JP5500410B1 - Water-based ink set for inkjet recording - Google Patents

Abstract

  An ink set for ink jet recording using at least two kinds of inks, wherein the first ink contains a coloring material, a resin having a hydroxy group and / or a carboxyl group, a water-soluble solvent and / or water, The ink is at least one polymer selected from the group consisting of vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), and core-shell amphoteric emulsion polymer (C), A water-based ink set for ink jet recording, comprising a water-soluble solvent and / or water.

Description

  The present invention relates to a water-based ink set for inkjet recording.

  Printing with an inkjet printer recording device is a method that ejects ink from nozzles and adheres to the recording material. Unlike conventional printing methods, this is a printing method that does not use a plate, so on-demand printing that can accommodate a small variety of products This printing method is expected to be used in a wide range of fields. Particularly in recent years, as a recording material, there have been many studies on printing on a non-absorbing substrate such as plastic from printing on a conventional absorbing substrate such as paper, and printing using pigment inks from the viewpoint of weather resistance, among others. Is being studied.

  In the case of printing using a plastic film as the recording material, since the plastic is non-absorbent, the use of water-based ink significantly reduces the drying property, resulting in non-uniform spreading of the ink when the ink is deposited. As a result, there are problems such as blurring of images such as bleeding and intercolor bleeding, and deterioration in image quality due to failure to obtain good color development. For this reason, usually, a receiving layer is provided on a plastic film (for example, refer to Patent Document 1). However, the surface of the plastic film has poor adhesion to the ink-jet ink, and a layer usually called an anchor layer, primer layer, undercoat layer, adhesive layer, etc. is formed on the film surface, and polyurethane, polyacryl, etc. The step of providing an ink receiving layer containing as a main component was essential. Such a surface treatment process not only leads to an increase in cost, but also requires a lot of time for production because the number of processes increases.

On the other hand, as a printing method of an aqueous inkjet recording method that is excellent in image quality and abrasion resistance and excellent in discharge stability regardless of ink absorption of the recording medium with respect to a non-absorbing substrate such as plastic, color ink, resin A printing method for printing an image by applying ink and reactive ink is known (see, for example, Patent Document 2). Specifically, a color ink containing a water-insoluble colorant, a water-soluble and / or water-insoluble resin component, a water-soluble solvent, and a surfactant, a water-soluble resin solvent, and water-soluble but not soluble in water. The resin resin solvent contains thermoplastic resin particles that are compatible, and the total content of the resin particles is greater than or equal to the content of the colorant contained in the color ink; a polyvalent metal salt; Three inks of a reactive agent selected from allylamine and its derivatives and a reactive ink containing a surfactant are applied to form an image.
However, this method must prepare at least three kinds of inks, and requires an ink jet apparatus having a high degree of ejection accuracy.

  Also, as a two-component printing method using two kinds of inks, a step of applying a liquid composition containing a cationic substance and an ink containing an anionic substance to a recording medium so as to contact each other on the recording medium There is known a method of eliminating image disturbance such as bleeding and intercolor bleeding by a printing method having a color (for example, see Patent Document 3). However, even in this method, as described above, although subtle gradations can be reproduced with an absorbing base material such as paper, there is a problem in that image disturbance still cannot be eliminated by printing on a non-absorbing base material such as plastic. It remained.

Japanese Patent Laid-Open No. 10-119428 JP 2010-115854 A JP 2000-43399 A

  An object of the present invention is to provide a two-component water-based ink set for ink-jet recording that is excellent in abrasion resistance immediately after printing without causing image disturbance such as bleeding and intercolor bleeding even when printed on a plastic film. .

  The present inventors have prepared a first pigment ink containing a resin having a hydroxy group and / or a carboxyl group, vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer ( B) and at least one polymer selected from the group consisting of a core-shell amphoteric emulsion polymer (C), a water-soluble solvent and / or a second ink containing water, and a two-component water-based ink set for inkjet recording By doing so, the above-mentioned problems were solved.

  That is, the present invention is an ink set for ink jet recording using at least two kinds of inks, and the first ink contains a color material, a resin having a hydroxy group and / or a carboxyl group, a water-soluble solvent and / or water. And the second ink is selected from the group consisting of vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), and core-shell amphoteric emulsion polymer (C). An aqueous ink set for ink jet recording comprising at least one polymer, a water-soluble solvent and / or water is provided.

  According to the present invention, it is possible to provide an aqueous ink set for ink jet recording that gives a printed matter that is excellent in abrasion resistance immediately after printing without causing image distortion such as bleeding or intercolor bleeding even when printed on a plastic film.

In the water-based ink set for inkjet recording of the present invention, the first ink is an ink containing a color material, a resin having a hydroxy group and / or a carboxyl group, a water-soluble solvent and / or water, and the second ink is vinyl. At least one polymer selected from the group consisting of pyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), and core-shell amphoteric emulsion polymer (C), a water-soluble solvent, and Ink containing water.
By overprinting both inks, the ink is quickly fixed to the substrate. As a result, it is possible to obtain an ink which is free from image disturbance such as bleeding and intercolor bleeding and has excellent abrasion resistance immediately after printing.

Although the mechanism is not clear about fast fixing with respect to a printing material by overprinting both inks, the following is estimated.
At least one polymer selected from the group consisting of vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), and core-shell amphoteric emulsion polymer (C) Contains a cationic group. The polymer becomes a trigger and grows into a large aggregate by intermolecular hydrogen bonding of a resin having a hydroxy group and / or a carboxyl group, and is bundled into a network by interaction such as van der Waals force. There is a possibility that entanglement interferes with movement and loses fluidity and is fixed on the surface of the printed matter. Alternatively, there is a possibility that a resin having a hydroxy group and / or a carboxyl group present in the first ink reacts with the polymer present in the second ink and is immobilized on the surface of the printed material.

(First Ink Resin having a hydroxy group and / or a carboxyl group)
The first ink used in the present invention contains a color material, a resin having a hydroxy group and / or a carboxyl group, a water-soluble solvent and / or water.

  The resin having a hydroxy group and / or carboxyl group is not particularly limited as long as a conventionally known resin having a hydroxy group and / or carboxyl group may be used.

The resin having a hydroxy group and / or a carboxyl group in the present invention may have a resin having at least a hydroxy group and / or a carboxyl group. The acquisition form of the resin which has the said carboxyl group is not specifically limited. In view of ease of handling, a dispersion of a resin in a water-soluble solvent and / or water, that is, a so-called resin emulsion is preferably used rather than a solid. Commercially available resin emulsions may also be used.
Among these, a resin characterized in that resin particles of polyolefin resin, polyester resin, polyester urethane resin, acrylic resin, vinyl chloride resin, vinyl acetate resin, or epoxy resin are dispersed in a water-soluble solvent and / or water. An emulsion is preferable, and a resin emulsion in which resin particles of a polyolefin resin are dispersed in a water-soluble solvent and / or water is more preferable.

  The content (% by mass) of the resin having a hydroxy group and / or a carboxyl group in the first ink is 2.0% by mass or more and 15.0% by mass or less based on the total mass of the ink. Preferably, 3.0 mass% or more and 8.0 mass% or less are still more preferable, and 3.0 mass% or more and 5.0 mass% or less are still more preferable.

The acid value of the resin having a hydroxy group and / or a carboxyl group is preferably 10 to 200 mgKOH / g per resin solid content. If the acid value is less than 10 mgKOH / g, the storage stability of the ink may be inferior. On the other hand, when the acid value exceeds 200 mgKOH / g, physical properties such as preferable durability and water resistance may not be obtained.
More preferably, it is the range of 5-100 mgKOH / g, More preferably, it is the range of 10-80 mgKOH / g, More preferably, it is the range of 15-60 mgKOH / g.

The hydroxyl value of the resin having a hydroxy group and / or a carboxyl group is preferably 30 mgKOH / g or less per resin solid content. If the hydroxyl value exceeds 30 mgKOH / g, the storage stability of the ink may be inferior. More preferably, it is 20 mgKOH / g or less, More preferably, it is 10 mgKOH / g or less.
In addition, the acid value and hydroxyl value here are the values measured by the method based on JIS0070.

  Moreover, it is preferable to set suitably the glass transition temperature (henceforth Tg) of resin which has the said hydroxyl group and / or carboxyl group according to the desired use. For example, when printing on a plastic film having flexibility such as for packaging materials for foods, flexibility (flexibility) is required, so that Tg is preferably not so high. In order to achieve both good adhesion to an appropriate film and flexibility, the Tg of the resin having a hydroxy group and / or a carboxyl group is preferably in the range of -80 ° C to 80 ° C, and -80 ° C to A range of 30 ° C. is particularly preferable.

The resin having a hydroxy group and / or carboxyl group has a weight average molecular weight (polystyrene conversion) of 10,000 or more and 1,000,000 or less, more preferably 20,000 or more and 700,000 or less. This is preferable because a physical property balance is easily developed.
In addition, the weight average molecular weight (Mw) here shall be calculated | required by GPC measurement on the following conditions.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “SuperHZ-L” manufactured by Tosoh Corporation (inner diameter 4.6 mm × 2 cm)
+ Tosoh Corporation “TSKgel SuperHZ4000” (inner diameter 4.6 mm × 15 cm)
+ Tosoh Corporation “TSKgel SuperHZ3000” (inner diameter 4.6 mm × 15 cm)
+ "TSKgel SuperHZ2000" manufactured by Tosoh Corporation (inner diameter 4.6 mm x 15 cm)
+ Tosoh Corporation “TSKgel SuperHZ1000” (inner diameter 4.6 mm × 15 cm)
Measurement conditions: Column temperature 40 ° C
Flow rate 0.35 ml / min Sample: A resin aqueous solution was dried and solidified, and a 0.5 mass% tetrahydrofuran (THF) solution in terms of resin solid content was filtered through a microfilter (10 μl).
Calibration curve: Monodisperse standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) A calibration curve with samples having a molecular weight of 4000000 to 250 was used.

In the case of a resin composition in which the resin having a hydroxy group and / or carboxyl group used in the present invention is dispersed in a water-soluble solvent and / or water, so-called resin emulsion, if the average particle size is too large, the cause of head clogging is caused. It causes discharge failure. Therefore, it is preferable that the average particle size of the resin particles having a hydroxy group and / or a carboxyl group is as small as possible because the influence on ejection failure is small. Specifically, the range of 10 nm to 500 nm is preferable, and the range of 10 to 300 nm is particularly preferable.
Here, the particle diameter can be measured by a known and common centrifugal sedimentation method, laser diffraction method (light scattering method), ESA method, capillary method, electron microscope method, or the like. Preferable is measurement by Microtrac UPA using a dynamic light scattering method.

  The resin emulsion that can be used in the ink of the present invention may contain an emulsifier without particular limitation as long as the desired physical properties are not impaired. For example, it may be a resin emulsion obtained by a method of dropping a monomer and a polymerization initiator in the presence of an emulsifier and polymerizing, or an emulsification method by stirring an aqueous solution or suspension of a resin. Of course, resin emulsions without addition of an emulsifier may be obtained by making full use of various emulsification / dispersion techniques such as an ultrasonic irradiation technique. As emulsifiers, nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene alkyl ether carboxylates, dialkyl sulfosuccinates, water-soluble acrylic resins Carboxylic acid types such as polycarboxylic acid salts, sulfonic acid types such as alkylbenzene sulfonates, anionic emulsifiers such as alcohol sulfate esters and alkylallyl sulfonates.

The polyolefin resin in the present invention has a polar group such as an amino group, a carboxyl group, and a hydroxyl group via a covalent bond to a hydrophobic polyolefin skeleton within a range that does not impair the effects of the present invention, depending on the desired physical properties, It can be set as the modified polyolefin which introduce | transduced the polymer chain.
As a method for producing a modified polyolefin, that is, a method for introducing a polar group or a polymer chain via a covalent bond to a polyolefin skeleton, a method for polymerizing a monomer having a polar group in the presence of a polyolefin, or a method for polymerizing a polymer chain into a polyolefin. Examples of the method include bonding. Depending on the properties of the target resin emulsion, the types and combinations of polyolefins, polar group-containing monomers and polymer chains can be appropriately selected. In other words, the chemical structure classification of the modified polyolefin is not particularly limited, and may be any of a random copolymer, a block copolymer, a graft modified product, and the like. As the polyolefin, any of a polyolefin having no reactive group or a polyolefin having a reactive group can be used.

  As the polyolefin having no reactive group, various known polyolefins and modified polyolefins can be used, and are not particularly limited. For example, ethylene or propylene homopolymer, ethylene / propylene copolymer, ethylene or / And copolymers of propylene and other comonomers. Examples of the comonomer include α-olefin comonomers having 2 or more carbon atoms such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, and norbornene. The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 8 carbon atoms, more preferably an α-olefin comonomer having 2 to 6 carbon atoms, and still more preferably an α-olefin comonomer having 2 to 4 carbon atoms. It is.

  Alternatively, two or more kinds of these α-olefin comonomers can also be used. Also, a hydrogenated product of a copolymer of two or more monomers selected from a copolymer of an α-olefin monomer and a comonomer such as vinyl acetate, acrylic acid ester, and methacrylic acid ester, and an aromatic vinyl monomer and a conjugated diene monomer. , Etc. can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer. The polyolefin may be linear or branched.

  Furthermore, chlorinated polyolefins obtained by chlorinating these polyolefins can also be used. The chlorination degree of the chlorinated polyolefin is usually 5% by weight or more, preferably 10% by weight or more, and the chlorination degree is usually 50% by weight or less, preferably 30% by weight or less. However, for the purpose of reducing the environmental load, it is desirable that the polyolefin does not substantially contain chlorine. The phrase “substantially containing no chlorine” means, for example, that the chlorination rate of polyolefin is less than 5% by weight.

  Examples of the polyolefin having a reactive group include a copolymer obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polyolefin polymerization, or radical polymerization having a reactive group. A polymer obtained by graft polymerization of a polymerizable unsaturated compound onto a polyolefin, or a polymer obtained by converting a polyolefin having an unsaturated end group into an element group of group 13 to group 17 can be used.

  Examples of the reactive group include a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, and the like, and a carboxylic acid group and a dicarboxylic acid anhydride group. And a dicarboxylic anhydride monoester group is more preferred. Carboxylic acid groups, dicarboxylic acid anhydride groups, and dicarboxylic acid anhydride monoester groups are not only highly reactive and easy to bond with hydrophilic polymers, but also contain many unsaturated compounds having these groups and are common to polyolefins. This is because polymerization or graft reaction is also easy, and so-called acid-modified polyolefin resins in which polyolefin has these groups are excellent in water dispersibility.

A copolymer obtained by copolymerizing an unsaturated compound having no reactive group at the time of polyolefin polymerization and an unsaturated compound having a reactive group is a copolymer in which an unsaturated compound having a reactive group is inserted into the main chain. It is. For example, α-olefin such as ethylene, propylene, butene, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid (dimethylamino) ) Ethyl, (meth) acrylic acid (2-isocyanato) ethyl, and α, β-unsaturated carboxylic acid such as maleic anhydride, the same ester or anhydride. (In the present invention, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”).)
Specific examples of these copolymers include propylene-butene-maleic anhydride copolymers. These may be used individually by 1 type and may be used in combination of 2 or more type. Of course, it is also possible to use a commercially available product.

  A polymer obtained by graft-polymerizing a radically polymerizable unsaturated compound having a reactive group to a polyolefin is obtained by graft-polymerizing a radically polymerizable unsaturated compound having a reactive group to a previously polymerized polyolefin. The unsaturated compound it has is grafted to the main chain. For example, polyolefins such as polyethylene and polypropylene, (meth) acrylic acid, fumaric acid, maleic acid or anhydride thereof, itaconic acid or anhydride thereof, crotonic acid, 2-hydroxyethyl (meth) acrylate and (meth) acrylic acid It is a polymer grafted with 2-hydroxypropyl, (meth) acrylamide, (meth) acrylic acid (dimethylamino) ethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid (2-isocyanato) ethyl, or the like. These may be used individually by 1 type and may be used in combination of 2 or more type. As polyolefin of this reaction, the polyolefin which does not have the above-mentioned reactive group can be used.

  Specific examples of a polymer obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group onto a polyolefin include, for example, maleic anhydride-modified polypropylene and its chlorinated product, maleic anhydride-modified propylene-ethylene copolymer and its chlorine. , A maleic anhydride modified propylene-butene copolymer and its chlorinated product, an acrylic acid modified polypropylene and its chlorinated product, an acrylic acid modified propylene-ethylene copolymer and its chlorinated product, an acrylic acid modified propylene-butene copolymer and Examples thereof include chlorinated substances. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The radical polymerization initiator used in the graft polymerization can be appropriately selected from ordinary radical initiators, such as organic peroxides such as benzoyl peroxide and t-butylperoxyisopropyl monocarbonate, azonitrile, etc. Can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

  A method for producing a polymer obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group onto a polyolefin is not particularly limited, and any production method may be used. For example, solution modification method (method of reacting by heating and stirring in a solution), melt modification method (method of reacting by melting and heating and stirring without a solvent, or method of reacting by heating and kneading with an extruder), etc. It is done.

  A polymer obtained by converting a polyolefin having an unsaturated end group into an element group of group 13 to group 17 is, for example, a double bond of a polyolefin having a terminal double bond as described in JP-A-2001-288372. A polyolefin having part thereof converted into a group 13 element group such as a boron group or an aluminum group, and a double bond part of a polyolefin having a terminal double bond as described in JP-A-2005-48172 is converted to a halogen element. Polyolefin, a polyolefin obtained by converting a double bond portion of a propylene-based polymer having a terminal double bond into a mercapto group as described in JP-A-2001-98140 can be used. Usually, a block copolymer is used as a block copolymer. Can be obtained.

  The polymer chain to be introduced into the hydrophobic polyolefin skeleton via a covalent bond can be used without particular limitation as long as the effects of the present invention are not impaired, depending on the desired physical properties. It may be linear or branched. For example, synthetic polymer such as poly (meth) acrylic resin, polyester resin, polyether resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, semi-synthetic polymer such as cationic starch, dextrin, hydroxyethyl cellulose, agar, gum arabic, gelatin, etc. Any of these natural polymers can be used. The polymer chain may have a reactive group.

  For the polymer chain, it is preferable to use a synthetic polymer because stable physical properties are easily obtained. Among these, poly (meth) acrylic resins, polyester resins, polyether resins, polyvinyl alcohol resins, and polyvinylpyrrolidone resins are more preferable, and amphiphilic polyether resins are even more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The poly (meth) acrylic resin used for the polymer chain is obtained by polymerizing an unsaturated carboxylic acid or an ester or anhydride thereof by radical polymerization, anionic polymerization, or cationic polymerization. Examples of the unsaturated carboxylic acid or ester or anhydride thereof include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, and (meth) acrylic acid (dimethyl). Amino) ethyl, (meth) acrylic acid (2-isocyanato) ethyl, maleic anhydride and the like. In addition, depending on the desired physical properties, a hydrophobic radical polymerizable compound (hydrophobic monomer) is used in order to provide good adhesion to various thermoplastic resin film substrates within a range that does not impair the effects of the present invention. Can be copolymerized. Examples of the copolymerizable hydrophobic monomer include a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group, and a hydrocarbon group having 1 to 12 carbon atoms. Examples thereof include polymerizable vinyl monomers.

  The polyvinyl alcohol resin used for the polymer chain can be usually obtained by polymerizing vinyl acetate to obtain polyvinyl acetate and then saponifying. The saponification degree may be complete saponification or partial saponification. Moreover, the polyvinyl pyrrolidone resin used for the polymer chain can be obtained by polymerizing vinyl pyrrolidone. Of course, a commercially available product may be used.

  The method for introducing the polymer chain into the polyolefin is not particularly limited. For example, a method of radical polymerization in the presence of a polyolefin, an acrylic system having a reactive group such as a hydroxyl group, an amino group, a glycidyl group, or an (anhydrous) carboxylic acid group. Examples thereof include a method of reacting a resin with a polyolefin having a reactive group.

  A polyether resin having amphiphilic properties used as a polymer chain introduced into a hydrophobic polyolefin skeleton via a covalent bond can be obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine. The method for bonding with polyolefin is not particularly limited. For example, a method of ring-opening polymerization of cyclic alkylene oxide in a polyolefin having a reactive group, a reaction of polyether polyol or polyether amine obtained by ring-opening polymerization, etc. Examples thereof include a method of reacting a polyether resin having a reactive group with a polyolefin having a reactive group.

Polyetheramine is a compound having a primary amino group as a reactive group at one or both ends of a resin having a polyether skeleton. As the polyetheramine, Jeffamine M series, D series, ED series, etc. manufactured by Huntsman, USA may be used.
Polyether polyol is a compound having hydroxyl groups as reactive groups at both ends of a resin having a polyether skeleton. Preferred examples of the polyalkylene oxide and polyalkyleneimine exhibiting hydrophilicity include polyethylene oxide, polypropylene oxide, and polyethyleneimine.

One or more reactive groups may be used, but it is more preferable to have only one reactive group. This is because when there are two or more reactive groups, there is a possibility that a three-dimensional network structure will be formed upon bonding with the polyolefin, resulting in gelation. However, even if it has a plurality of reactive groups, the gelation described above can be avoided if there is only one reactive group having a higher reactivity than others. For example, a hydrophilic polymer having a plurality of hydroxyl groups and one amino group having a higher reactivity is one preferred example. The reactivity here is the reactivity with the reactive group which polyolefin has.
As the polyolefin resin in the present invention, an olefin resin marketed as an aqueous dispersion can be preferably used. For example, the Hardren series manufactured by Toyobo Co., Ltd., the Aptolock series manufactured by Mitsubishi Chemical Corporation, the Allobase series manufactured by Unitika Ltd., etc. can be used.

(First ink coloring material)
The color material used in the present invention is not particularly limited, and color materials usually used in water-based inkjet inks can be used, and examples thereof include pigments and dyes.
If the application requires weather resistance and water resistance, it is preferable to use a pigment. As the pigment, known and commonly used organic pigments or inorganic pigments can be used.

The pigment used in the present invention is at least one pigment selected from known and commonly used organic pigments or inorganic pigments. In addition, the present invention can be applied to either an untreated pigment or a treated pigment.
In the case of printing using plastic as a recording material, as ink-jet ink, in addition to yellow ink, cyan ink, magenta ink, black ink, etc., white ink is also used for the purpose of improving visibility. These pigments used are not particularly limited, and those usually used as pigments for water-based inkjet recording inks can be used. Specifically, it can be dispersed in water or a water-soluble organic solvent, and a known inorganic pigment or organic pigment can be used. Examples of the inorganic pigment include carbon black produced by a known method such as iron oxide, a contact method, a furnace method, and a thermal method. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelates, acidic dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like.

  For example, the pigment used in the black ink is carbon black, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200B, no. 900, no. 960, no. 980, no. 33, no. 40, No, 45, No. 45L, no. 52, HCF88, MA7, MA8, MA100, etc. are Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. manufactured by Columbia, Regal 400R, Regal 330R, Regal 660R, Mull 660R, Mull 660R Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. are Degussa's Color Black FW1, FW2, FW2V, FW18, FW200, S170, U, S150, S35, P , V, 1400U, Special Bla k 6, the 5, 4, 4A, NIPEX150, NIPEX160, NIPEX170, NIPEX180 and the like.

  Specific examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.

  Specific examples of pigments used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, etc. It is done.

  Specific examples of pigments used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, 63, 66, and the like.

  Specific examples of pigments used in white inks include silicas such as alkaline earth metal sulfates, carbonates, finely divided silicic acids, synthetic silicates, calcium silicates, alumina, alumina hydrates, Examples thereof include titanium oxide, zinc oxide, talc, and clay. The inorganic white pigment may be surface-treated by various surface treatment methods.

  Examples of the dye include C.I. I. Acid Black 1, 2, 7, 16, 17, 24, 26, 28, 31, 41, 48, 52, 58, 60, 63, 94, 107, 109, 112, 118, 119, 121, 122, 131, 155, 156; C.I. I. Acid Yellow 1, 3, 4, 7, 11, 12, 13, 14, 17, 18, 19, 23, 25, 29, 34, 38, 40, 41, 42, 44, 49, 53, 55, 59, 61, 71, 72, 76, 78, 79, 99, 111, 114, 116, 122, 135, 142, 161, 172; I. Acid Orange 7, 8, 10, 19, 20, 24, 28, 33, 41, 45, 51, 56, 64; C.I. I. Acid Red 1, 4, 6, 8, 13, 14, 15, 18, 19, 21, 26, 27, 30, 32, 34, 35, 37, 40, 42, 44, 51, 52, 54, 57, 80, 82, 83, 85, 87, 88, 89, 92, 94, 97, 106, 108, 110, 111, 114, 115, 119, 129, 131, 133, 134, 135, 143, 143: 1, 144, 152, 154, 155, 172, 176, 180, 184, 186, 187, 249, 254, 256, 289, 317, 318; I. Acid Violet 7, 11, 15, 34, 35, 41, 43, 49, 51, 75; C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 49, 51, 53, 55, 56, 59, 62, 78, 80, 81, 83, 90, 92, 93, 102, 104, 111, 113, 117, 120, 124, 126, 138, 145, 167, 171, 175, 183, 229, 234, 236, 249; I. Acid Green 3, 9, 12, 16, 19, 20, 25, 27, 41, 44; C.I. I. Acid dyes such as Acid Brown 4 and 14,

  C. I. Basic Black 2.8; C.I. I. Basic yellow 1, 2, 11, 12, 14, 21, 32, 36; I. B. Basic Orange 2, 15, 21, 22; C.I. I. Basic Red 1, 2, 9, 12, 13, 37; I. B. Basic violet 1, 3, 7, 10, 14; I. Basic blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29; I. Basic green 1, 4; basic dyes such as basic brown 1 and 12,

  C. I. Direct Black 2, 4, 9, 11, 14, 17, 19, 22, 27, 32, 36, 38, 41, 48, 49, 51, 56, 62, 71, 74, 75, 77, 78, 80, 105, 106, 107, 108, 112, 113, 117, 132, 146, 154, 168, 171, 194; C. Direct Yellow 1, 2, 4, 8, 11, 12, 24, 26, 27, 28, 33, 34, 39, 41, 42, 44, 50, 51, 58, 72, 85, 86, 87, 88, 98, 100, 110, 127, 135, 141, 142, 144; C.I. I. Direct orange 6, 8, 10, 26, 29, 41, 49, 52, 102; C.I. I. Direct Red 1, 2, 4, 8, 9, 11, 13, 15, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 47, 48, 51, 59, 62, 63, 73, 75, 77, 80, 81, 83, 84, 85, 87, 89, 90, 94, 95, 99, 101, 108, 110, 145, 189, 197, 220, 224, 225, 226, 227, 230, 250, 254, 256, 257; I. Direct violet 1, 7, 9, 12, 35, 48, 51, 90, 94; I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 34, 69, 70, 71, 72, 75, 76, 78, 80, 81, 82, 83, 86, 90, 98, 106, 110, 110, 120, 123, 158, 163, 165, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 218, 236, 237, 239, 246, 258, 287; Direct Green 1, 6, 8, 28, 33, 37, 63, 64; C.I. I. Direct dyes such as direct brown 1A, 2, 6, 25, 27, 44, 58, 95, 10, 101, 106, 112, 173, 194, 195, 209, 210, 211,

  C. I. Reactive black 1, 3, 5, 6, 8, 12, 14; I. Reactive yellow 1, 2, 3, 13, 14, 15, 17; I. Reactive Blue 2, 5, 7, 16, 20, 24; Reactable Red 6, 7, 11, 12, 15, 17, 21, 23, 24, 35, 36, 42, 63, 66, 84, 184; C . I. Reactive violet 2, 4, 5, 8, 9; I. Reactive Blue 2, 5, 7, 12, 13, 14, 15, 17, 18, 19, 20, 21, 25, 27, 28, 37, 38, 40, 41; C.I. I. Reactive dyes 5, 7; reactive dyes such as Reacteve Brown 1, 7, 16, etc.

  C. I. Food black 1, 2; C.I. I. Food yellow 3, 4, 5; C.I. I. Food Red 2, 3, 7, 9, 14, 52, 87, 92, 94, 102, 104, 105, 106; C.I. I. Food violet 2; C.I. I. Food Blue 1, 2; I. Examples include food dyes such as Food Green 2 and 3.

In the present invention, a so-called self-dispersing pigment (surface-treated pigment) having a water dispersibility-imparting group on the pigment surface and capable of stably maintaining the dispersion state without a dispersant may be used. So-called capsule pigments (water-dispersible polymer-containing pigments) that can be stably maintained without a dispersant, or pigments dispersed with a dispersant may be used.
The average particle size of the pigment is preferably a particle size usually used for inkjet inks, specifically 50 to 500 nm is preferable, and 50 to 300 nm is more preferable for color ink.

The pigment may be dispersed in water using a known and commonly used pigment dispersant or binder, or a surfactant may be used.
The pigment dispersant is preferably an aqueous resin, and preferable examples include acrylic resins such as polyvinyl alcohols, polyvinyl pyrrolidones, and acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, and styrene-methacrylic acid. Styrene-acrylic such as copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer Examples include resins, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and salts of the aqueous resins.
The compounds for forming the copolymer salt include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, Examples include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, and morpholine. The amount of the compound used to form these salts is preferably equal to or greater than the neutralization equivalent of the copolymer.
Of course, it is also possible to use a commercial item. As a commercially available product, Ajinomoto Fine Techno Co., Ltd. product Ajisper PB series, Big Chemie Japan Co., Ltd. Disperbyk series, BYK-series, Ciba Specialty Chemicals EFKA series, etc. can be used.

(First ink, water-soluble solvent and / or water)
The water-soluble solvent and / or water used in the present invention may be water alone or a mixed solvent composed of water and a water-soluble solvent. Examples of the water-soluble solvent include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone; methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-methoxyethanol, Alcohols such as tetrahydrofuran; 1,4-dioxane; 1,2-dimethoxyethane; and the like; amides such as dimethylformamide and N-methylpyrrolidone; And a compound selected from the group consisting of alcohols having 1 to 5 carbon atoms.

(First ink production method)
The first ink used in the present invention is to prepare a dispersion (pigment paste) of the pigment, dilute it with water, add the resin having the hydroxy group and / or carboxyl group, and wet as necessary. An ink can be prepared by adding an agent (drying inhibitor), a penetrating agent, or other additives.

(Pigment paste)
As a method for preparing the pigment paste, the following method can be employed.
(1) A method of preparing a pigment paste by adding a pigment to an aqueous medium containing a pigment dispersant and water and then dispersing the pigment in the aqueous medium using a stirring / dispersing device.
(2) The pigment and the pigment dispersant are kneaded using a kneader such as two rolls or a mixer, and the resulting kneaded product is added to an aqueous medium containing water, and the pigment is then mixed using a stirring / dispersing device. A method of preparing a paste.
(3) After adding a pigment to a solution obtained by dissolving a pigment dispersant in an organic solvent compatible with water such as methyl ethyl ketone and tetrahydrofuran, the pigment is added to the organic solution using a stirring / dispersing device. And then phase-emulsifying using an aqueous medium, and then the organic solvent is distilled off to prepare a pigment paste.

The kneader is not particularly limited, and examples thereof include a Henschel mixer, a pressure kneader, a Banbury mixer, and a planetary mixer. Also, the stirring / dispersing device is not particularly limited, and examples thereof include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, an SC mill, and a nanomizer.
One of these may be used alone, or two or more devices may be used in combination.

  The amount of pigment in the pigment paste is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass. When the pigment amount is less than 5% by mass, the water-based ink prepared from the pigment paste is insufficiently colored, and a sufficient image density tends not to be obtained. On the other hand, when the amount is more than 60% by mass, the dispersion stability of the pigment tends to decrease in the pigment paste.

  In addition, in the ink preparation example, coarse particles cause nozzle clogging and other image characteristics, and therefore it is preferable to remove the coarse particles by centrifugation or filtration after ink preparation. .

(Wetting agent)
The wetting agent is added for the purpose of preventing the ink from drying. The content of the wetting agent in the ink for the purpose of preventing drying is preferably 3 to 50% by mass.
The wetting agent used in the present invention is not particularly limited, but a wetting agent that is miscible with water and can prevent clogging of the head of an inkjet printer is preferable. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butane Examples include diol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol, and the like. Among them, the inclusion of propylene glycol and 1,3-butanediol is safe and has excellent effects in ink drying properties and ejection performance.

(Penetration agent)
The penetrant is added for the purpose of improving the permeability to a recording medium and adjusting the dot diameter on the recording medium. Examples of the penetrant include lower alcohols such as ethanol and isopropyl alcohol, ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether, and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether.
The penetrant content in the ink is preferably 0.01 to 10% by mass.

(Surfactant)
The surfactant is added to adjust ink properties such as surface tension. The surfactant that can be added for this purpose is not particularly limited, and examples include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Of these, anionic surfactants and nonionic surfactants are preferred.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol ether. Sulfate salts and sulfonates of the above, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Specific examples include dodecylbenzene sulfonate, isopropyl naphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, dibutylphenylphenol disulfate. , And the like salts.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Polyethylene glycol polypropylene glycol block copolymer, etc. Among them, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid Preference is given to alkylolamide, acetylene glycol, oxyethylene adducts of acetylene glycol and polyethylene glycol polypropylene glycol block copolymers.

  Other surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. Biosurfactants such as spicrispolic acid, rhamnolipid, lysolecithin and the like can also be used.

  These surfactants can be used alone or in combination of two or more. In consideration of the dissolution stability of the surfactant, the HLB is preferably in the range of 7-20. When the surfactant is added, the addition amount is preferably in the range of 0.001 to 2% by mass, more preferably 0.001 to 1.5% by mass, based on the total mass of the ink. More preferably, it is in the range of 01 to 1% by mass. When the addition amount of the surfactant is less than 0.001% by mass, the effect of adding the surfactant tends to be not obtained, and when it exceeds 2% by mass, problems such as blurring of the image are likely to occur. .

  Moreover, antiseptic | preservative, a viscosity modifier, a pH adjuster, a chelating agent, a plasticizer, antioxidant, an ultraviolet absorber etc. can be added as needed.

  The amount of pigment in the ink jet recording ink prepared from the pigment paste is 1 to 20% by mass in order to obtain a sufficient image density and to ensure the dispersion stability of the pigment in the ink. preferable.

  In the present invention, the surface tension of the first ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 20 mN / m or more and 40 mN / m or less. If the surface tension is less than 20 mN / m, the liquid may overflow on the nozzle surface and printing may not be performed normally. On the other hand, when it exceeds 60 mN / m, there is a tendency that the non-absorbing base material is easily repelled.

In the present invention, the viscosity of the first ink is preferably 1.2 mPa · s or more and 20.0 mPa · s or less, more preferably 2.0 mPa · s or more and less than 15.0 mPa · s, and still more preferably. 3.0 mPa · s or more and less than 12.0 mPa · s. When the viscosity is within this range, it is possible to achieve excellent dischargeability and good jetability over a long period of time.
The surface tension and viscosity of the first ink can be maintained in the above preferred ranges by adjusting the type and amount of surfactant and water-soluble solvent to be contained.

(Second ink vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A))
The vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A) used in the present invention is represented by the general formula (1), the INCI code is POLYQUATERNIUM-11, and the display name is polyquaternium-11. It is a compound called.

（１）

(1)

In the general formula (1), the ratio of t and u is preferably in the range of t / u = 2/8 to 8/2. Outside this range, curing may be insufficient.

  The molecular weight of the vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A) is preferably in the range of 5,000 to 500,000 in terms of weight average molecular weight, and 10,000 to 200,000. The range of is more preferable. When the weight average molecular weight is less than 5,000, the curing tends to be insufficient, and when it exceeds 500,000, the discharge stability tends to be difficult to ensure.

  The K value of the vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylic acid polymer sulfate (A) as measured by the fixture method is preferably 10-100, more preferably 10-90. More preferably, it is 10-80, Most preferably, it is 10-70. Note that the K value measured by the Fikencher method is measured as follows.

<K value>
Using ion-exchanged water, a 1% solution of the polymer solution obtained in the following examples was prepared, the viscosity of the solution was measured with a capillary viscometer at 25 ° C., and the obtained value was used by the following Fikencher method. calculate.

Where C is the number of grams of polymer in 100 cm ³ of solution, η _rel is the measured viscosity of the polymer solution (relative viscosity; viscosity of 1% solution of the polymer with respect to ion-exchanged water), and K _o is related to the K value. Indicates a variable.

  As the vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), a commercially available product can be used. For example, “HC Polymer” series manufactured by Osaka Organic Chemical Industry Co., Ltd., BASF Corporation "Ruby cut PQ11PN" and the like.

  The vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A) is preferably contained in an amount of 0.1% by mass to 5% by mass in terms of solid content in the second ink. A range of 3% to 3% by weight is still more preferred. If the amount is less than 0.1% by mass, there is a problem that sufficient curing cannot be obtained. If the amount exceeds 3% by mass, the ejection stability is inferior and the image sharpness may be deteriorated.

(Second ink modified polyethyleneimine (B))
The modified polyethyleneimine (B) used in the present invention may modify polyethyleneimine obtained by polymerizing ethyleneimine by a known method, or may modify commercially available polyethyleneimine. Examples of commercially available polyethyleneimines are commercially available from Nippon Shokubai Co., Ltd. as polyethyleneimine series such as SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000. These can be used either linearly or branched.

The modification method may be performed by a known method. For example, it can be modified by reacting an amino group of polyethyleneimine with a compound x having a functional group that reacts with the amino group to form an amide bond at one end. Examples of the functional group that reacts with an amino group to form an amide bond by using the compound x having a function to be imparted include a haloformyl group such as a carboxyl group and a chloroformyl group, and an oxycarbonyl group such as a methoxycarbonyl group. .
When a polymer is used as the compound x, for example,
(B-b1) Acrylic copolymer having a functional group that reacts with an amino group at one end
(B-b2) polyester having a functional group that reacts with an amino group at one end;
(B-b3) Polyamide having a functional group that reacts with an amino group at one end
(B-b4) Polyesteramide having a functional group that reacts with an amino group at one end
Etc.

  (B-b1) As an acrylic copolymer having a functional group that reacts with an amino group at one end, for example, to obtain a vinyl copolymer having a carboxyl group at one end, a chain transfer agent having a carboxyl group at the time of polymerization is used. The method of making it coexist is mentioned. Examples of the chain transfer agent having a carboxyl group include thiocarboxylic acids such as mercaptoacetic acid, 2-mercaptopropionic acid, and 3-mercaptopropionic acid. It can also be obtained by a method of synthesizing a polymerizable monomer by a living radical polymerization method using a polymerization initiator having a carboxyl group such as 4,4'-azobis-4-cyanopentanoic acid.

  Further, (B-b2) a polyester having a functional group that reacts with an amino group at one end is specifically a polyester having a carboxyl group at the end. This can be synthesized by various methods as follows. For example, an addition reaction for adding a lactone compound to a monocarboxylic acid compound, an addition reaction for adding a lactone compound to a hydroxycarboxylic acid compound, or a condensation reaction for condensing three components of a monocarboxylic acid compound, a hydroxycarboxylic acid compound, and a lactone compound , Etc.

  The (B-b3) polyamide having a functional group that reacts with an amino group at one end is specifically a polyamide having a carboxyl group at the end. This is prepared using a lactam such as ε-caprolactam or an aminocarboxylic acid such as aminocaproic acid or 11-aminoundecanoic acid as a raw material.

  The (B-b4) polyester amide having a functional group that reacts with an amino group at one end is specifically a cocondensate of an ester and an amide having a carboxyl group at the end. This can be prepared by co-condensing hydroxycarboxylic acid, lactone and the like used in the production of the polyester and polyamide with aminocarboxylic acid and lactam.

  Alternatively, the modified polyethyleneimine (B) is an ethyleneimine in an aqueous medium in the presence of a small amount of an acid or acid-forming compound (eg, a halogenated hydrocarbon such as chloroform, carbon tetrachloride, tetrachloroethane, or ethyl chloride). A polymer of ethyleneimine obtained by polymerization, or a condensate of epichlorohydrin and an amino group-containing compound (for example, monoamine, dimethylamine or diethylamine, ethylenediamine, diethylenetriamine, polyamine such as triethylenetetramine, or ammonia) A compound having a primary amino group or a secondary amino group, for example, a graft polymer obtained by grafting a dicarboxylic acid polyamidoamine or polyamine with ethyleneimine can also be used. The polyamidoamine grafted with ethyleneimine may optionally be further reacted with a bifunctional cross-linking agent such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols. Among these, a polyethyleneimine polymer crosslinked with polyethylene glycol dichlorohydrin ether and neutralized with formic acid is preferably used. These molar masses Mw are, for example, 500 to 1,000,000, preferably 1,000 to 500,000 g / mol.

  Moreover, a commercial item can also be used as a modified polyethyleneimine (B). For example, it is sold by BASF under the trade name of Polymin (registered trademark), for example, Polymin (registered trademark) SK.

  The modified polyethyleneimine (B) is preferably contained in an amount of 0.1% by mass to 5% by mass in terms of solid content in the second ink, and more preferably in the range of 0.3% by mass to 3% by mass. . If the amount is less than 0.1% by mass, there is a problem that sufficient curing cannot be obtained. If the amount exceeds 3% by mass, the ejection stability is inferior and the image sharpness may be deteriorated.

(Core-shell amphoteric emulsion resin (C))
Specifically, the core-shell type amphoteric emulsion resin (C) used in the present invention is:
(C-c1) Cationic polymerizable water-soluble polymer (C-A1), unreacted organic acid group-containing polymerizable compound (CB), and the cationic polymerizable water-soluble polymer (C-A1) By emulsion polymerization of a polymerizable compound (C—C) that is copolymerizable with (C-C2) and does not contain an organic acid group and amino group, or (Cc2) an anionic polymerizable water-soluble polymer (C—B1) , An unreacted amino group-containing polymerizable compound (CA), and a polymerizable compound that is copolymerizable with the anionic polymerizable water-soluble polymer (C-B1) and does not contain an organic acid group and an amino group It is an emulsion resin obtained by emulsion polymerization of (CC).

  The cationic polymerizable water-soluble polymer (C-A1) is a polymer containing an amino group-containing polymerizable compound (CA) as an essential polymerization component. Specific examples of the amino group-containing polymerizable compound (CA) include dimethylaminomethyl acrylate, diethylaminomethyl acrylate, dibutylaminomethyl acrylate, dihexylaminomethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and di (t-butyl). ) Acrylates such as aminoethyl acrylate, diisohexylaminoethyl acrylate, dihexylaminopropyl acrylate, di (t-butyl) aminohexyl acrylate, and corresponding methacrylates are included. These compounds may be used alone or in a complex system.

  Specific examples of the organic acid group-containing polymerizable compound (CB) include acrylic acid, itaconic acid, maleic acid, t-butylacrylamide sulfonic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl. Included are acrylates such as phthalic acid and the corresponding methacrylates. These may be used alone or in a complex system.

  Specific examples of the polymerizable compound (CC) that does not include the organic acid group and amino group include alkyl or cycloalkyl esters of acrylic acid or methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl Monomers such as methacrylate; vinyl such as styrene, vinyltoluene, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, etc. Le monomers; hydroxyalkyl esters of acrylic acid or methacrylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, monomers such as hydroxypropyl methacrylate and the like. These may be used alone or in a complex system.

  The anionic polymerizable water-soluble polymer (C-B1) is a polymer containing the organic acid group-containing polymerizable compound (CB) as an essential polymerization component.

  The cationic polymerizable water-soluble polymer (C-A1) or the anionic polymerizable water-soluble polymer (C-B1) can be obtained by a conventionally known solution polymerization method using a known polymerization initiator. it can. The weight average molecular weight of the copolymer is not particularly limited but is preferably in the range of 5000 to 50,000.

  The cationic polymerizable water-soluble polymer (C-A1) is preferably an organic acid group-containing polymerizable compound in a ratio range of 0.5 to 1.5 equivalents relative to 1 equivalent of the amino group of the polymer (C-A1) ( It is obtained by reacting CB). By the above reaction, the amino acid group in the polymer (C-A1) is partially neutralized by the organic acid group-containing polymerizable compound (CB) to become a cationic polymerizable water-soluble polymer (C-A1). . Since the unreacted organic acid group-containing polymerizable compound (CB) serves as a core component, there is no problem.

  The anionic polymerizable water-soluble polymer (C-B1) preferably contains an amino group in a ratio range of 0.5 to 1.5 equivalents relative to 1 equivalent of the organic acid group of the polymer (C-B1). Obtained by reacting a polymerizable compound (C-A). By the above reaction, the organic acid group in the polymer (C-B1) is partially neutralized by the amino group-containing polymerizable compound (C-A) to become an anionic polymerizable water-soluble polymer (C-A1). . Since the unreacted amino group-containing polymerizable compound (C-A) is a core component, there is no problem.

In the emulsion polymerization, the water-soluble polymer (C-A1) or (C-B1) also serves as an emulsifier. Although it does not specifically limit as a polymerization initiator for emulsion polymerization, A well-known redox polymerization initiator can be used, For example, hydrogen peroxide is included. As an emulsion polymerization medium, water is preferably used. The emulsion polymerization is preferably performed at a temperature of 60 to 90 degrees.
The polymerizable compound (CC) used in the emulsion polymerization is a polymerizable compound containing no acid group and amino group used in the synthesis of the water-soluble polymer (C-A1) or (C-B1). It may be the same as (C-C) or different.

  The core-shell type amphoteric emulsion resin (C) localizes the cationic aqueous polymer and the anionic aqueous polymer in the core part and the shell part, respectively, and is stable depending on whether the shell is an anion or a cation. In addition, adhesion to various substrates is good. The core / shell ratio is not particularly limited and may be determined according to desired performance requirements.

  In addition, as the core-shell type amphoteric emulsion resin (C), a commercially available product may be used. For example, a polymer ion complex “Acryt RKW-620” manufactured by Taisei Fine Chemical Co., Ltd. may be used.

  The core-shell type amphoteric emulsion resin (C) is preferably included in the second ink in an amount of 0.1% by mass to 5% by mass in terms of solid content, and the range of 0.3% by mass to 3% by mass is preferable. Further preferred. If the amount is less than 0.1% by mass, there is a problem that sufficient curing cannot be obtained. If the amount exceeds 3% by mass, the ejection stability is inferior and the image sharpness may be deteriorated.

The second ink used in the present invention may be prepared by appropriately adding a coloring material used in the first ink, a wetting agent (drying inhibitor), a penetrating agent, or other additives. it can.
The surface tension of the second ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 20 mN / m or more and 40 mN / m or less. If the surface tension is less than 20 mN / m, the liquid may overflow on the nozzle surface and printing may not be performed normally. On the other hand, when it exceeds 60 mN / m, the permeability to the recording medium is lowered and the repelling occurs, so that the image reproducibility tends to be inferior.

The viscosity of the second ink is preferably 1.2 mPa · s or more and 20.0 mPa · s or less, more preferably 2.0 mPa · s or more and less than 15.0 mPa · s, and further preferably 3.0 mPa · s. s or more and less than 12.0 mPa · s. When the viscosity is within this range, it is possible to achieve excellent dischargeability and good jetability over a long period of time.
The surface tension and viscosity of the second ink can be maintained in the above preferred ranges by adjusting the type and amount of the surfactant and water-soluble solvent to be contained.

(Ink set)
The water-based ink set for ink-jet recording of the present invention includes at least the first ink and the second ink, and the first ink and the second ink are non-absorbing so that they are in contact with each other. An image is formed on the substrate.

(Non-absorbing substrate)
As a plastic film which is a non-absorbing substrate used in the present invention, for example, those used for food packaging materials can be used, and known plastic films can be used. Specific examples include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films such as nylon, polystyrene films, polyvinyl alcohol films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, Examples include biodegradable films such as lactic acid films. Polyester film, polyolefin film, and polyamide film are particularly preferable, and polyethylene terephthalate, polypropylene, and nylon are more preferable. Moreover, the above-mentioned film coated with polyvinylidene chloride or the like for imparting a barrier property may be used, and if necessary, a film in which a deposited layer of a metal oxide such as aluminum or a metal oxide such as silica or alumina is used in combination. May be.

The plastic film may be an unstretched film, but is preferably stretched uniaxially or biaxially. Further, the surface of the film may be untreated, but those subjected to various treatments for improving adhesive properties such as corona discharge treatment, ozone treatment, low temperature plasma treatment, flame treatment, glow discharge treatment and the like are preferable.
The film thickness of the plastic film is appropriately changed according to the use. For example, in the case of a flexible packaging application, the film thickness is 10 μm to 100 μm as having flexibility, durability, and curl resistance. Preferably there is. More preferably, it is 10 micrometers-30 micrometers.

The water-based ink set for ink-jet recording according to the present invention includes not only a normal ink-jet recording apparatus but also a recording apparatus equipped with a heater for controlling ink drying or the like, or an intermediate transfer mechanism, and a recording material as an intermediate. It can also be used in a recording apparatus or the like that prints on a recording medium such as a non-absorbing substrate after printing.
Any conventionally known method can be used as the ink jet recording method. For example, a method of ejecting droplets using vibration of a piezoelectric element (a recording method using an ink jet head that forms ink droplets by mechanical deformation of an electrostrictive element) or a method of using thermal energy can be given.

  In the method of the present invention, when the first ink and the second ink are applied on the non-absorbing substrate so as to be in contact with each other, there is no particular limitation on the order of the application, and the application of the first ink The second ink may be applied later, the first ink may be applied after the second ink application, or may be applied simultaneously.

  The applied amounts of the first ink and the second ink applied to form one pixel are not necessarily equal, but are within a range of 1:10 to 10: 1 in mass ratio. Thus, it is a preferable aspect to apply ink.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to the following Example at all. In addition, the part in an Example below represents a mass part.

(Synthesis Example 1) NVP-HEA1
Add 282 g of water, 121 g of 2-propanol, and 10 g of N-vinylpyrrolidone as an initial charge to a reaction vessel made of SUS304 (with a cooling tube, a nitrogen introduction line, and a thermometer), introduce nitrogen while stirring, The dissolved oxygen was 0.2 ppm or less. After the polymerization vessel was heated to an internal temperature of 80 ° C., 182 g of N-vinylpyrrolidone was mixed with a monomer solution in which 41 g of 2-hydroxylethyl acrylate, 0.36 g of triethanolamine, and 97 g of water were mixed with dimethyl-2,2 ′. -An initiator solution prepared by dissolving 3.6 g of azobisisobutyrate in 31 g of 2-propanol was added dropwise over 150 minutes. Subsequently, a monomer solution in which 7 g of 2-hydroxylethyl acrylate, 5 g of water, and 14 g of 2-propanol were mixed was added over 60 minutes. Thereafter, the jacket was heated and distilled for 90 minutes to obtain a colorless and transparent polymer solution (NVP-HEA1). NVP-HEA1 had a solid content of 40% and a weight average molecular weight of 18,000.

(Preparation example cyan ink)
Stir 20 parts of DIC Corporation Cyan Pigment “FANTOGEN BLUE FSJ-SD”, 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, and 45 parts of pure water. Mixed. Next, after the kneaded meat was dispersed using a bead mill, coarse particles were removed by a centrifugal separator, and pure water was added to obtain a cyan pigment dispersion prepared to have a pigment concentration of 15% by mass. 27 parts of the cyan pigment dispersion, 3 parts of resin part (solid content), 15 parts of propylene glycol, 10 parts of 1.3-butanediol, 0.5 part of Surfinol 440, and remaining amount of pure water were mixed. The liquid was filtered through a 0.5 μm filter to obtain cyan inks (C-1) to (C-7) and (HC-8).

(Preparation example Yellow ink)
20 parts of a yellow pigment “NOVOPERM YELLOW 4G-01” manufactured by Clariant Japan Co., Ltd., 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, and 45 parts of pure water Stir and mix. Next, after the kneaded meat was dispersed using a bead mill, coarse particles were removed by a centrifugal separator, and pure water was added to obtain a yellow pigment dispersion prepared to have a pigment concentration of 15% by mass.
34 parts of the yellow pigment dispersion, 3 parts of resin part (solid content), 15 parts of propylene glycol, 10 parts of 1.3-butanediol, 0.5 part of Surfinol 440, and the remaining amount of pure water were mixed. The liquid was filtered through a 0.5 μm filter to obtain yellow inks (Y-1) to (Y-7).

(Preparation example Magenta ink)
20 parts of magenta pigment “Irgazin Magenta 2012” manufactured by BASF Corporation, 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, and 45 parts of pure water were mixed. . Next, after the kneaded meat was dispersed using a bead mill, coarse particles were removed by a centrifugal separator, and pure water was added to obtain a magenta pigment dispersion prepared to have a pigment concentration of 15% by mass.
47 parts of the magenta pigment dispersion, 3 parts of resin part (solid content), 15 parts of propylene glycol, 10 parts of 1.3-butanediol, 0.5 part of Surfinol 440, and pure water (remaining amount) are mixed. The mixture was filtered through a 0.5 μm filter to obtain magenta inks (M-1) to (M-7) and (HM-8).

(Preparation example Black ink)
20 parts of black pigment “Carbon Black # 960” manufactured by Mitsubishi Chemical Corporation, 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd., 5 parts of isopropyl alcohol and 45 parts of pure water as a pigment dispersant are stirred. Mixed. Next, after kneading with a bead mill, coarse particles were removed by a centrifugal separator, and pure water was added to obtain a black pigment dispersion prepared to have a pigment concentration of 15% by mass.
30 parts of the black pigment dispersion, 3 parts of resin part (solid content), 15 parts of propylene glycol, 10 parts of 1.3-butanediol, 0.5 part of Surfinol 440, pure water (remaining amount) are mixed. The mixture was filtered through a 0.5 μm filter to obtain black inks (K-1) to (K-7) and (HK-8).

Details of the substances described in the table below are as follows. Unless otherwise indicated, the reagents were used as they were.
Aptolock BW-5550 (trade name): olefin resin emulsion (acid-modified polyolefin resin having a polyether polymer chain, manufactured by Mitsubishi Chemical Corporation, pH: 8, acid value: 18 mgKOH / g, solid content 30%)
Hardren NA-3002 (trade name): Olefin resin emulsion (acid-modified polyolefin resin, manufactured by Toyobo Co., Ltd., pH: 8, acid value: 33 mg KOH / g, solid content 30%)
Vylonal MD-2000: polyester resin emulsion (polyester resin, manufactured by Toyobo Co., Ltd., pH: 6, solid content 40%)
Arrow base TC-4010 (trade name): polyolefin resin emulsion (acid-modified polyolefin resin, manufactured by Unitika Ltd., pH: 10, acid value: 23 mg KOH / g, solid content 25%)
Hydran AP-40F (trade name): Polyester urethane resin emulsion (urethane resin, manufactured by DIC Corporation, pH: 7, acid value: 25 mg KOH / g, solid content 22%)
Boncoat WKA-565 (trade name): acrylic resin emulsion (urethane acrylic resin, manufactured by DIC Corporation, pH: 9, acid value: 16 mgKOH / g, solid content 36%)
Jonkrill 780 (trade name): acrylic resin emulsion (acrylic resin, manufactured by BASF Corp., pH: 8, acid value: 46 mg KOH / g, solid content 48%)
Surfynol 440 (trade name): Surfactant H. manufactured by Air Products Japan Co., Ltd. C. Polymer 1S (M) (trade name): Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer sulfate (Osaka Organic Chemical Co., Ltd., solid content 20%)
H. C. Polymer 2 (trade name): Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer sulfate (Osaka Organic Chemical Co., Ltd., solid content 20%)
Catiofast SF (trade name): modified polyethyleneimine (BASF, solid content 25%)
Modified polyethyleneimine crosslinked with polyethylene glycol dichlorohydrin ether and neutralized with formic acid PolyminSK (trade name): Modified polyethyleneimine (BASF, solid content 25%)
Epomin SP-018 (trade name): Polyethyleneimine (Nippon Shokubai Co., Ltd. Molecular weight: 1800)
ACRYT RKW-620 (trade name): an emulsion containing core-shell type acrylic amphoteric copolymer particles (manufactured by Taisei Fine Chemical Co., Ltd., pH 5.2, solid content 29%)
PAA-01 (trade name): allylamine polymer (manufactured by Nitto Bo Medical Co., Ltd.), molecular weight 1,600, concentration 15%, pH: 11
PAA-1112 (trade name): allylamine / dimethylallylamine copolymer (manufactured by Nitto Bo Medical Co., Ltd.), molecular weight 1,000, concentration: 15%, pH: 11

＊＊＊ 測定不可能もしくは定量下限以下

*** Cannot be measured or below the lower limit of quantification

* Is an abbreviation for vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A).

(Measurement method of acid value)
The acid value was measured by a method based on JIS K0070. In the present invention, the following solvents were used as measurement solvents.
10 g of the resin obtained by drying and solidifying the resin aqueous solution is weighed into a 300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of ethanol: benzene = 1: 2 is added to dissolve the resin. Subsequently, using a phenolphthalein indicator, titration was performed with a 0.1 mol / L potassium hydroxide ethanol solution that had been standardized in advance, and the acid value ( mgKOH / g) is determined.

  In the formula, A is the acid value of the resin (mgKOH / g), B is the amount of 0.1 mol / L potassium hydroxide ethanol solution used for titration (ml), and f is the 0.1 mol / liter potassium hydroxide ethanol solution. The factor, S is the mass (g) of the resin, and 5.611 is a value (56.11 / 10) of 1/10 of the formula weight of potassium hydroxide.

  For resins that do not dissolve in about 50 ml of a mixed solvent of ethanol: benzene = 1: 2, select either 50 ml of ethanol or about 50 ml of a mixed solvent of ethanol / pure water = 1: 1. The others are titrated by the same operation.

(Measurement method of hydroxyl value)
The hydroxyl value was measured by a method based on JIS K0070. In this invention, the solvent shown below was used as a solvent for a measurement.
3 g of resin obtained by drying and solidifying the above resin aqueous solution is weighed into a 100 ml Erlenmeyer flask, 10.0 ml of acetic anhydride solution is added and stirred for 15 minutes. Add 2 ml of water and 10.0 ml of pyridine + water (3 + 1) and stir for 5 minutes. 10.0 ml of pyridine was added, titration was performed with a 0.5 mol / l potassium hydroxide aqueous ethanol solution, and the hydroxyl value (mgKOH / g) was determined according to the calculation formula (2).

  In the formula, A is the hydroxyl value of the resin (mgKOH / g), B is the blank value, C is the amount of 0.5 mol / l potassium hydroxide aqueous ethanol solution used for titration (ml), f is the factor of the titrant, D Is a concentration conversion factor, E is a unit conversion factor, and S is a sampled amount.

(Measurement method of Tg (glass transition temperature))
The DSC measurement was performed at a heating rate of 5 ° C./min according to JIS7122 using a thermal analyzer DSC10 manufactured by DuPont.

(Method for measuring weight average molecular weight (Mw) of a resin having a hydroxyl group and / or a carboxyl group)
Mw of a resin having a hydroxyl group and / or a carboxyl group was determined by GPC measurement under the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “SuperHZ-L” manufactured by Tosoh Corporation (inner diameter 4.6 mm × 2 cm)
+ Tosoh Corporation “TSKgel SuperHZ4000” (inner diameter 4.6 mm × 15 cm)
+ Tosoh Corporation “TSKgel SuperHZ3000” (inner diameter 4.6 mm × 15 cm)
+ "TSKgel SuperHZ2000" manufactured by Tosoh Corporation (inner diameter 4.6 mm x 15 cm)
+ Tosoh Corporation “TSKgel SuperHZ1000” (inner diameter 4.6 mm × 15 cm)
Measurement conditions: Column temperature 40 ° C
Flow rate 0.35 ml / min Sample: A resin aqueous solution was dried and solidified, and a 0.5 mass% tetrahydrofuran (THF) solution in terms of resin solid content was filtered through a microfilter (10 μl).
Calibration curve: Monodisperse standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) A calibration curve with samples having a molecular weight of 4000000 to 250 was used.

(Measurement method of weight average molecular weight (Mw))
The weight average molecular weight was determined by GPC measurement under the following conditions.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Showa Denko "Shodex SB-G", "Shodex SB-"
806 "," Shodex SB-804 "," Shodex SB-803 "," Sh
odex SB-802.5 "
Measurement conditions: column temperature 40 ° C., flow rate 1.0 ml / min mobile phase: detector in which sodium nitrate is added to a mixed solvent of acetonitrile / water = 50/50 (mass ratio) to 0.1 mol / dm ³ . : Differential refractometer (detector temperature 35 ℃)
Sample concentration: 0.5%
Calibration curve: standard polyethylene glycol Calibration curves with samples with molecular weights up to 4,000,000 to 10,000 were used.

(Examples 1-168, Comparative Examples 1-4)
Each ink set was loaded into an inkjet recording apparatus (EB-100 manufactured by Konica Minolta Co., Ltd.) having 256 nozzles × 2 rows of piezo-type inkjet nozzles, and an OPP film (Futamura Chemical Co., Ltd. FOR # manufactured as a recording material) 20 and a film thickness of 20 μm). The droplet size was about 42 pl so that it could be ejected at a resolution of 360 × 360 dpi (dpi is the number of dots per 2.54 cm) and was driven at a driving frequency of 2 kHz. While preheating with a heater so that the surface of the film was about 60 ° C., printing was performed according to the following ink application sequence, followed by drying (80 ° C./60 seconds).

(Ink application order)
Type A: The second ink is applied after the first ink is applied.
Type B: The first ink is applied after the second ink is applied.
Type C: First ink and second ink are applied simultaneously.

(Viscosity measurement method)
Using an E-type viscometer “V-25 type (manufactured by Toki Sangyo Co., Ltd.)”, measurement was performed (ink temperature 25 ° C.).

(PH measurement method)
Measurement was performed using MM-60R (manufactured by Toa DKK Co., Ltd.) (ink temperature 25 ° C.).

(Evaluation method)
The following physical properties (1) to (5) were evaluated in a constant temperature and humidity chamber (room temperature: 25 ° C., humidity: 50%) for the ejection properties and the obtained printing.

(1) Dischargeability The nozzle clogging after continuous 12 sheets printing was evaluated.
○: Ink does not adhere around the nozzle, and the nozzle is not clogged.
Δ: Ink adheres around the nozzle, but the nozzle is not clogged.
×: Nozzle clogged.

(2) Breathability (bleed)
○: Ink does not bleed at the boundary between halftone dots and solid portions.
Δ: There is a slight blur at the boundary between halftone dots and solid portions.
X: The dot of a halftone dot and a solid part spread.

(3) Repelling ○: Ink does not repel at halftone dots and solid areas.
Δ: Ink is slightly repelled at halftone dots and solid portions.
X: Ink repels at halftone dots and solid areas.

(4) Solid part reproducibility ○: Ink is reproduced without density unevenness in the solid image printing part.
(Triangle | delta): The density nonuniformity of a solid image printing part is less than 20% with respect to a printing part.
X: Density unevenness of the solid image printing part is 20% or more with respect to the printing part.
The evaluation results are shown in Tables 12 to 38.

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having a hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone · N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): resin having no hydroxy group and carboxyl group (solid content) / vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): resin having no hydroxy group and carboxyl group (solid content) / vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

Ink application order type A: Application of the second ink after application of the first ink Type B: Application of the first ink after application of the second ink Type C: Application of the first ink and the second ink simultaneously Ink mixing ratio (mass ratio): resin having no hydroxy group and carboxyl group (solid content) / vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)

As a result, all of the ink sets obtained in Examples 1 to 168 had good bleeding, repelling, and solid portion reproducibility. On the other hand, Comparative Examples 1 to 5 were examples in which a resin having no hydroxy group and carboxyl group was used as the binder resin in the first ink, and the evaluations of the printed matter were all x.
Comparative Examples 6 to 14 are vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer sulfate (A) and / or modified polyethyleneimine polymer (B) and / or core-shell type acrylic resin amphoteric copolymer particles. Although it is an example which does not have (C), the desired effect was not acquired.

Claims (4)

An ink set for ink jet recording using at least two kinds of inks, wherein the first ink contains a color material, a resin having a hydroxy group and / or a carboxyl group, a water-soluble solvent and / or water,
The second ink is at least one selected from the group consisting of vinyl pyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), and core-shell amphoteric emulsion polymer (C). Two polymers, a water-soluble solvent and / or water,
The resin having the hydroxy group and / or carboxyl group of the first ink is a polyolefin resin having a weight average molecular weight of 10,000 or more and 1,000,000 or less and an acid value of 1 to 200 mgKOH / g. A water-based ink set for ink-jet recording characterized by the above. 2. The ink set for water-based inkjet recording according to claim 1, wherein the color material is a pigment, and the resin having the hydroxy group and / or carboxyl group is dispersed in a water-soluble solvent and / or water. The aqueous ink jet recording ink set according to claim 2 , wherein the polyolefin resin is a polyolefin resin having a polyether polymer chain. The water-based ink set for inkjet recording according to any one of claims 1 to 3 , which prints on a non-absorbent substrate.