that is at least one of the following.   The ink composition for a water-based ink receiving layer according to claim 1, wherein the resin is a resin that does not destabilize the acidic component. The water-based ink receiving layer ink composition;
A water-based ink recording material containing a cation neutralized product of a resin having an anionic functional group;
A water-based ink set comprising:   It forms using the water-based ink set of Claim 3, The water-based ink printed matter characterized by the above-mentioned. A method for producing a water-based ink print using the water-based ink set according to claim 3,
A water-based ink printed matter comprising: a step of forming a water-based ink receiving layer comprising an ink composition for a water-based ink receptive layer on a recording medium; and a step of forming a water-based ink layer comprising a water-based ink recording material. Manufacturing method.   The step of forming the water-based ink receiving layer and the step of forming the water-based ink layer include a silk screen printing method, a gravure printing method, an offset printing method, a flexographic printing method, a roller coater method, a brush coating method, a spray method, At least one selected from knife jet coater method, ink jet printing method, pad printing method, gravure offset printing method, die coater method, bar coater method, spin coater method, comma coater method, impregnation coater method, dispenser method, and metal mask method The method for producing a water-based ink printed matter according to claim 5, comprising:   It forms using the water-based ink printed matter of Claim 4, The packaging bag characterized by the above-mentioned.   It forms using the water-based ink printed matter of Claim 4, The packaging container characterized by the above-mentioned.