JP2021075645A - Aqueous gravure ink - Google Patents

Abstract

To provide aqueous gravure ink which can achieve both improvement of defoaming property in gravure printing and suppression of a cissing phenomenon even on a low liquid-absorptive printing medium such as a resin film, is further excellent in blocking resistance and can obtain a printed matter of high quality, and a gravure printing method using the same.SOLUTION: [1] The aqueous gravure ink contains crosslinked polymer particles containing a pigment, a water-insoluble polyurethane resin, a water-soluble organic solvent, a surface active agent and water. The water-soluble organic solvent contains 0.5-11 mass% of specific ethylene glycol ether, and a content of the water is 55-70 mass%. [2] The gravure printing method performs printing on a low liquid-absorptive printing medium using the aqueous gravure ink.SELECTED DRAWING: None

Description

The present invention relates to a water-based gravure ink and a gravure printing method using the same.

Gravure printing is a printing method in which ink is transferred to a printing substrate using a gravure plate having cells that receive ink. The print quality can be controlled by the cell depth and cell spacing (number of lines), and it is widely used because it enables high-definition printing.
Oil-based inks that use water-insoluble organic solvents are often used as gravure inks for gravure printing, but there are problems in terms of working environment, global environment, disaster prevention, and residual solvents when used in food-related fields. There is a problem. Further, in gravure printing using oil-based ink, since the amount of ink used is large, there is a problem that it is difficult to meet the market needs of high-mix low-volume production.
For this reason, safe and secure water-based gravure inks with less environmental impact are attracting attention.

Patent Document 1 describes a water-soluble urethane resin (A), a polyethylene glycol component having a number average molecular weight of 1000 to 6000, and a hexagon as a water-based gravure ink having reduced plate fog and good gradation transfer property with respect to a resin film. It has a polyethylene glycol-modified urethane resin (B) having a number average molecular weight of 20,000 to 50,000 containing a methylene diisocyanate component, and contains 0.1 to 8% by mass of the modified urethane resin (B) with respect to the urethane resin (A). Aqueous gravure inks are disclosed.
Patent Document 2 describes an ink composition containing a solvent, a polyurethane resin and an acetylene glycol compound as a water-based ink composition for gravure printing having good printability such as leveling property, wherein the solvents are water and propylene. An ink composition containing glycol ether and containing propylene glycol ether in an amount of 10% by weight or less based on the total amount of the ink composition is disclosed.
Patent Document 3 describes an ink containing a pigment, a polymer, a water-soluble organic solvent, an acetylene glycol-based surfactant, and water as a water-based gravure ink having a low environmental load and excellent leveling property, and the water-soluble organic solvent has a boiling point. An ink containing glycol ether at 100 to 260 ° C., the content of glycol ether in the ink is 1 to 10% by mass, the total amount of water-soluble organic solvent is 15% by mass or less, and the content of water is 50 to 70% by mass. Is disclosed.

Japanese Unexamined Patent Publication No. 2006-8929 Japanese Unexamined Patent Publication No. 2016-44282 JP-A-2018-83938

When printing on a highly oil-friendly printing medium such as a resin film, the water-based ink has a low affinity between the ink and the printing medium, so that the ink repellent phenomenon occurs and an area where the ink cannot adhere to the printing medium occurs. May be done. In addition, water-based inks are more likely to generate bubbles than oil-based inks, which may affect print quality.
Further, when printed matter printed with water-based ink is stacked for a long time, the overlapped printed matter sticks to each other, and there is a problem that ink peeling (blocking) occurs on the printed surface when the sticking is peeled off.
The water-based ink described in Patent Document 1 is insufficient to eliminate the blocking property, and the water-based ink described in Patent Documents 2 and 3 is generated when printing on a low water-absorbing printing medium such as a resin film. There was a problem that bubbles and repellent could not be sufficiently suppressed.
Under such circumstances, even when printing on a low-liquid absorption printing medium such as a resin film, a water-based gravure ink that can sufficiently suppress the bubble generation phenomenon and the repelling phenomenon, has excellent blocking resistance, and has a low environmental load is required. Was there.
INDUSTRIAL APPLICABILITY The present invention can achieve both improvement of defoaming property during gravure printing and suppression of repelling phenomenon even for a low liquid absorption printing medium such as a resin film, and further has excellent blocking resistance and obtains a high-quality printed matter. It is an object of the present invention to provide a water-based gravure ink capable of providing a gravure printing method using the same.

The present inventors use a water-insoluble polyurethane resin as a fixing resin in an aqueous gravure ink containing pigment-containing crosslinked polymer particles, a fixing resin, a water-soluble organic solvent, a surfactant, and water, and use the water-soluble organic solvent. It has been found that the above-mentioned problems can be solved by containing a specific amount of a specific ethylene glycol ether and a specific amount of water.
That is, the present invention provides the following [1] and [2].
[1] A water-based gravure ink containing crosslinked polymer particles containing a pigment, a water-insoluble polyurethane resin, a water-soluble organic solvent, a surfactant, and water.
The water-soluble organic solvent contains a compound represented by the following general formula (I), and contains the compound represented by the following general formula (I).
R ¹ O- (C ₂ H ₄ O) _n- H (I)
(In the formula, R ¹ indicates an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms, and n indicates the number of added moles and is 2 or 3.)
The content of the compound represented by the general formula (I) is 0.5% by mass or more and 11% by mass or less.
A water-based gravure ink having a water content of 55% by mass or more and 70% by mass or less.
[2] A gravure printing method for printing on a low liquid absorption printing medium using the water-based gravure ink according to the above [1].

According to the present invention, even for a low liquid absorption printing medium such as a resin film, it is possible to improve the defoaming property at the time of gravure printing and suppress the repelling phenomenon, and further to have excellent blocking resistance and high image quality printed matter. A water-based gravure ink capable of obtaining the above, and a gravure printing method using the same can be provided.

[Aqueous gravure ink]
The water-based gravure ink of the present invention (hereinafter, also simply referred to as “the ink of the present invention”) is a water-based gravure ink containing a pigment-containing crosslinked polymer particle, a water-insoluble polyurethane resin, a water-soluble organic solvent, a surfactant, and water. And
The water-soluble organic solvent contains a compound represented by the following general formula (I) and contains.
R ¹ O- (C ₂ H ₄ O) _n- H (I)
(In the formula, R ¹ indicates an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms, and n indicates the number of added moles and is 2 or 3.)
The content of the compound represented by the general formula (I) is 0.5% by mass or more and 11% by mass or less, and the water content is 55% by mass or more and 70% by mass or less.

The above-mentioned content in the ink of the present invention means a composition in an ink tank equipped in a printing machine used for printing. That is, the ink of the present invention may be adjusted so as to have the composition of the ink of the present invention by keeping the liquid component concentrated during transportation or storage and diluting it with a liquid component such as water during printing.
As used herein, the term "water-based" means that water accounts for the largest proportion of the ink medium.
"Low liquid absorption" is a concept including low liquid absorption and non-liquid absorption of water-based ink. Low liquid absorption can be evaluated by the water absorption of pure water. More specifically, it means that the amount of water absorption per surface area of the print medium at a contact time of 100 msec between the print medium and pure water is 0 g / m ² or more and 10 g / m ² or less. The amount of water absorption can be measured using an automatic scanning liquid absorption meter.
"Printing" is a concept including printing and printing for recording characters and images.

The ink of the present invention can achieve both improvement of defoaming property and suppression of repelling phenomenon at the time of gravure printing even for a low liquid absorption printing medium such as a resin film, and further has excellent blocking resistance and high image quality printed matter. Obtainable. The reason is not clear, but it can be considered as follows.
The ink of the present invention contains crosslinked polymer particles containing a pigment, a water-insoluble polyurethane resin, a water-soluble organic solvent, a surfactant, and water, and comprises a compound represented by the general formula (I) as a water-soluble organic solvent. It is considered that by containing a specific amount of water as a component and a specific amount of water, the wettability to the printing medium can be enhanced, the repelling phenomenon can be suppressed, and the generation of bubbles can be suppressed to enhance the defoaming property. Further, by using the crosslinked polymer particles containing the pigment, the swelling of the polymer due to the compound represented by the general formula (I) can be suppressed, and by using the water-insoluble polyurethane resin as the fixing resin, the printing medium can be printed. It is considered that the sticking property of the ink is significantly improved and the blocking resistance is improved.

<Crosslinked polymer particles containing pigment>
In the present invention, from the viewpoint of suppressing the swelling of the pigment particles due to the compound represented by the general formula (I) and improving the blocking resistance of the obtained printed matter, the pigment is a crosslinked polymer particle containing the pigment (hereinafter, hereinafter, It is also used in the form of "pigment-containing crosslinked polymer particles").
In the present specification, the crosslinked polymer particles containing a pigment are particles in the form in which the polymer contains the pigment, particles in the form in which a part of the pigment is exposed on the surface of the particles composed of the polymer and the pigment, and the polymer is the pigment. It means any of the particles in the form adsorbed on a part of the polymer or a mixture thereof, and means that the polymer has a crosslinked structure.
The pigment-containing crosslinked polymer particles are preferably those that can maintain a dispersed state in an aqueous ink with an average particle size of 350 nm or less.

(Pigment)
The pigment used in the present invention may be either an inorganic pigment or an organic pigment, but an organic pigment is more preferable.
Examples of the inorganic pigment include carbon black and metal oxide, and carbon black is preferable for black ink. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black. Examples of the white ink include metal oxides such as titanium dioxide, zinc oxide, silica, alumina and magnesium oxide. These inorganic pigments may be surface-treated with a known hydrophobizing agent such as a titanium coupling agent, a silane coupling agent, or a higher fatty acid metal salt.
Examples of the organic pigment include azo pigment, diazo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, dioxazine pigment, perylene pigment, perinone pigment, thioindigo pigment, anthraquinone pigment, quinophthalone pigment and the like.
The hue is not particularly limited, and any chromatic pigment such as yellow, magenta, cyan, red, blue, orange, and green can be used in the chromatic ink.
The pigment can be used alone or in combination of two or more.

(Polymer constituting pigment-containing crosslinked polymer particles)
The pigment-containing crosslinked polymer particles are a component derived from the pigment and a polymer having an ability to disperse the pigment (hereinafter, also referred to as “polymer a”), and a compound that forms a crosslinked structure (hereinafter, “crosslinking agent a””. It also means a component derived from (also called).
The polymer a may be a water-soluble polymer or a water-insoluble polymer, but a water-insoluble polymer is more preferable.
As used herein, the term "water-insoluble" means that a polymer that has been dried at 105 ° C. for 2 hours and has reached a constant weight is dissolved in 100 g of water at 25 ° C. in an amount of less than 10 g. This means that the dissolved amount of the polymer is preferably 5 g or less, more preferably 1 g or less. When the polymer is an anionic polymer, the dissolved amount is the dissolved amount when the anionic group of the polymer is 100% neutralized with sodium hydroxide.

(Polymer a)
The polymer a is a polymer having a pigment-dispersing ability to disperse a pigment in an aqueous medium containing water as a main component. The polymer a can have any structure, but from the viewpoint of improving the dispersion stability of the pigment in the ink of the present invention, it is a vinyl type obtained by addition polymerization of vinyl monomers such as vinyl compounds, vinylidene compounds and vinylene compounds. Polymers are preferred.
The vinyl-based polymer preferably contains a structural unit derived from the (a-1) ionic monomer (hereinafter, also referred to as “(a-1) component”), and contains the (a-1) component and (a-2). ) A vinyl polymer obtained by copolymerizing a monomer mixture A (hereinafter, also referred to as “monomer mixture A”) containing a hydrophobic monomer (hereinafter, also referred to as “component (a-2)”) is more preferable. In this case, the vinyl polymer contains a structural unit derived from the component (a-1) and a structural unit derived from the component (a-2).

[(A-1) Ionic Monomer]
The (a-1) ionic monomer is preferably used as a monomer component of the polymer a from the viewpoint of improving the dispersion stability of the pigment.
(A-1) As the ionic monomer, an anionic monomer is preferable.
Examples of the anionic monomer include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer. Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethylsuccinic acid.
Among these, from the same viewpoint as above, the carboxylic acid monomer is more preferable, and one or more selected from acrylic acid and methacrylic acid is further preferable.

[(A-2) Hydrophobic monomer]
The hydrophobic monomer (a-2) is preferably used as a monomer component in addition to the component (a-1) from the viewpoint of improving the dispersion stability of the pigment.
Examples of the component (a-2) include aromatic group-containing monomers, alkyl (meth) acrylates, macromonomers, and the like, and specific examples thereof include paragraphs [0020] to [0022] of JP-A-2018-83938. The ones described in are mentioned. Among these, one selected from styrene-based monomers such as styrene and α-methylstyrene, benzyl (meth) acrylates, alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms, and styrene-based macromonomers. The above is preferable.

[(A-3) Nonionic monomer]
The (a-3) nonionic monomer (hereinafter, also referred to as “component (a-3)”) can be used from the viewpoint of improving the dispersion stability of the pigment.
The component (a-3) is a monomer having a high affinity for water or a water-soluble organic solvent, and is, for example, a monomer containing a hydroxyl group or a polyalkylene glycol chain.
Specific examples of the component (a-3) include those described in paragraph [0018] of JP-A-2018-83938. Among these, one or more selected from methoxypolyethylene glycol (n = 1 to 30) (meth) acrylate and polypropylene glycol (n = 2 to 30) (meth) acrylate are preferable.
As the above-mentioned components (a-1) to (a-3), the monomer components contained in each component can be used alone or in combination of two or more.

(Content of each component in the monomer mixture A or each structural unit in the polymer a)
The content of the components (a-1) to (a-3) in the monomer mixture A at the time of producing the polymer a (content as an unneutralized amount; the same applies hereinafter) or (a-1) to the polymer a. The content of the structural unit derived from the component (a-3) is as follows from the viewpoint of improving the dispersion stability of the pigment.
The content of the component (a-1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass. % Or less, more preferably 20% by mass or less.
The content of the component (a-2) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass. % Or less, more preferably 75% by mass or less.
When the component (a-3) is contained, the content thereof is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less. is there.
The mass ratio of the component (a-1) to the component (a-2) [(a-1) / (a-2)] is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0. It is .25 or more, and preferably 1.2 or less, more preferably 1.0 or less, still more preferably 0.8 or less.

In the present invention, the content of the structural units derived from the components (a-1) to (a-3) in the polymer a can be determined by measurement, and (a-1) to (a) at the time of producing the polymer a. -3) It is also possible to substitute the charging ratio of the raw material monomer containing the component. Of these, the content of the component (a-1) is preferably determined by the potentiometric titration method, and the content of the component (a-2) and the component (a-3) is preferably the charging ratio of the raw material monomer. Is.

(Manufacturing of polymer a)
The polymer a can be produced by copolymerizing the monomer mixture A by a known polymerization method. As the polymerization method, a solution polymerization method is preferable.
The solvent used in the solution polymerization method is not limited, but polar solvents such as water, lower aliphatic alcohols, ketones, ethers and esters are preferable, and from the viewpoint of solubility of the polymer in the solvent, the number of carbon atoms is 3 or more and 5 or less. Ketone is preferable, and methyl ethyl ketone is more preferable.
At the time of polymerization, a polymerization initiator such as a persulfate or a water-soluble azo compound, or a polymerization chain transfer agent such as a mercaptan can be used.
The polymerization temperature varies depending on the type of polymerization initiator, monomer, solvent and the like used, but is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and preferably 95 ° C. or lower, more preferably 80 ° C. or lower. is there.
The polymerization atmosphere is preferably a nitrogen gas or an inert gas atmosphere.
After completion of the polymerization reaction, the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation and solvent distillation.
The polymer a is preferably neutralized with a neutralizing agent as described later.

The weight average molecular weight of the polymer a is preferably 10,000 or more, more preferably 15,000 or more, and preferably 300,000 or less, more preferably 200,000 or less, from the viewpoint of improving the dispersion stability of the pigment. , More preferably 100,000 or less.
The acid value of the polymer a is preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, still more preferably 100 mgKOH / g or more, and from the viewpoint of the dispersibility of the pigment and the adsorptivity of the polymer to the pigment. It is preferably 300 mgKOH / g or less, more preferably 280 mgKOH / g or less, and even more preferably 260 mgKOH / g or less.
The weight average molecular weight and acid value of polymer a are measured by the methods described in Examples.

As the polymer a, commercially available ones may be used. Examples of commercially available polymers a are "John Krill 67", "John Krill 611", "John Krill 678", "John Krill 680", "John Krill 690", "John Krill 819" (above, BASF Japan Ltd.) Examples include styrene-acrylic resin such as (manufactured by the company).

(Crosslinking agent a)
The cross-linking agent a is a compound that forms a chemical bond within a polymer having a pigment-dispersing ability or between polymers having a pigment-dispersing ability, and has two or more functional groups capable of chemically reacting with the polymer a in the molecule.
Examples of the functional group capable of chemically reacting with the polymer a include a compound having an epoxy group, an oxazoline group, or an isocyanate group. Of these, epoxy groups are preferred.
Specific examples of the cross-linking agent a include trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and the like, and among these, trimethylolpropane polyglycidyl ether is preferable. The constituent component derived from the cross-linking agent a preferably contains a constituent component derived from trimethylolpropane polyglycidyl ether.
The abundance ratio of the constituent components derived from the cross-linking agent a is the ratio of the molar equivalents of the cross-linking functional groups of the cross-linking agent a to the molar equivalents of the carboxy groups of the polymer a (the molar equivalents of the cross-linking functional groups of the cross-linking agent a / The molar equivalent of the carboxy group of the polymer a) is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, still more preferably 30 mol% or more, and preferably. It is 80 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, still more preferably 60 mol% or less.

[Manufacture of pigment-containing crosslinked polymer particles]
From the viewpoint of efficient production, the pigment-containing crosslinked polymer particles are preferably produced as the pigment dispersion A in which the pigment-containing crosslinked polymer particles are dispersed in an aqueous medium by a method having the following steps I and III.
Step I: After dissolving the polymer a in a solvent to obtain a solution of the polymer a, a pigment and, if necessary, a neutralizing agent, a surfactant and the like are added and mixed to obtain a pigment dispersion A composed of a pigment mixture. Step of obtaining In step I, in order to efficiently contain the pigment in the polymer particles, the solvent preferably contains an organic solvent, and in that case, in addition to step I, the following step II may be further provided.
Step II: The organic solvent is removed from the pigment mixture obtained in Step I to obtain a pigment dispersion A. Step III: The pigment dispersion A obtained in Step I or Step II is mixed with the cross-linking agent a. Steps to Obtain Pigment-Containing Crosslinked Polymer Particles In the present specification, in the pigment dispersion A, the pigment-containing polymer particles are dispersed in an aqueous medium, and the pigment-containing crosslinked polymer particles are dispersed in an aqueous medium. Means both of what is.

(Step I)
In step I, the solvent for dissolving the polymer a is not limited, but from the viewpoint of wettability to the pigment, solubility of the polymer a, and adsorption to the pigment, water, lower aliphatic alcohols, ketones, ethers, etc. One or more selected from esters and the like are preferable, one or more selected from water and ketones having 3 or more and 5 or less carbon atoms are more preferable, and the combined use of water and ketone is further preferable. When the polymer a is synthesized by the solution polymerization method, the solvent used in the polymerization may be used as it is.
When the polymer a is an anionic polymer, it is preferable to use a neutralizing agent to neutralize the anionic groups in the polymer a. When a neutralizing agent is used, it is preferable to neutralize the pH so that the pH is 7 or more and 11 or less. Examples of the neutralizing agent include bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia, and various amines. Further, the polymer a may be neutralized in advance.
The degree of neutralization of the anionic group of the polymer a is the ratio of the molar equivalent of the neutralizing agent to the molar equivalent of the anionic group of the polymer a, preferably 30 mol, from the viewpoint of improving the storage stability of the ink of the present invention. % Or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and preferably 250 mol% or less, more preferably 200 mol% or less, still more preferably 150 mol% or less.

In step I, it is preferable to apply mechanical force to the obtained pigment mixture for dispersion treatment. The method for applying the mechanical force is not particularly limited, and examples thereof include the method described in paragraph [0032] of JP-A-2018-83938. As a device for applying mechanical force, a media type disperser is preferable from the viewpoint of efficiently reducing the particle size of the pigment.
When the dispersion treatment is performed, the pigment can be adjusted to have a desired particle size by controlling the dispersion pressure and the like.

(Step II)
Step II is an arbitrary step, but when the solvent contains an organic solvent in step I, the step II is a step of removing the organic solvent from the pigment mixture obtained in step I to obtain a pigment dispersion A containing water. ..
It is preferable that the organic solvent in the obtained pigment dispersion A is substantially removed, but it may remain as long as the object of the present invention is not impaired. The amount of the residual organic solvent is preferably 0.1% by mass or less, more preferably 0.01% by mass or less.

The average particle size of the polymer particles containing the pigment in the pigment dispersion A is preferably 100 nm or more, more preferably 150 nm or more, still more preferably 180 nm from the viewpoint of improving storage stability and performing high-definition printing. The above, and preferably 380 nm or less, more preferably 360 nm or less, still more preferably 340 nm or less.
Even when the cross-linking treatment is performed in the following step III, the average particle size of the pigment-containing cross-linked polymer particles in the obtained pigment dispersion A is equivalent to the average particle size of the pigment-containing polymer particles.
The average particle size is measured by the method described in Examples.

(Step III)
Step III is a step of mixing and reacting the pigment dispersion A obtained in step I or step II with the cross-linking agent a to obtain cross-linked pigment-containing cross-linked polymer particles.
In step III, a part of the carboxy group of the polymer a constituting the pigment-containing polymer particles is crosslinked to form a crosslinked structure on a part or all of the surface layer portion of the pigment-containing polymer particles, and the pigment-containing crosslinked polymer is formed. It can be a particle. It is considered that this cross-linking treatment suppresses the swelling and the like of the polymer a, and improves the storage stability of the obtained ink and the blocking resistance of the obtained printed matter. That is, from the viewpoint of strengthening the content of the pigment by the polymer a, the cross-linking agent a is preferably reacted with the polymer a constituting the polymer particles containing the pigment in the pigment dispersion A.
When the polymer a is an anionic polymer having an anionic group, the cross-linking agent a is preferably a compound having a functional group capable of reacting with the anionic group, and a compound having 2 or more and 6 or less the functional group in the molecule is preferable. More preferred.
The temperature of the crosslinking treatment is preferably 40 ° C. or higher, more preferably 55 ° C. or higher, and preferably 95 ° C. or lower, more preferably 80 ° C. or lower, from the viewpoint of reactivity and economy.

The solid content concentration of the pigment dispersion A is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably from the viewpoint of improving the dispersion stability of the pigment dispersion and facilitating ink production. Is 45% by mass or less, more preferably 40% by mass or less.
The solid content concentration is measured by the method described in Examples.
From the viewpoint of dispersion stability, the content of the pigment in the pigment dispersion A is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 45% by mass. % Or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.
The total of the polymer a and the cross-linking agent a constituting the pigment-containing cross-linked polymer particles in the pigment dispersion A and the mass ratio of the pigment [(polymer a + cross-linking agent a) / pigment] are preferably 0.1 or more, more preferably. Is 0.15 or more, more preferably 0.2 or more, and preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.5 or less.

<Water-insoluble polyurethane resin>
The ink of the present invention contains a water-insoluble polyurethane resin from the viewpoint of improving the blocking resistance of the obtained printed matter.
In the ink of the present invention, the water-insoluble polyurethane resin is preferably in the form of particles, preferably mainly composed of a resin component, and more preferably composed only of a resin. That is, the water-insoluble polyurethane resin is preferably pigment-free resin particles (hereinafter, also referred to as "resin particles B"), and more preferably resin particles made of polyurethane having a urethane group on the main chain.
The polyurethane constituting the resin particles B preferably has a crosslinked structure. The crosslinked structure may be formed by a method of synthesizing polyurethane using a trifunctional or higher functional monomer (method A), or a linear polyurethane may be obtained using a bifunctional monomer and then an isocyanate group at the terminal. Alternatively, it may be formed by a method (method B) of reacting with a trifunctional or higher cross-linking agent that reacts with a hydroxyl group. Among these, method B is preferable from the viewpoint of ease of production, and it is preferable to react a polyurethane having an isocyanate group remaining at the terminal with a cross-linking agent to produce a polyurethane having a cross-linked structure.
Here, "water-insoluble" is the same as the definition in the polymer a.

(Polyurethane)
Polyurethane undergoes a double addition reaction of a (b-1) diol compound (hereinafter, also referred to as “(b-1) component”) and (b-2) diisocyanate (hereinafter, also referred to as “(b-2) component”). Can be obtained by

[(B-1) Diol compound]
The component (b-1) is a compound having two hydroxyl groups in its molecular structure.
The component (b-1) is obtained from an aliphatic diol which may contain a chain or cyclic structure having 4 to 18 carbon atoms, a polyether diol obtained by polymerizing 2 to 45 molecules of alkylene glycol, and a diol and a diester. Examples thereof include polyester diols.
Among these, a polyether diol obtained by polymerizing 10 to 40 molecules of alkylene glycol is preferable, and one or more selected from polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol having a number average molecular weight of 1000 to 2500 are selected. More preferred. The hydroxyl value of these diol compounds is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, and preferably 80 mgKOH / g or less, more preferably 70 mgKOH / g or less.

[(B-2) Diisocyanate]
The component (b-2) is a compound having two isocyanate groups in its molecular structure.
Examples of the component (b-2) include aliphatic diisocyanates having a cyclic structure such as 1,4-cyclohexanediisocyanate and isophorone diisocyanate, hexamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, and the like. Examples thereof include chain aliphatic diisocyanates, tolylene diisocyanates, diphenylmethane diisocyanates α, α, α, α-tetramethylxylylene diisocyanates, and aromatic aliphatic diisocyanates such as xylylene diisocyanates.
Among these, an aliphatic diisocyanate compound capable of achieving both toughness and flexibility is preferable from the viewpoint of improving blocking resistance, and among them, an aliphatic diisocyanate compound having a cyclic structure is more preferable, and isophorone diisocyanate is further preferable.
As the above-mentioned components (b-1) and (b-2), the monomer components contained in each component can be used alone or in combination of two or more.

((B-3) acid component)
In the ink of the present invention, from the viewpoint of forming polyurethane in the form of particles, the monomer component includes the (b-1) component and the (b-2) component, as well as the (b-3) acid component (hereinafter, “(b-3)”. ) Ingredients ”).
The component (b-3) has a carboxy group in addition to the diol structure and / or the diisocyanate structure. Specific examples of the component (b-3) include dimethylolpropionic acid and dimethylolbutanoic acid, but dimethylolpropionic acid is preferable.
As will be described later, the component (b-3) is preferably used so that the acid value of the polyurethane of the present invention is 5 mgKOH / g or more and 40 mgKOH / g or less.

(Manufacturing of water-insoluble polyurethane resin)
In the water-insoluble polyurethane resin, a mixture containing the component (b-1) and the component (b-2), preferably the component (b-3) is further added by a known method, and then reacted with the cross-linking agent b. Those having a crosslinked structure are preferable.
The cross-linking agent b is preferably a compound having a trifunctional or higher functional group capable of reacting with an isocyanate group at the terminal of polyurethane or a hydroxyl group. Examples of the cross-linking agent b include compounds having three or more hydroxyl groups or amino groups in one molecule when the end of the polyurethane is an isocyanate group, and three isocyanate groups in one molecule when the end of the polyurethane is a hydroxyl group. Examples thereof include the compounds having the above.
In the present invention, the end of the polyurethane is preferably an isocyanate group, and the cross-linking agent b is preferably a compound having three or more hydroxyl groups or amino groups in one molecule. Examples of such compounds include polyhydric alcohols such as glycerin and amines such as polyethylene polyamines such as diethylenetriamine, triethylenetetramine and polyethyleneimine, but amines are preferable, and diethylenetriamine is more preferable.
At the time of polymerization, a polymerization catalyst such as an aliphatic amine compound or an organic tin compound may be used.

The average particle size of the water-insoluble polyurethane resin in the aqueous medium is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and from the viewpoint of improving the storage stability and fixability of the ink of the present invention. It is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less.
The average particle size is measured by the method described in Examples.

When the water-insoluble polyurethane resin has a crosslinked structure, it is difficult to measure the weight average molecular weight of the polyurethane constituting the water-insoluble polyurethane resin, but the portion soluble in the solvent shown in the molecular weight measurement method by the GPC method described in the examples. Is preferably 200,000 or more, more preferably 300,000 or more, further preferably 400,000 or more, and preferably 2.5 million or less, more preferably 1 million or less, still more preferably 600,000 or less. is there.
The acid value of the polyurethane constituting the water-insoluble polyurethane resin after cross-linking is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 10 mgKOH / g or more, from the viewpoint of improving the storage stability and fixability of the ink of the present invention. It is 20 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 38 mgKOH / g or less, still more preferably 34 mgKOH / g or less.
The weight average molecular weight and acid value of the polymer are measured by the method described in Examples.

<Water-soluble organic solvent>
The ink of the present invention contains a water-soluble organic solvent from the viewpoint of improving the defoaming property at the time of gravure printing and suppressing the repelling phenomenon and improving the blocking resistance.
Here, the "water-soluble organic solvent" refers to an organic solvent having a dissolution amount of 10 ml or more when the organic solvent is dissolved in 100 ml of water at 25 ° C., and is liquid at room temperature (25 ° C.). May also be solid.
From the same viewpoint as above, the boiling point of the water-soluble organic solvent is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, further preferably 150 ° C. or higher, and preferably 280 ° C. or lower, more preferably 260 ° C. Hereinafter, it is more preferably 250 ° C. or lower.
Here, the "boiling point" means a standard boiling point (boiling point under 1 atm), and the boiling point is measured according to JIS K2254. When two or more kinds of water-soluble organic solvents are used, the boiling point value is a weighted average value weighted by the content (mass%) of each water-soluble organic solvent.

In the ink of the present invention, the water-soluble organic solvent contains a compound represented by the following general formula (I), that is, di or triethylene glycol ether. Its content is 0.5% by mass or more and 11% by mass or less, and as will be described later, it is preferably 1% by mass or more and 10% by mass or less.
R ¹ O- (C ₂ H ₄ O) _n- H (I)
(In the formula, R ¹ indicates an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms, and n indicates the number of added moles and is 2 or 3.)
Specific examples of the compound represented by the general formula (I) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, and diethylene glycol monoisobutyl ether. Examples thereof include triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol mono-n-propyl ether, triethylene glycol monoisopropyl ether, and triethylene glycol mono-n-butyl ether.
Among these, diethylene glycol monomethyl ether (194 ° C.), diethylene glycol monoisopropyl ether (207 ° C.), and diethylene glycol from the viewpoint of improving antifoaming property and suppressing repellent phenomenon during gravure printing and improving blocking resistance. One or more selected from monoisobutyl ether (220 ° C.), diethylene glycol mono-n-butyl ether (230 ° C.), and triethylene glycol monomethyl ether (248 ° C.) are preferable, and diethylene glycol monoisopropyl ether (207 ° C.) is more preferable. The numerical value in parentheses is the boiling point.

The ink of the present invention can further contain glycol as a water-soluble organic solvent.
Examples of the glycol include ethylene glycol, propylene glycol (1,2-propanediol), 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol 1,2-octanediol, and 1,2-decane. 1,2-Alkanediols such as diols having 2 or more and 10 or less carbon atoms, preferably 2 or more and 6 or less carbon atoms; 1,3-propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3, 1,3-Alkanediol having 3 or more and 8 or less carbon atoms, preferably 3 or more and 6 or less carbon atoms such as 3-butanediol and 2-ethyl-1,3-hexanediol; polyalkylene glycol such as dipropylene glycol and diethylene glycol. And so on.
Among these, 1,2-alkanediol having 2 or more and 6 or less carbon atoms is preferable, propylene glycol (188 ° C.) and 1,2-butanediol (194 ° C.) are more preferable, and propylene glycol is further preferable.

The content of glycol in the ink of the present invention is preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less, still more preferably 10% by mass, from the viewpoint of maintaining an appropriate ink viscosity. From the viewpoint of suppressing the repelling phenomenon, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more.
When the ink of the present invention contains propylene glycol, it is preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably 10% by mass or less, and the repelling phenomenon from the viewpoint of maintaining an appropriate ink viscosity. From the viewpoint of suppressing the above, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more.
The water-soluble organic solvent is an ethylene glycol monoalkyl ether such as ethylene glycol monoisopropyl ether other than the compound represented by the general formula (I), and other water-soluble organic solvents, as long as the effects of the present invention are not impaired. May include. Examples of other water-soluble organic solvents include monohydric alcohols having a boiling point of less than 100 ° C. such as isopropyl alcohol, trihydric and higher alcohols, and cyclic amide compounds such as N-methyl-2-pyrrolidone and 2-pyrrolidone. Be done.

<Surfactant>
The ink of the present invention further contains a surfactant from the viewpoint of achieving both improvement of defoaming property and suppression of repellent phenomenon during gravure printing.
Examples of the surfactant include anionic surfactants, nonionic surfactants, amphoteric surfactants and the like, but nonionic surfactants are preferable, and acetylene glycol-based surfactants and silicone-based surfactants are selected. One or more of them are more preferable.

(Acetylene glycol-based surfactant)
From the same viewpoint as above, the acetylene glycol-based surfactant is preferably acetylene glycol having 8 or more and 22 or less carbon atoms and an ethylene oxide adduct thereof, and more preferably acetylene glycol having 8 or more and 22 or less carbon atoms. The carbon number of the acetylene glycol is preferably 10 or more, more preferably 12 or more, and preferably 20 or less, more preferably 18 or less, still more preferably 16 or less.
The HLB (hydrophilic lipophilic balance) value of the acetylene glycol-based surfactant is preferably 0 or more, more preferably 1 or more, still more preferably 2 or more, still more preferably 2.5 or more, and preferably. It is 5.5 or less, more preferably 5.0 or less, still more preferably 4.5 or less. The HLB value can be determined by the Griffin method.

Specific examples of the acetylene glycol-based surfactant include 2,4,7,9-tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 2, , 5,8,11-Tetramethyl-6-dodecine-5,8-diols and other acetylene-based diols, and ethylene oxide adducts thereof are mentioned, and examples of commercially available products thereof are manufactured by Air Products and Chemicals Co., Ltd. or Japan. Examples thereof include the "surfinol" series and "olphin" series manufactured by Shinkagaku Kogyo Co., Ltd., and the "acetylenol" series manufactured by Kawaken Fine Chemical Co., Ltd.
Among these, Surfinol 104 (2,4,7,9-tetramethyl-5-decine-4,7-diol, HLB: 3), 104E (50% diluted ethylene glycol of Surfinol 104), the same. 104PG-50 (50% dilution of propylene glycol of Surfinol 104), Surfinol 420 (Eo average 1.3 mol addition of Surfinol 104, HLB: 4.7), Acetylenol E13T (EO average addition molar number: 1) 3.3, HLB: 4.7) and the like are preferable.

(Silicone-based surfactant)
Examples of the silicone-based surfactant include dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone, and carboxy-modified silicone, but from the same viewpoint as described above, polyether-modified silicone is preferable.
The polyether-modified silicone has a structure in which the hydrocarbon groups at the side chains and / or terminals of the silicone oil are replaced with the polyether groups. As the polyether group, a polyalkyleneoxy group in which a polyethyleneoxy group, a polypropyleneoxy group, an ethyleneoxy group (EO) and a propyleneoxy group (PO) are added in a block shape or at random is preferable, and a polyalkyleneoxy group is added to the silicone main chain. A compound in which an ether group is grafted, a compound in which a silicone and a polyether group are bonded in a block shape, and the like can be used.

From the same viewpoint as above, the HLB value of the polyether-modified silicone-based surfactant is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more.
Specific examples of the polyether-modified silicone include PEG-3 dimethicone, PEG-9 dimethicone, PEG-9 PEG-9 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-11 methyl ether dimethicone, and PEG / PPG-. Examples thereof include 20/22 butyl ether dimethicone, PEG-32 methyl ether dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, and lauryl PEG-9 polydimethylsiloxyethyl dimethicone.
Examples of commercially available products of polyether-modified silicones include silicones from Shin-Etsu Chemical Co., Ltd .: KF-6011, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6028, KF-6038. , KF-6043 and the like.
When a silicone-based surfactant and an acetylene glycol-based surfactant are used in combination in the ink of the present invention, bubbles are efficiently arranged at the gas-liquid interface due to the strong hydrophobicity of the acetylene glycol-based surfactant. It is more preferable because water is rapidly discharged from the water film and the silicone-based surfactant lowers the surface tension of the ink, so that the wettability of the ink to the printing medium can be improved.

(Carbodiimide-based curing agent)
The ink of the present invention preferably further contains a carbodiimide-based curing agent.
The carbodiimide-based curing agent means a polymer having a plurality of carbodiimide groups in the molecule. The carbodiimide group reacts with the carboxyl group of the polymer a constituting the pigment-containing crosslinked polymer particles in the pigment dispersion A and the carboxyl group of the polymer b constituting the resin particles B, so that the water of the ink of the present invention is discharged from the printing medium. It has the effect of improving the strength of the coating film after volatilization. Further, by using the carbodiimide-based curing agent in combination with the ink of the present invention in which the crosslinked polymer particles containing the pigment, the water-insoluble polyurethane resin and the compound represented by the general formula (I) are combined, the coating strength is improved at the same time. , Improvement of defoaming property and suppression of repellent phenomenon can be achieved at a higher level.
Examples of commercially available carbodiimide-based curing agents include carbodilites E-01, E-02, E-03A, and E-04 manufactured by Nisshinbo Chemical Co., Ltd.

[Manufacturing of water-based gravure ink]
The ink of the present invention comprises a pigment dispersion in which crosslinked polymer particles containing a pigment are dispersed in an aqueous medium, a compound represented by the general formula (1), a water-insoluble polyurethane resin, a surfactant, and if necessary. Further, it can be efficiently produced by mixing it with another organic solvent, a carbodiimide-based curing agent, or the like. There is no particular limitation on the mixing method thereof. Further, the ink of the present invention may be used as it is by adjusting each component to the content and density at the time of printing, and the base ink prepared in advance is diluted with water or the like and adjusted to the content and density at the time of printing. You may use it.

The content of each component of the ink of the present invention and the physical characteristics of the ink are as follows. The content of each component in the ink is the content at the time of printing.
(Pigment content)
From the viewpoint of printing density, the content of the pigment in the ink of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more. And, preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably 10% by mass or less, still more preferably 9% by mass or less.

(Content of crosslinked polymer particles containing pigment)
The content of the pigment-containing crosslinked polymer particles in the ink of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and from the viewpoint of improving the printing density. From the viewpoint of improving storage stability, it is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
The content of the polymer a in the ink of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5, from the viewpoint of improving the blocking resistance of the obtained printed matter. It is 5% by mass or more, and preferably 10% by mass or less, more preferably 6% by mass or less, and further preferably 4% by mass or less.
The total mass ratio of the polymer a and the cross-linking agent a to the pigment in the ink of the present invention [(polymer a + cross-linking agent a) / pigment] is preferably 0.06 or more from the viewpoint of improving the storage stability of the ink. It is preferably 0.1 or more, more preferably 0.2 or more, and preferably 1 or less, more preferably 0.8 or less, still more preferably 0.6 or less, still more preferably 0.5 or less, and more. More preferably, it is 0.4 or less.

(Content of water-insoluble polyurethane resin)
The content of the water-insoluble polyurethane resin in the ink of the present invention is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, from the viewpoint of improving the blocking resistance of the obtained printed matter. Yes, and preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably 11% by mass or less.

The mass ratio of the polymer to the pigment in the ink of the present invention [polymer / pigment] is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0.8 or more from the viewpoint of storage stability of the ink. Yes, and preferably 4 or less, more preferably 3 or less, still more preferably 2 or less.
In the ink of the present invention, the amount of polymer in the mass ratio [polymer / pigment] is the total amount of polymer a, cross-linking agent a, and polyurethane. At this time, if both the polymer a and the polyurethane are neutralized, the mass including the neutralizing agent is calculated.

(Content of water-soluble organic solvent)
The total content of the water-soluble organic solvent in the ink of the present invention is preferably 2% by mass or more from the viewpoint of improving the defoaming property and suppressing the repelling phenomenon at the time of gravure printing and improving the blocking resistance. , More preferably 4% by mass or more, further preferably 6% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.
From the same viewpoint as above, the content of the compound represented by the general formula (I) in the ink of the present invention is 0.5% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more. , More preferably 3% by mass or more, still more preferably 5% by mass or more, and 11% by mass or less, preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 8% by mass. It is as follows.

(Surfactant content)
The content of the surfactant in the ink of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass, from the viewpoint of achieving both improvement of defoaming property and suppression of repelling phenomenon during gravure printing. As mentioned above, it is more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.
The contents of the acetylene glycol-based surfactant and the silicone-based surfactant in the ink of the present invention are preferably 0.02% by mass or more, more preferably 0.04% by mass or more, respectively, from the same viewpoints as described above. It is more preferably 0.06% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less.
The mass ratio of the acetylene glycol-based surfactant in the ink of the present invention to the total amount of the surfactant [acetylene glycol-based surfactant / total amount of surfactant] is preferably 0.1 or more, more preferably 0.2 or more, and further. It is preferably 0.4 or more, and preferably 1 or less.

(Content of carbodiimide-based curing agent)
The content of the carbodiimide-based curing agent in the ink of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of achieving both improvement of defoaming property and suppression of repelling phenomenon during gravure printing. It is more preferably 1.5% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.

(Water content)
The content of water in the ink of the present invention is 55% by mass or more, preferably 58% by mass, from the viewpoint of improving the defoaming property and suppressing the repelling phenomenon at the time of gravure printing and improving the blocking resistance. As mentioned above, it is more preferably 62% by mass or more, and from the viewpoint of ensuring the print density, it is preferably 72% by mass or less.
The ink of the present invention may contain various additives such as a pH adjuster, a viscosity adjuster, a preservative, and a rust preventive as optional components depending on its use.

(Ink physical characteristics)
Zahn cup No. of the ink of the present invention at 20 ° C. The 3 viscosity is preferably 10 seconds or longer, more preferably 12 seconds or longer, still more preferably 14 seconds or longer, from the viewpoint of improving the defoaming property and suppressing the repelling phenomenon at the time of gravure printing and improving the blocking resistance. And preferably 25 seconds or less, more preferably 24 seconds or less, still more preferably 23 seconds or less.
The pH of the ink of the present invention at 20 ° C. is preferably 5.5 or more, more preferably 6.5 or more from the viewpoint of improving dispersion stability, and preferably from the viewpoint of member resistance and skin irritation. It is 11 or less, more preferably 9 or less.

[Gravure printing method]
The gravure printing method of the present invention is a method of printing on a low liquid absorption printing medium using the water-based gravure ink of the present invention.
Examples of gravure printing include printing using printing plates such as intaglio printing, lithographic printing, and letterpress printing. By printing the ink of the present invention on a low liquid absorption printing medium by a gravure printing method, it is possible to obtain a gravure printed matter having excellent blocking resistance while achieving both improvement in defoaming property and suppression of repelling phenomenon during gravure printing. it can.

(Print medium)
As the printing medium, a non-liquid absorbing medium such as processed paper, synthetic paper, art paper, low liquid absorbing coated paper, and resin film is preferable.
Examples of the coated paper include general-purpose glossy paper and multicolor foam gloss paper.
Examples of the resin film include a transparent synthetic resin film, and examples thereof include a resin film made of polyester, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyamide and the like, but polyester film and polypropylene film are preferable. These resin films may be a biaxially stretched film, a uniaxially stretched film, or a non-stretched film.
Among these, a corona discharge-treated polyethylene terephthalate (PET) film and a corona discharge-treated biaxially stretched polypropylene (OPP) film are more preferable from the viewpoint of improving gravure printability.

In the following production examples, examples and comparative examples, "parts" and "%" are "parts by mass" and "% by mass" unless otherwise specified. The measurement method for each physical property is as follows.

(1) Measurement of weight average molecular weight of polymer Gel permeation chromatography using a solution prepared by dissolving phosphoric acid and lithium bromide in N, N-dimethylformamide at concentrations of 60 mmol / L and 50 mmol / L, respectively, as an eluent. Molecular weight as a standard substance according to the method [GPC apparatus (HLC-8320GPC) manufactured by Tosoh Corporation, column (TSKgel SuperAWM-H, TSKgel SuperAW3000, TSKgel superAW-H) manufactured by Tosoh Corporation, flow velocity: 0.5 mL / min]. Known monodisperse polystyrene kits [PStQuick B (F-550, F-80, F-10, F-1, A-1000), PStQuick C (F-288, F-40, F-4, A-5000, A-500), manufactured by Tosoh Corporation] was used for measurement.
For the measurement sample, 0.1 g of the polymer was mixed with 10 mL of the eluate in a glass vial, stirred at 25 ° C. for 10 hours with a magnetic stirrer, and a syringe filter (DISMIB-13HP, made of PTFE, 0.2 μm, Advantech Co., Ltd.) was used. The one filtered by (manufactured by the company) was used.

(2) Measurement of average particle size of crosslinked polymer particles and resin particles containing pigment Cumulant analysis was performed using a laser particle analysis system "ELS-8000" (manufactured by Otsuka Electronics Co., Ltd.), and the average particle size was measured. A dispersion diluted with water was used so that the concentration of the particles to be measured was 5 × 10 ⁻³ % by weight (in terms of solid content concentration). The measurement conditions were a temperature of 25 ° C., an angle between the incident light and the detector of 90 °, and the number of integrations was 100 times. The refractive index of water (1.333) was input as the refractive index of the dispersion solvent, and the obtained cumulant average was obtained. The particle size was defined as the average particle size of the crosslinked polymer particles and resin particles containing the pigment.

(3) Measurement of solid content concentration Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), 5 g of the measurement sample was dried at a drying temperature of 150 ° C. After drying under the condition of width 0.05%), the water content (%) of the measurement sample was measured, and the solid content concentration was calculated by the following formula.
Solid content concentration (%) = 100-Moisture content (%) of the measurement sample

(4) Measurement of acid value of polymer In an automatic potential difference titrator (manufactured by Kyoto Denshi Kogyo Co., Ltd., electric burette, model number: APB-610), the polymer was dissolved in a titration solvent in which toluene and acetone (2: 1) were mixed. It was titrated with a 0.1N potassium hydroxide / ethanol solution by the potential difference titration method, and the inflection point on the titration curve was taken as the end point. The acid value was calculated from the titration to the end point of the potassium hydroxide solution.

(5) Measurement of boiling point of water-soluble organic solvent Measurement was performed according to JIS K2254, and the initial distillate point was taken as the boiling point.

Production Example A1 (Production of crosslinked polymer particles (A-1) containing a pigment)
(1) Weigh 236 parts of ion-exchanged water in a 2 L flask, and weigh 60 parts of a styrene-acrylic polymer (manufactured by BASF, trade name: John Krill 690, weight average molecular weight: 16500, acid value: 240 mgKOH / g), 5N water. 36.5 parts of sodium oxide solution (neutralization degree 60 mol%) was added. The mixture was stirred at 200 rpm for 2 hours using an anchor blade to obtain 332.5 parts of a polymer aqueous solution (solid content concentration 19.9%).
Put 331.7 parts of the polymer aqueous solution and 448.3 parts of ion-exchanged water in a container having a volume of 2 L and having a disper wing, and while cooling in a water bath at 0 ° C., the disper (manufactured by Asada Iron Works Co., Ltd., trade name: Ultra Disper) Was stirred at 1400 rpm for 15 minutes.
(2) Next, 200 parts of cyan pigment (CI Pigment Blue 15: 3) was added, and the mixture was stirred at 6400 rpm for 1 hour. Wet disperser (manufactured by Hiroshima Metal & Machinery Co., Ltd., trade name: Ultra Apex Mill UAM05) filled with 80% by volume of the obtained dispersion liquid with zirconia beads (manufactured by Nikkato Co., Ltd., trade name: XTZ ball, 0.3 mmφ). ), While cooling with cooling water at 5 ° C., dispersion was performed for 5 passes at a peripheral speed of 8 m / s and a flow rate of 200 g / min, and then filtration was performed using a 200 mesh wire mesh.
(3) 500 parts of the filtrate (150 parts of pigment, 45 parts of polymer) obtained in (2) above, a cross-linking agent (manufactured by Nagase ChemteX Corporation, Denacol EX-321L, trimethylolpropane polyglycidyl ether, epoxy equivalent: 129). , Water content: 27%) 9.93 parts (equivalent to 40 mol% with respect to the carboxylic acid that becomes the cross-linking reaction point contained in the acrylic acid in the polymer), Antifungal agent (Proxel LV (S) manufactured by Ronza Japan Co., Ltd.) , Effective component concentration 20%) 1.2 parts is added, and 91.6 parts of ion-exchanged water is further added, and after stirring at 70 ° C. for 3 hours, the mixture is filtered through a 200 mesh wire net and contains (encapsulates) a pigment. Crosslinked polymer particles (A-1) were obtained as an aqueous dispersion.
The yield was 602.7 parts (solid content concentration: 34.0%, pigment: 24.9%, polymer a1: 9.1%), and the average particle size was 280 nm.

Production Example A2 (Production of crosslinked polymer particles (A-2) containing a pigment)
In the same manner as in Production Example A1, the crosslinked polymer particles (A-2) containing (encapsulating) the pigment, except that 9.93 parts of the crosslinking agent was changed to 4.97 parts in (3) of Production Example A1. An aqueous dispersion was obtained.
The yield was 598.2 parts (solid content concentration: 34.0%, pigment: 25.5%, polymer a2: 8.5%), and the average particle size was 270 nm.

Production Example A3 (Production of crosslinked polymer particles (A-3) containing a pigment)
(1) Production of styrene-acrylic polymer 20 parts of methyl ethyl ketone (MEK) and 0.03 part of polymerization chain transfer agent (2-mercaptoethanol) in the reaction vessel, 10% of the total of 200 parts of each monomer shown in Table 1. Was added and mixed, and nitrogen gas substitution was sufficiently performed to obtain a mixed solution.
On the other hand, the remaining 90% of the monomers shown in Table 1 was charged into the dropping funnel, and 0.27 parts of the polymerization chain transfer agent, 60 parts of MEK and a radical polymerization initiator (2,2'-azobis (2,4-dimethylvalero)) were charged. Nitrile) and Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-65) 1.2 parts were added and mixed, and the mixture was sufficiently substituted with nitrogen gas to obtain a mixed solution.
Under a nitrogen atmosphere, the temperature of the mixed solution in the reaction vessel was raised to 65 ° C. with stirring, and the mixed solution in the dropping funnel was gradually added dropwise over 3 hours. After 2 hours have passed at 65 ° C. from the end of the dropwise addition, a solution prepared by dissolving 0.3 part of the radical polymerization initiator in 5 parts of MEK is added, and the mixture is further aged at 65 ° C. for 2 hours and 70 ° C. for 2 hours to have a weight average molecular weight of 62, A polymer solution having an acid value of 104 mgKOH / g was obtained.

The details of the compounds shown in Table 1 are as follows.
(A-2) Styrene macromer: manufactured by Toagosei Co., Ltd., trade name: AS-6 (S), number average molecular weight: 6000, polymerizable functional group: metacloyloxy group, solid content concentration 50%
(A-3) Polyethylene glycol monomethacrylate: manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: NK ester EH-4E, average number of moles of ethylene oxide added: 4, terminal: 2-ethylhexyl group.

(2) 60 parts of the polymer obtained by drying the polymer solution obtained in (1) above under reduced pressure was dissolved in 100 parts of MEK, and 18.3 parts of a 5N sodium hydroxide solution (neutralization degree 60 mol%) was dissolved therein. And 570 parts of ion-exchanged water are placed in a container having a volume of 2 L having a hydroxide wing, and 200 parts of a cyan pigment (CI pigment blue 15: 3) is further added thereto, manufactured by Primex Co., Ltd., trade name: TK Robo. Mix + TK homodisper 2.5 type at a rotation speed of 1400 rpm for 15 minutes, and fill the obtained dispersion with 80% by volume of zirconia beads (manufactured by Nikkato Co., Ltd., trade name: XTZ ball, 0.3 mmφ). Put it into a wet disperser (manufactured by Hiroshima Metal & Machinery Co., Ltd., trade name: Ultra Apex Mill UAM05), and disperse 5 passes at a peripheral speed of 8 m / s and a flow rate of 200 g / min while cooling with cooling water at 5 ° C. Filtering was performed using a 200 mesh wire net.
250 parts of ion-exchanged water was added to the obtained dispersion and stirred, and then MEK was removed at 60 ° C. under reduced pressure, a part of water was further removed, and water-insoluble polymer particles containing (encapsulating) a pigment were added. A pigment aqueous dispersion (solid content concentration 25%) in the form of the above was obtained.
780 parts of the obtained filtrate (150 parts of pigment, 45 parts of polymer) and 5 parts of a cross-linking agent (Denacol EX-321L, manufactured by Nagase ChemteX Corporation) (to a carboxylic acid to be a cross-linking reaction point contained in methacrylic acid in the polymer). (Equivalent to 40 mol%), 1.2 parts of antifungal agent (Proxel LV (S) manufactured by Ronza Japan Co., Ltd.) was added, 91.6 parts of ion-exchanged water was further added, and the mixture was stirred at 70 ° C. for 3 hours. Then, it was filtered through a 200-mesh wire net to obtain an aqueous dispersion of polymer particles (A-3) containing (encapsulating) the pigment.
The yield was 600.2 parts (solid content concentration: 34.0%, pigment: 25.5%, polymer a3: 8.5%), and the average particle size was 320 nm.

Production Example A4 (Production of non-crosslinked polymer particles containing pigment)
An aqueous dispersion of non-crosslinked polymer particles containing a pigment was obtained in the same manner as in Production Example A1 except that a cross-linking agent was not used in Production Example A1.
The yield was 592.8 parts (solid content concentration: 32.9%, pigment: 25.3%, non-crosslinked polymer: 7.6%), and the average particle size was 260 nm.

Production Example B1 (Production of water-insoluble polyurethane resin emulsion 1)
Polytetramethylene glycol (hydroxyl value: 56.1 mgKOH / g) 152 having a number average molecular weight of 2000 while introducing nitrogen gas in a reactor equipped with a thermometer, a stirrer, a reflux cooling tube, and a nitrogen gas introduction tube. 30 parts of polyethylene glycol (hydroxyl value: 56.1 mgKOH / g) having a number average molecular weight of 2000, 22 parts of 2,2-dimethylolpropionic acid, 3 parts of cyclohexanedimethanol and 84 parts of isophorone diisocyanate in 200 parts of MEK. The reaction was carried out at the boiling point to obtain a terminal isocyanate prepolymer, and then cooled to 40 ° C. and then 100 parts of MEK was added to obtain a MEK solution of the terminal isocyanate prepolymer. While cooling the obtained solution in an ice bath, an emulsion was formed by gradually adding a mixture of 38 parts of a 5N sodium hydroxide aqueous solution and 700 parts of ion-exchanged water to neutralize the solution, and further diethylenetriamine (crosslinking agent; Tokyo Kasei Kogyo). (Manufactured by Co., Ltd.) After adding 0.5 part and stirring at room temperature for 2 hours, MEK is removed under reduced pressure, further heated to 60 ° C. to distill off a part of water, and then a 200 mesh wire net is used. Emulsion 1 (weight average molecular weight: 1.1 million, acid value after cross-linking: 31 mgKOH / g) emulsion 1 having a crosslinked structure was obtained (solid content concentration: 45%, average particle size: 200 nm).

Production Example B2 (Production of water-insoluble polyurethane resin emulsion 2)
A water-insoluble polyurethane resin having a crosslinked structure (weight average molecular weight: 1 million, after cross-linking) in the same manner as in Production Example B1 except that 64 parts of hexamethylene diisocyanate was used instead of 84 parts of isophorone diisocyanate in Production Example B1. Acid value: 31 mgKOH / g) Emulsion 2 was obtained (solid content concentration: 45%, average particle size: 250 nm).

Production Example B3 (Production of an aqueous solution of a water-soluble polyurethane resin)
(1) In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser, and a nitrogen gas introduction tube, 171 parts of a condensate of neopentyl glycol and adipic acid having a molecular weight of 2000 and a number. 151 parts of a mixture of 100 parts of polytetramethylene glycol (hydroxyl value: 56.1 mgKOH / g) having an average molecular weight of 2000 and 51 parts of polypropylene glycol (hydroxyl value: 56.1 mgKOH / g) having a number average molecular weight of 2000, dimethylol propionic acid Twenty parts were charged, nitrogen gas was flowed, and the temperature was raised to 70 ° C. with stirring. Subsequently, 77 parts of isophorone diisocyanate was added, and the reaction was carried out at 90 ° C. until the content (NCO%) of the isocyanate (NCO) groups remaining in the prepolymer became 3.4%, and linear with isocyanate groups at both ends. Urethane prepolymer was obtained.
Subsequently, in a 4-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser, and a nitrogen gas introduction tube, 157 parts of ethyl acetate, 400 parts of isopropyl alcohol, 496 parts of acetone, and then isophorone diamine 30 The temperature was raised to 40 ° C. by adding 1.6 parts of dinormal butylamine. Next, 419 parts of the linear urethane prepolymer was added and reacted at 40 ° C. for 4 hours to obtain an organic solvent solution of a polyurethane resin. Next, 900 parts of deionized water containing 38 parts of a 5N sodium hydroxide aqueous solution was added and neutralized to make it water-based, and an organic solvent and a part of water were distilled off to distill off a water-soluble polyurethane resin having a solid content concentration of 45%. Was obtained.

Production Example B4 (Production of water-insoluble styrene-acrylic resin emulsion)
163 parts of ion-exchanged water was weighed in a 2 L flask, and 60 parts of the styrene-acrylic polymer (manufactured by BASF, trade name: John Krill 690) and 13.7 parts of dimethylaminoethanol (neutralizer) used in Production Example A1 were weighed. (Neutralization degree 60 mol%) was added. After stirring at 200 rpm for 2 hours at room temperature using an anchor blade, 16.3 parts of a cross-linking agent (Denacol EX-321L, manufactured by Nagase ChemteX Corporation) (carboxylic acid serving as a cross-linking reaction point contained in the acrylic acid in the polymer). (Equivalent to 40 mol%), 1.2 parts of antifungal agent (Proxel LV (S) manufactured by Lonza Japan Co., Ltd.), 37 parts of ion-exchanged water were added, and the mixture was stirred at 70 ° C. for 3 hours and then 200. The mixture was filtered through a mesh wire net to obtain a water-insoluble styrene-acrylic resin emulsion.
The yield was 200 parts (solid content concentration 45%, average particle size: 60 nm), and the acid value (after cross-linking) of the water-insoluble styrene-acrylic resin emulsion was 186 mgKOH / g.

<Preparation of water-based ink>
Example 1 (Preparation of water-based ink 1)
29.3 parts of an aqueous dispersion of the crosslinked polymer particles (A-1) containing the pigment obtained in Production Example A1 (corresponding to a pigment concentration of 7.3% in ink), and water obtained in Production Example B1. Insoluble polyurethane resin emulsion 1 (fixing resin) 33.3 parts (corresponding to 10% solid content concentration of fixing resin in ink), diethylene glycol monoisopropyl ether (iPDG) 1 part, propylene glycol 12.5 parts, silicone-based surfactant Agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KF6011, PEG-11 methyl ether dimethicone, HLB: 12) 0.5 part, acetylene glycol-based surfactant (manufactured by Nisshin Chemical Industry Co., Ltd., trade name: Surfinol) 104PG-50, 2,4,7,9-tetramethyl-5-decine-4,7-diol, 50% effective content, propylene glycol solution, HLB: 3) 1.0 part, and thickener (Co., Ltd.) Made by ADEKA, trade name: Adecanol UH-420, effective content 30% aqueous solution) 0.5 parts and the amount of ion-exchanged water adjusted to add 100 parts as a whole, and the Zahn cup viscosity (No. 3) is 21 After adjusting so as to be ± 1 second per second, the mixture was filtered through a stainless wire mesh (200 mesh) to obtain water-based ink 1.
The results are shown in Table 2. The amount of each component in Table 2 is an effective amount.

Examples 2 to 13 and Comparative Examples 1 to 8 (preparation of water-based inks 2 to 13 and 21 to 28)
In Example 1, water-based inks 2 to 13 and 21 to 28 were obtained in the same manner as in Example 1 except that the ink composition was changed as shown in Table 2. The results are shown in Table 2.

The details of the water-soluble organic solvent in Table 2 are as follows.
-MTG: Triethylene glycol monomethyl ether (boiling point 248 ° C)
BDG: Ethylene glycol monobutyl ether (boiling point 230 ° C)
-IBDG: Diethylene glycol monoisobutyl ether (boiling point 220 ° C)
-IPDG: Diethylene glycol monoisopropyl ether (boiling point 207 ° C)
MDG: Diethylene glycol monomethyl ether (boiling point 194 ° C)
The above water-soluble organic solvents are all reagents manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
The carbodiimide-based curing agent is carbodilite E-02 (effective content 40%) manufactured by Nisshinbo Chemical Co., Ltd.

Using the water-based inks obtained in Examples and Comparative Examples, the defoaming property, repelling property, and blocking resistance were evaluated by the methods shown below. The results are shown in Table 2.

<Evaluation of defoaming property>
Put 30 g of water-based ink in each 50 mL screw tube, lay the screw tube sideways, and shake with a multi-shaker (manufactured by Tokyo Rika Kikai Co., Ltd., product name: MMS-210) at 150 rpm for 300 seconds. The time until defoaming was visually measured, and the defoaming property was evaluated according to the following evaluation criteria.
The shorter the time until defoaming, the better the defoaming property and the better the practical use.
(Evaluation criteria)
5: Defoaming time is less than 5 seconds 4: Defoaming time is 5 seconds or more and less than 10 seconds 3: Defoaming time is 10 seconds or more and less than 30 seconds 2: Defoaming time is 30 seconds or more Less than 60 seconds 1: If the time to defoaming is 60 seconds or more and the evaluation standard is 3 or more, there is no practical problem in defoaming property.

<Evaluation of repellentness>
Using water-based ink, apply to the corona discharge-treated surface of OPP film (manufactured by Futamura Chemical Co., Ltd., trade name: FOR-AQ # 20, laminate grade) with an applicator at a wet film thickness of 0.076 mm (7 cm x 10 cm). ), The number of repellent marks immediately after application was counted, and the repellent property was evaluated by the number.
When the number of repellent marks is close to 0, the repellent is small and it is practically superior.

<Evaluation of blocking resistance>
Printing was performed on the corona discharge-treated surface of the OPP film (manufactured by Futamura Chemical Co., Ltd., trade name: FOR-AQ # 20, laminate grade) using a water-based ink.
For printing, a desktop gravure printing test machine (manufactured by Matsuo Sangyo Co., Ltd., product name: K printing proofer) is used to perform gradation printing with a laser plate-making gravure 250 line, 8 μm plate (manufactured by Nabe Process Co., Ltd.). went. The obtained printed matter was subsequently dried in a dryer (Yamato Scientific Co., Ltd., trade name: Drying Oven DSV402) set at 60 ° C. for 10 minutes.
A 100% gradation part of the obtained printed matter is cut out, an unused OPP film is overlapped, ^{a load of 1 kg / cm 2} is applied from above, and the mixture is held at 20 ° C. for 12 hours, 24 hours, and 36 hours. After holding for 48 hours, the OPP film was peeled off, the peeled state of the ink was confirmed, and the blocking resistance was evaluated according to the following evaluation criteria.
(Evaluation criteria)
No ink peeling even after leaving for 5:48 hours.
Ink peels off after being left for 4:48 hours, but the area ratio is 5% or less.
Ink peels off after being left for 3:36 hours.
Ink peels off after being left for 2:24 hours.
Ink peels off after being left for 1:12 hours.
If the evaluation result is 3 or more, there is no practical problem in blocking resistance.

From Table 1, the water-based ink of the example has both improved defoaming property and suppression of the cissing phenomenon as compared with the water-based ink of the comparative example, has excellent blocking resistance, and can obtain a high-quality printed matter. I know I can do it.

Claims (7)

A water-based gravure ink containing pigment-containing crosslinked polymer particles, water-insoluble polyurethane resin, water-soluble organic solvent, surfactant, and water.
The water-soluble organic solvent contains a compound represented by the following general formula (I) and contains.
R ¹ O- (C ₂ H ₄ O) _n- H (I)
(In the formula, R ¹ indicates an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms, and n indicates the number of added moles and is 2 or 3.)
The content of the compound represented by the general formula (I) is 0.5% by mass or more and 11% by mass or less.
A water-based gravure ink having a water content of 55% by mass or more and 70% by mass or less. The water-based gravure ink according to claim 1, wherein the polymer constituting the crosslinked polymer particles is a vinyl polymer. Claim 1 or 2 in which the compound represented by the general formula (I) is at least one selected from diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol monomethyl ether. The water-based gravure ink described in. The aqueous gravure ink according to any one of claims 1 to 3, wherein the surfactant contains at least one selected from an acetylene glycol-based surfactant and a silicone-based surfactant. The water-based gravure ink according to any one of claims 1 to 4, further comprising a carbodiimide-based curing agent. A gravure printing method for printing on a low liquid absorption printing medium using the water-based gravure ink according to any one of claims 1 to 5. The gravure printing method according to claim 6, wherein the low liquid absorption printing medium is a resin film.