JP5679155B2 - Aqueous pigment dispersion-containing composition for inkjet recording, and aqueous ink for inkjet recording - Google Patents

Description

  The present invention relates to a composition containing an aqueous pigment dispersion for inkjet recording, and an aqueous ink for inkjet recording using the same.

In recent years, the development of water-based ink for ink-jet recording using a pigment (hereinafter abbreviated as water-based pigment ink) has been promoted as a water-based ink for ink-jet recording.
An aqueous pigment ink is a pigment dispersion in which pigment particles are uniformly dispersed in an aqueous solvent such as water. For example, an aqueous pigment ink in which a pigment is dispersed with a surfactant or a polymer dispersant, or water dispersion on a pigment surface. There have been proposed aqueous pigment inks using self-dispersing pigments to which various functional groups have been added, aqueous pigment inks using colored fine particles coated with a resin capable of dispersing the pigment in water, and the like.
Since pigment ink is colored by forming an ink film containing pigment particles on the recording medium after recording, it is particularly excellent in color development on plain paper compared to the color that penetrates into the recording medium like dye ink. In addition, the printed image is excellent in water resistance and light resistance. However, there are problems such as insufficient dispersion stability of the pigment and fixability to the recording member, problems such as poor or changed gloss of the formed image, and poor abrasion resistance.

  On the other hand, for example, an inkjet comprising a pigment, water, polymer particles of a water-insoluble vinyl polymer obtained by polymerizing a monomer composition containing a monomer having a polyethylene glycol chain or a polypropylene glycol chain, and a urethane resin. A water-based ink for recording is known (for example, see Patent Document 1). An ink composition capable of obtaining an image having excellent color developability for plain paper and excellent glossiness for a glossy recording medium by using a water-insoluble vinyl polymer and a urethane resin, A print image with improved gloss change can be obtained. However, the water-based pigment ink cannot satisfy both satisfactory gloss and initial scratch resistance.

Japanese Patent Application No. 2006-282760 Japanese Patent Laid-Open No. 10-60353 JP 2006-63276 A JP 2007-131753 A JP 2005-272790 A

  The problem to be solved by the present invention is to provide a water-based ink for ink jet recording excellent in gloss change and abrasion resistance.

  The present inventors have (1) a pigment, and (2) a polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure and a polymerizable unsaturated monomer (b) having a polyurethane structure. It has been found that the above-mentioned problems can be solved by using an aqueous pigment dispersion-containing composition for inkjet recording, which contains a copolymer (A) having an essential component as a component.

An aqueous pigment ink containing a (meth) acrylic copolymer having a polyurethane-containing structural unit to which a pendant structure containing polyurethane is bonded is known. For example, in Patent Document 2, polyacrylic acid or a derivative thereof is refluxed with thionyl chloride. A water-based pigment ink containing an acrylic-urethane copolymer emulsion obtained by reacting with an acid chloride and then reacting with the polyurethane and a polymer dispersant is described. (See Patent Document 2, paragraphs 0010 to 0011)
In Patent Documents 3 and 4, pigment dispersants in which a polyurethane structure is introduced at the end of an acrylic main chain are known as pigment dispersants for oil-based pigment inks.

  In Patent Document 5, a water-dispersible polymer containing a (meth) acrylic acid ester having a polyurethane structure as a constituent component is known. However, these inks do not provide satisfactory gloss on special paper.

  In the present application, unlike the pigment dispersants described in Patent Documents 2 to 5, at least two kinds of a structural unit having a polyoxyalkylene group or a polylactone group and a polyurethane structure are pendant on the copolymer main chain. It is a feature. It has been found that such a structure is excellent in gloss change and abrasion resistance.

  That is, the present invention comprises (1) a pigment, and (2) a polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure and a polymerizable unsaturated monomer (b) having a polyurethane structure. An aqueous pigment dispersion-containing composition for ink-jet recording comprising a copolymer (A) having an essential component as a component is provided.

  The present invention also provides an aqueous ink for ink jet recording using the above-described composition containing an aqueous pigment dispersion for ink jet recording.

  According to the present invention, a water-based ink for ink-jet recording having excellent gloss change and abrasion resistance can be obtained.

(Pigment)
The pigment used in the present invention may be an organic pigment or an inorganic pigment.
Organic pigments include insoluble azo pigments, soluble azo pigments, indanthrene pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, isoindolinone pigments, quinophthalone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments And pigments.
As the inorganic pigment, titanium oxide, iron oxide, carbon black and the like can be used.

  As for the particle diameter of the pigment, the primary particle diameter is preferably in the range of 1 to 500 nm, and more preferably in the range of 20 to 200 nm. The particle diameter of the pigment after being dispersed in the medium is preferably in the range of 10 to 300 nm, and more preferably in the range of 50 to 150 nm. The primary particle diameter of the pigment can be measured by an electron microscope, a gas or solute adsorption method, an air flow method, an X-ray small angle scattering method, and the like. The pigment particle diameter after dispersion 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.

(Polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure)
In the polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or polylactone structure (hereinafter sometimes referred to as “polymerizable unsaturated monomer (a)”), the polyoxyalkylene structure is specifically Is represented by — (CH _m H _2m —O) _n — (where m and n represent integers). As typical examples, in addition to various polyoxyalkylene structures such as a polyoxyethylene structure, a polyoxypropylene structure or a polyoxybutylene structure, the above-described oxyalkylene moiety such as a poly (oxyethylene-oxypropylene) structure is used. Randomly copolymerized, polyoxyethylene-polyoxypropylene structures, etc., which have different polyoxyalkylene structures bonded in block form, polyoxyalkylene structures obtained by ring-opening polymerization of dioxolane rings, etc. It is done.

  The number average molecular weight of the polyoxyalkylene structure is preferably in the range of 150 to 5,000, more preferably 200 to 3, from the viewpoint of water dispersibility of the pigment dispersant of the present invention and desired image gloss. Within the range of 000, most preferably within the range of 300 to 2,000.

The polylactone structure is obtained by ring-opening polymerization of a lactone, and is specifically represented by — (C _m H _2m —CO—O) _n — (where m and n represent integers). Although there is no restriction | limiting in the lactone used, 4-7 membered lactone is preferable. Specifically, β-lactone (such as β-propiolactone), γ-lactone (such as γ-butyrolactone), δ-lactone (such as δ-valerolactone), ε-lactone (such as ε-caprolactone), macrocycle Lactone (enanthlactone, undecanolactone, dodecalactone, etc.) and the like can be mentioned. The alkylene group constituting the lactone may be linear or branched.

  The number average molecular weight of the polylactone group is preferably in the range of 100 to 2,000 from the viewpoint of the water dispersibility of the pigment dispersant of the present invention and the desired image gloss.

  From the viewpoint of desired image gloss, in the polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure, at least one kind may be a polymerizable unsaturated monomer having an oxyethylene structure. desirable.

  As the polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure, polyethylene glycol monovinyl ether, methoxypolyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate caprolactone adduct, polyethylene glycol-polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol- Tetremethylene glycol) mono (meth) acrylate and the like.

(Polymerizable unsaturated monomer having polyurethane structure (b))
The polymerizable unsaturated monomer (b) having a polyurethane structure is obtained by reacting a polymerizable unsaturated monomer (c) having a hydroxyl group with a polyurethane having an isocyanate group to convert an excess isocyanate group such as a hydroxyl group or an amino group. It is obtained by sealing with a compound having an active hydrogen group.

  The polyurethane having an isocyanate group may be any polyurethane diisocyanate comprising a diisocyanate compound and a diol compound, but a polyurethane diisocyanate having a carboxyl group is preferred from the viewpoint of water dispersibility. The carboxyl group is usually introduced by reacting a diol compound having one or more carboxyl groups in one molecule with a diisocyanate compound.

Examples of the diol compound having one or more carboxyl groups in one molecule used in the present invention include esters obtained by reaction of polyhydric alcohols and polybasic acid anhydrides, 2,2-dimethylol lactic acid, 2, Examples thereof include dihydroxyalkanoic acids such as 2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and 2,2-dimethylolvaleric acid. Preferable compounds include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. Among them, dimethylolpropionic acid or dimethylolbutanoic acid is preferable because it is easily available.
The carboxyl group is preferably introduced in the polyurethane diisocyanate so as to be 1% to 15% in terms of weight ratio, and more preferably in the range of 3% to 10%.

  Of course, general-purpose diol compounds having no carboxyl group can also be used, and these can be appropriately selected depending on the printability of the desired ink. Examples of the diol compound include a polymer diol compound such as polyester polyol, polyether polyol, polyhydroxy polycarbonate, polyhydroxy polyacetal, polyhydroxy polyacrylate, polyhydroxy polyester amide and polyhydroxy polythioether, ethylene glycol, Examples thereof include low molecular weight diol compounds such as diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol and the like. One of these diol compounds may be reacted, or several may be mixed and reacted.

Examples of the diisocyanate compound used in the present invention include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4 -An alicyclic diisocyanate compound such as cyclohexylmethane diisocyanate, an araliphatic diisocyanate compound such as xylylene diisocyanate and tetramethylxylene diisocyanate, an aromatic diisocyanate compound such as toluylene diisocyanate and phenylmethane diisocyanate Can be mentioned.
Among these, an aliphatic diisocyanate compound or an alicyclic diisocyanate compound is preferable from the viewpoint that light discoloration of a printed image hardly occurs.

In order to obtain a polyurethane having an isocyanate group by reacting the diisocyanate compound and the diol compound, the isocyanate group of the diisocyanate compound may be excessively reacted with respect to the hydroxyl group of the diol compound. The excess amount can be appropriately determined so that the polyurethane diisocyanate has a desired molecular weight.
The molecular weight of the polyurethane diisocyanate is the theoretical molecular weight calculated from the reaction ratio, preferably in the range of 500 to 100,000, more preferably in the range of 1,000 to 50,000, most preferably in the range of 2,000 to 30,000. preferable.

  Specific reaction methods include, for example, a method in which the total amount of the diol compound and the diisocyanate compound are reacted in a solvent, a method in which the diol compound is reacted stepwise with the diisocyanate compound in a solvent while considering reactivity. is there.

The polymerization solvent is preferably a solvent that does not react with the isocyanato group. Examples include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, ethyl acetate, isobutyl acetate, dibutyl ether, tetrahydrofuran, dioxane and the like.
Moreover, you may use well-known urethanation catalysts, such as an inorganic tin type and an organic tin type, as a reaction catalyst.

  The reaction of the polyurethane diisocyanate obtained by the reaction of the diol compound and the diisocyanate compound with the polymerizable unsaturated monomer (c) having a hydroxyl group may be in any isocyanato group to hydroxyl group molar ratio.

  In the reaction between the polyurethane diisocyanate and the polymerizable unsaturated monomer (c) having a hydroxyl group, the polymerizable unsaturated monomer (c) having a hydroxyl group may be added after the polyurethane diisocyanate is synthesized, A polymerizable unsaturated monomer (c) having a hydroxyl group may be added during the synthesis of the polyurethane diisocyanate.

  When adding the polymerizable unsaturated monomer (c) having a hydroxyl group, it is desirable to add a polymerization inhibitor at the same time. When the polymerization inhibitor is not added, the polymerization reaction of the polymerizable unsaturated monomer (c) having a hydroxyl group may occur and the target product may not be obtained.

  Examples of the polymerization inhibitor include methoquinone, hydroquinone, t-butylhydroquinone, 4-t-butylcatechol and the like.

  The polymerization inhibitor is preferably added at 10 ppm to 1000 ppm, more preferably between 100 ppm and 1000 ppm, based on the solid matter in the reaction system.

  As the polymerizable unsaturated monomer (c) having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate , Polypropylene glycol mono (meth) acrylate, caprolactone adduct of 2-hydroxyethyl (meth) acrylate, polyethylene glycol monovinyl ether, and the like.

  After the reaction, the remaining isocyanato group is sealed with a compound having an active hydrogen group such as a hydroxyl group or an amino group. This reaction may be a known method.

(Copolymer (A) having a polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure and a polymerizable unsaturated monomer (b) having a polyurethane structure as essential components)
A copolymer (A) comprising a polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure and a polymerizable unsaturated monomer (b) having a polyurethane structure as essential constituents is at least And a polymerizable unsaturated monomer (a) having the polyoxyalkylene structure or polylactone structure and a polymerizable unsaturated monomer (b) mixture having the polyurethane structure obtained in the step. It can be obtained by polymerizing a saturated monomer.

  A known method can be used for the polymerization reaction. Among these, a solution polymerization method using a radical polymerization initiator in a solvent is desirable.

In the solution polymerization, the polymerization solvent to be used is not particularly limited. For example, methanol, ethanol, isopropanol, 1-butanol, tertiary butanol, isobutanol, diacetone alcohol, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, diethylene glycol Examples include monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, butyl cellosolve, toluene, xylene, ethyl acetate, and isobutyl acetate.
These solvents may be used alone or in combination.

  The polymerization temperature in solution polymerization is generally in the range of 50 ° C to 120 ° C.

Examples of radical polymerization initiators used in solution polymerization include organic peroxides such as t-butylperoxy (2-ethylhexanoate) and t-butylperoxybenzoate, and 2,2′-azobisisobutyrate. An azo compound such as rhonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), or the like can be used.
The amount of radical polymerization initiator used is preferably 1% by weight or more and 10% by weight or less based on the total amount of monomers.

  Moreover, the gel by the polyfunctional polymerizable unsaturated monomer contained in the polymerizable unsaturated monomer (a) which has a polyoxyalkylene structure or a polylactone structure, and the polymerizable unsaturated monomer (b) which has a polyurethane structure In order to prevent the formation, the 10-hour half-life temperature of the radical polymerization initiator used is desirably lower by 10 ° C. or more than the reaction temperature.

  In addition to the polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure and the polymerizable unsaturated monomer (b) having a polyurethane structure, other polymerizable unsaturated monomers (hereinafter referred to as “polymerizable unsaturated monomers”) (It may be called a polymerizable unsaturated monomer (t)). Specifically, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, ( Examples include cyclohexyl methacrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, maleic anhydride, butadiene, and vinyl acetate. A polymerizable unsaturated monomer (t) can be added to such an extent that the effect of this application is not impaired.

(Introduction ratio of polyoxyalkylene structure or polylactone structure)
The introduction ratio of the polyoxyalkylene structure or polylactone structure in the copolymer (A) is preferably such that the ratio calculated by the formula (1) is 45% to 100%, and 45% to 95%. A range is still preferred, with a range of 50% to 90% being most preferred. By setting such a ratio, particularly when applied to glossy paper, a desired image gloss can be obtained, which is particularly preferable.

W: Charge amount (parts by weight) of the polymerizable unsaturated monomer (c) having a hydroxyl group, which is a raw material of the mixture containing the polymerizable unsaturated monomer (b) having a polyurethane structure. However, the mixture containing a polymerizable unsaturated monomer (b) having a polyurethane structure is reacted with a polymerizable unsaturated monomer (c) having a hydroxyl group and a polyurethane having an isocyanate group to convert an excess isocyanate group to a hydroxyl group or It is a mixture sealed with a compound having an active hydrogen group such as an amino group.
X: A polymerizable unsaturated monomer (c) having a hydroxyl group in W, which is a charged amount (part by weight) of a polymerizable unsaturated monomer containing a hydroxyl group and a polyoxyalkylene group or a polylactone group
Y: Charge amount (parts by weight) of the polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure
Z: Charge amount of polymerizable unsaturated monomer (t) (parts by weight)

(Polyurethane introduction ratio)
The introduction ratio of the polyurethane structure in the copolymer (A) is desirably blended so that the value calculated by the formula (2) is 1% to 200%, and more preferably in the range of 3% to 150%. A range of 5% to 100% is most preferred.

V: Charge amount (parts by weight) of the mixture containing the polymerizable unsaturated monomer (b) having a polyurethane structure. However, the mixture containing a polymerizable unsaturated monomer (b) having a polyurethane structure is reacted with a polymerizable unsaturated monomer (c) having a hydroxyl group and a polyurethane having an isocyanate group to convert an excess isocyanate group to a hydroxyl group or It is a mixture sealed with a compound having an active hydrogen group such as an amino group.
W, Y, Z: Same as formula (1)

  The molecular weight of the copolymer (A) having a polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure and a polymerizable unsaturated monomer (b) having a polyurethane structure as essential components Although it does not restrict | limit in particular, From a viewpoint of the pigment dispersibility after adjusting as an inkjet ink and ink discharge property, it is preferable that it is 5,000-50,000 in conversion to a weight average molecular weight.

  The acid value of the copolymer (A) is preferably 150 mgKOH / g or less from the viewpoint of dispersibility and dischargeability.

  The copolymer (A) obtained through the above steps is a mixture containing, in addition to the copolymer (A), a copolymer having no polyurethane structure, a urethane resin, and the like. Substances other than the copolymer (A) may be removed or used in the form of a mixture.

(Aqueous pigment dispersion-containing composition for inkjet recording)
The aqueous pigment dispersion-containing composition for inkjet recording of the present application contains a pigment dispersed using a mixture containing the copolymer (A).

  When it is set as the aqueous pigment dispersion containing composition for inkjet recording, it is desirable that the carboxyl group which the said copolymer (A) has is neutralized, and the neutralization rate is 50-100% normally, especially 70-. It is preferable to set it in the range of 100%.

  As the basic substance to be neutralized, any known and commonly used substances can be used. For example, inorganic basic substances such as sodium hydroxide, potassium hydroxide and ammonia, and organic basic substances such as triethylamine and alkanolamine. Can be used.

  The copolymer (A) is preferably used in an amount of 1 to 150 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the pigment.

  As the dispersing device that can be used when dispersing the pigment and the mixture containing the copolymer (A), any of various known devices can be used. For example, a method that uses the kinetic energy of a spherical dispersion medium made of steel, stainless steel, zirconia, alumina, silicon nitride, glass, etc., with a diameter of about 0.1 to 10 mm, a method that uses shear force by mechanical stirring, and a high speed Examples of the dispersion device include a dispersion method such as a method using a pressure change of a supplied dispersed flow bundle, a flow path change, or a force generated by a collision. Specific dispersing devices include RED DEVIL paint conditioner, Toyo Seiki Co., Ltd. test disperser, Mitsui Mining Co., Ltd. SC mill SC100 / 32 type, Hamada Tekko Co., Ltd. planetary mixer PVM. -5, Dino mill manufactured by Willy et Bakkofen (WAB).

(Water-based ink for inkjet recording)
The water-based ink for ink-jet recording of the present invention is obtained by adding various additives and liquid media that are well-known and commonly used in the technical field of water-based ink for ink-jet recording to the water-based pigment dispersion-containing composition for ink-jet recording. be able to.

  Specifically, the aqueous pigment dispersion-containing composition for inkjet recording is diluted with water or other liquid medium so as to have a pigment solid content of 1 to 10% on a weight basis to obtain an aqueous pigment ink for inkjet recording. . Ultracentrifugation or filtration with a microfilter may be further performed in order to remove coarse particles and undersized particles and to adjust the particle size distribution of dispersed particles.

When adjusting the water-based ink for inkjet recording, a water-soluble resin such as an acrylic resin, a polyurethane resin, or a polyester resin may be further added in order to improve various properties of the ink and its printed matter. A polyurethane resin is particularly preferable, and a carboxyl group-containing polyurethane resin is most preferable because it can impart abrasion resistance.
The water-soluble resin may be added to the aqueous pigment dispersion-containing composition for inkjet recording after the dispersion step.

  The carboxyl group-containing polyurethane resin may be any carboxyl group-containing polyurethane resin comprising a diisocyanate compound, a diol compound having one or more carboxyl groups in one molecule, and other diol compounds.

Examples of the diol compound having one or more carboxyl groups in one molecule include esters obtained by reaction of polyhydric alcohols and polybasic acid anhydrides, 2,2-dimethylol lactic acid, 2,2-dimethylol propion. Examples thereof include dihydroxyalkanoic acids such as acid, 2,2-dimethylolbutanoic acid and 2,2-dimethylolvaleric acid. Preferable compounds include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. Among them, dimethylolpropionic acid or dimethylolbutanoic acid is preferable because it is easily available.
The carboxyl group is preferably introduced in the polyurethane diisocyanate so as to be 1% to 15% in terms of weight ratio, and more preferably in the range of 3% to 10%.

  Examples of other diol compounds that do not have a carboxyl group include polymeric polyols such as polyester polyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides and polyhydroxy polythioethers. In addition to the diol compound, low molecular weight diol compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol and the like can be mentioned. One of these diol compounds may be reacted, or several may be mixed and reacted. It is preferable that a high molecular diol compound is essential in order to impart abrasion resistance to the printed matter.

Examples of the diisocyanate compound include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4-cyclohexylmethane diisocyanate and the like. And alicyclic diisocyanate compounds such as xylylene diisocyanate, aromatic methyl diisocyanate compounds such as tetramethylxylene diisocyanate, aromatic diisocyanate compounds such as toluylene diisocyanate and phenylmethane diisocyanate.
Among these, an aliphatic diisocyanate compound or an alicyclic diisocyanate compound is preferable from the viewpoint that light discoloration of a printed image hardly occurs.

The polymerization solvent is preferably a solvent that does not react with the isocyanato group. Examples include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, ethyl acetate, isobutyl acetate, dibutyl ether, tetrahydrofuran, dioxane and the like.
Moreover, you may use well-known urethanation catalysts, such as an inorganic tin type and an organic tin type, as a reaction catalyst.

  The carboxyl group-containing polyurethane resin usually has a weight average molecular weight, preferably in the range of 2,000 to 100,000, more preferably in the range of 1,000 to 50,000, and further in the range of 3,000 to 50,000. The range of 5,000 to 30,000 is most preferable.

  The addition amount is usually preferably in the range of 0 to 100 parts, more preferably in the range of 1 to 50 parts, with respect to 100 parts of pigment in terms of weight, based on the nonvolatile content of the polyurethane resin.

  The aqueous pigment ink for ink-jet recording thus obtained can be recorded on a known recording medium. As the recording medium at this time, for example, plain paper such as PPC paper, exclusive paper for inkjet such as photographic paper (glossy), photographic paper (silk), synthetic resin film such as OHP film, Various films and sheets, such as metal foils, such as aluminum foil, are mentioned.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following examples and comparative examples, “parts” and “%” are both based on weight.

<Synthesis Example 1> (Synthesis of polymerizable unsaturated monomer mixture M-1 having a polyurethane structure)
In a four-necked flask equipped with a thermometer, stirrer, nitrogen introduction tube, and cooling tube, 465 parts of methyl ethyl ketone (hereinafter abbreviated as MEK), 174 parts of bis (isocyanatomethyl) cyclohexane, 226 parts of polypropylene glycol (OH group equivalent 160) Then, 66 parts of dimethylolpropionic acid and 0.03 part of dibutyltin dilaurate as a catalyst were charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued for 3 hours. Thereafter, a mixture of 30 parts Plaxel FM-5 (manufactured by Daicel Chemical Industries, Ltd., 5 mol of caprolactone of hydroxyethyl methacrylate), 0.3 parts of methoquinone and 150 parts of MEK was added. The reaction was continued at 80 ° C. until the isocyanato group content was 0.46%. 50 parts of ethanol was added, and the reaction was further continued at 80 ° C. until the isocyanato group content was 0.02% or less. After completion of the reaction, a part of MEK as a solvent was distilled off under reduced pressure to obtain a 50% solution of a mixture M-1 containing a (meth) acrylic acid ester having a polyurethane structure.

<Synthesis Example 2> (Synthesis of polymerizable unsaturated monomer mixture M-2 having a polyurethane structure)
In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, 201 parts of MEK, 140 parts of isophorone diisocyanate, 274 parts of polytetramethylene ether glycol (OH group equivalent 56), 56 parts of dimethylolpropionic acid, and catalyst Then, 0.03 part of dibutyltin dilaurate was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued for 3 hours. Thereafter, a mixture of 26 parts Plaxel FM-5, 0.3 parts methoquinone and 294 parts MEK was added. The reaction was continued at 80 ° C. until the isocyanato group content was 0.44%. 50 parts of ethanol was added, and the reaction was further continued at 80 ° C. until the isocyanato group content was 0.02% or less. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 50% solution of a mixture M-2 containing a (meth) acrylic acid ester having a polyurethane structure.

<Synthesis Example 3> (Synthesis of polymerizable unsaturated monomer mixture M-3 having a polyurethane structure)
In a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube, 384 parts of methyl ethyl ketone (hereinafter abbreviated as MEK), 176 parts of bis (isocyanatomethyl) cyclohexane, 228 parts of polypropylene glycol (OH group equivalent 160) Then, 66 parts of dimethylolpropionic acid and 0.02 part of dibutyltin dilaurate as a catalyst were charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued for 3 hours. Thereafter, a mixture of 24 parts Plaxel FM-5, 0.2 parts methoquinone and 110 parts MEK was added. The reaction was continued at 80 ° C. until the isocyanato group content was 0.56%. 50 parts of ethanol was added, and the reaction was further continued at 80 ° C. until the isocyanato group content was 0.02% or less. After completion of the reaction, a part of MEK as a solvent was distilled off under reduced pressure to obtain a 50% solution of a mixture M-3 containing a (meth) acrylic acid ester having a polyurethane structure.

<Synthesis Example 4> (Synthesis of polymerizable unsaturated monomer mixture M-4 having a polyurethane structure)
In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, MEK 456 parts, bis (isocyanatomethyl) cyclohexane 171 parts, polypropylene glycol (OH group equivalent 160) 221 parts, dimethylolpropionic acid 64 parts, Then, 0.03 part of dibutyltin dilaurate as a catalyst was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued for 3 hours. Thereafter, a mixture of 39 parts Plaxel FM-5, 0.3 parts methoquinone and 150 parts MEK was added. The reaction was continued at 80 ° C. until the isocyanato group content was 0.41%. 50 parts of ethanol was added, and the reaction was further continued at 80 ° C. until the isocyanato group content was 0.02% or less. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 50% solution of a mixture M-4 containing a (meth) acrylic acid ester having a polyurethane structure.

<Synthesis Example 5> (Synthesis of polymerizable unsaturated monomer mixture M-5 having a polyurethane structure)
In a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube, MEK 440 parts, bis (isocyanatomethyl) cyclohexane 165 parts, polypropylene glycol (OH group equivalent 160) 214 parts, dimethylolpropionic acid 62 parts, Then, 0.03 part of dibutyltin dilaurate as a catalyst was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued for 3 hours. Thereafter, a mixture of 56 parts Plaxel FM-5, 0.3 parts methoquinone and 150 parts MEK was added. The reaction was continued at 80 ° C. until the isocyanato group content was 0.30%. 50 parts of ethanol was added, and the reaction was further continued at 80 ° C. until the isocyanato group content was 0.02% or less. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 50% solution of a mixture M-5 containing (meth) acrylic acid ester having a polyurethane structure.

<Synthesis Example 6> (Synthesis of polymerizable unsaturated monomer mixture M-6 having a polyurethane structure)
In a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube, MEK 425 parts, bis (isocyanatomethyl) cyclohexane 159 parts, polypropylene glycol (OH group equivalent 160) 206 parts, dimethylolpropionic acid 60 parts, Then, 0.03 part of dibutyltin dilaurate as a catalyst was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued for 3 hours. Thereafter, a mixture of 73 parts Plaxel FM-5, 0.3 parts methoquinone and 150 parts MEK was added. The reaction was continued at 80 ° C. until the isocyanato group content was 0.19%. 50 parts of ethanol was added, and the reaction was further continued at 80 ° C. until the isocyanato group content was 0.02% or less. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 50% solution of a mixture M-6 containing (meth) acrylic acid ester having a polyurethane structure.

<Synthesis Example 7> (Synthesis of polymerizable unsaturated monomer mixture M-7 having a polyurethane structure)
In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 398 parts of MEK, 149 parts of bis (isocyanatomethyl) cyclohexane, 193 parts of polypropylene glycol (OH group equivalent 160), 56 parts of dimethylolpropionic acid, Then, 0.03 part of dibutyltin dilaurate as a catalyst was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued for 3 hours. Thereafter, a mixture of 102 parts Plaxel FM-5, 0.3 parts methoquinone and 202 parts MEK was added. The reaction was continued at 80 ° C. until the isocyanato group content was 0.02%. 50 parts of ethanol was added and the reaction was continued at 80 ° C. for an additional hour. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 50% solution of a mixture M-7 containing (meth) acrylic acid ester having a polyurethane structure.

<Synthesis Example 8> (Synthesis of polymerizable unsaturated monomer mixture M-8 having a polyurethane structure)
In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 489 parts of MEK, 183 parts of bis (isocyanatomethyl) cyclohexane, 237 parts of polypropylene glycol (OH group equivalent 160), 69 parts of dimethylolpropionic acid, Then, 0.0 part of dibutyltin dilaurate as a catalyst was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued for 2 hours. Thereafter, a mixture of 5.6 parts of 2-hydroxyethyl methacrylate, 0.3 part of methoquinone and 150 parts of MEK was added. The reaction was continued at 80 ° C. until the isocyanato group content was 0.30%. 50 parts of ethanol was added, and the reaction was further continued at 80 ° C. until the isocyanato group content was 0.02% or less. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 50% solution of a mixture M-8 containing (meth) acrylic acid ester having a polyurethane structure.

  Table 1 shows the theoretical molecular weight of polyurethane diisocyanate, the weight ratio of carboxyl groups in polyurethane diisocyanate, and the molar ratio of isocyanate groups to hydroxyl groups of the obtained mixtures M-1 to M-8.

＊） ポリウレタンジアイソシアネートと水酸基を有する重合性不飽和単量体との反応におけるイソシアナト基と水酸基とのモル比

*) Molar ratio of isocyanato group to hydroxyl group in the reaction of polyurethane diisocyanate with a polymerizable unsaturated monomer having a hydroxyl group.

<Synthesis Example 9> (Synthesis of urethane resin U-1)
MEK 495 parts, isophorone diisocyanate 172 parts, polytetramethylene ether glycol (OH group equivalent 56) 252 parts, dimethylolpropionic acid 69 parts, neopentyl in a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube 7 parts of glycol and 0.03 part of dibutyltin dilaurate as a catalyst were charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued at 80 ° C. until the content of isocyanato groups reached 0.54%, 50 parts of ethanol was added, and the isocyanate group was added at 80 ° C. The reaction was continued until the content was 0.02% or less. After completion of the reaction, 5% KOH aqueous solution was added so that the carboxyl group in the resin was neutralized 100%, and water was further added to dissolve the resin. A part of the solvent was distilled off under reduced pressure to obtain a 50% solution of an aqueous urethane resin solution U-1.

<Synthesis Example 10> (Synthesis of urethane resin U-2)
In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 492 parts of MEK, 184 parts of bis (isocyanatomethyl) cyclohexane, 239 parts of polypropylene glycol (OH group equivalent 160), 69 parts of dimethylolpropionic acid, Then, 0.03 part of dibutyltin dilaurate as a catalyst was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, and then the reaction was continued at 80 ° C. until the isocyanate group content was 0.48%, and 50 parts of ethanol was added and the isocyanate group was added at 80 ° C. The reaction was continued until the content was 0.02% or less. After completion of the reaction, 5% KOH aqueous solution was added so that the carboxyl group in the resin was neutralized 100%, and water was further added to dissolve the resin. A part of the solvent was distilled off under reduced pressure to obtain a 50% solution of urethane resin aqueous solution U-2.

<Synthesis Example 11> (Synthesis of copolymer (A) mixture AU-1)
MEK347 parts was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature inside the reaction vessel to 80 ° C. while maintaining a nitrogen atmosphere, 52 parts of benzyl methacrylate, 17 parts of methacrylic acid, Blemmer PME-1000 (manufactured by NOF Corporation, methoxypolyethylene glycol monomethacrylate:- 207 parts of CH ₂ CH ₂ O-units (about 23), 66 parts of Plaxel FM-5, 116 parts of M-1 solution obtained in Synthesis Example 1, V-65 (manufactured by Wako Pure Chemical Industries, Ltd. 2,2 A mixed solution of 10.4 parts of '-azobis (2,4-dimethylvaleronitrile)) and 218 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of the dropping, 1.7 parts of perbutyl O (t-butyl peroxy 2-ethylhexanoate manufactured by NOF Corporation) was added. After completion of the reaction, part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer (A) mixture AU-1.

<Synthesis Example 12> (Synthesis of copolymer (A) mixture AU-2)
344 parts of MEK was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature in the reaction vessel to 80 ° C. while maintaining a nitrogen atmosphere, 46 parts of benzyl methacrylate, 15 parts of methacrylic acid, 182 parts of Blemmer PME-1000, 55 parts of Plaxel FM-5, M- A mixed solution of 205 parts of 1 solution, 9.1 parts of V-65 and 173 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of dropping, 1.5 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer (A) mixture AU-2.

<Synthesis Example 13> (Synthesis of Copolymer (A) Mixture AU-3)
MEK347 parts was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature inside the reaction vessel to 80 ° C. while maintaining a nitrogen atmosphere, 104 parts of benzyl methacrylate and M-5300 (ω-carboxypolycaprolactone monoacrylate caprolactone units, about 2 from Toagosei Co., Ltd.) from the dropping device. 17 parts, 173 parts of Bremer PME-1000, 48 parts of Plaxel FM-5, 116 parts of M-1 solution, V-65 (2,2′-azobis (2,4-dimethyl) manufactured by Wako Pure Chemical Industries, Ltd. Valeronitrile)) 10.4 parts and MEK 218 parts of a mixed solution was added dropwise over 2 hours 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of the dropping, 1.7 parts of perbutyl O (t-butyl peroxy 2-ethylhexanoate manufactured by NOF Corporation) was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer (A) mixture AU-3.

<Synthesis Example 14> (Synthesis of copolymer (A) mixture AU-4)
MEK 346 parts was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, and then 101 parts of benzyl methacrylate, 17 parts of methacrylic acid, 169 parts of Blemmer PME-1000, 47 parts of Plaxel FM-5 from the dropping device, synthesis example A mixture of 132 parts of the M-2 solution obtained in 2, 10.1 parts of V-65 and 210 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of the dropping, 1.7 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer (A) mixture AU-4.

<Synthesis Example 15> (Synthesis of Copolymer (A) Mixture AU-5)
MEK418 parts were charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, and then 50 parts of benzyl methacrylate, 17 parts of methacrylic acid, 200 parts of Blemmer PME-1000, 63 parts of Plaxel FM-5 from the dropping device, synthesis example A mixture of 149 parts of the M-3 solution obtained in 3 above, 10 parts of V-65 and 233 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of the dropping, 1.7 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer AU-5.

<Synthesis Example 16> (Synthesis of copolymer (A) mixture AU-6)
MEK347 parts was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, 54 parts of benzyl methacrylate, 18 parts of methacrylic acid, 215 parts of Blemmer PME-1000, 68 parts of Plaxel FM-5 from the dropping device, synthesis example A mixture of 92 parts of the M-4 solution obtained in 4 and 10.7 parts of V-65 and 230 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of dropping, 1.8 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer AU-6.

<Synthesis Example 17> (Synthesis of Copolymer (A) Mixture AU-7)
348 parts of MEK was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, and from a dropping device, 56 parts of benzyl methacrylate, 19 parts of methacrylic acid, 223 parts of Bremer PME-1000, 70 parts of Plaxel FM-5, Synthesis Example A mixture of 66 parts of the M-5 solution obtained in Step 5, 11.1 parts of V-65 and 243 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of dropping, 1.8 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer AU-7.

<Synthesis Example 18> (Synthesis of copolymer (A) mixture AU-8)
420 parts of MEK was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and from a dropping device, 52 parts of benzyl methacrylate, 17 parts of methacrylic acid, 208 parts of Blemmer PME-1000, 60 parts of Plaxel FM-5, Synthesis Example A mixture of 127 parts of the M-6 solution obtained in 6 and 10.4 parts of V-65 and 137 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of the dropping, 1.7 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer AU-8.

<Synthesis Example 19> (Synthesis of Copolymer (A) Mixture AU-9)
MEK452 parts were charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, 56 parts of benzyl methacrylate, 19 parts of methacrylic acid, 223 parts of Blemmer PME-1000, 67 parts of Plaxel FM-5, Synthesis Example A mixture of 83 parts of the M-7 solution obtained in 7 and 11.1 parts of V-65 and 126 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of the dropping, 1.9 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer AU-9.

<Synthesis Example 20> (Synthesis of copolymer (A) mixture AU-10)
MEK345 parts was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, and then 46 parts of benzyl methacrylate, 15 parts of methacrylic acid, 183 parts of Blemmer PME-1000, 37 parts of Plaxel FM-5 from the dropping device, synthesis example A mixed solution of 272 parts of the M-7 solution obtained in 7, 9.1 parts of V-65 and 123 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of dropping, 1.5 parts of perbutyl O was added. After completion of the reaction, part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer AU-10.

<Synthesis Example 21> (Synthesis of Copolymer (A) Mixture AU-11)
MEK434 parts were charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, 43 parts of benzyl methacrylate, 15 parts of methacrylic acid, 177 parts of Bremer PME-1000, 59 parts of Plaxel FM-5 from the dropping device, synthesis example A mixed solution of 213 parts of the M-8 solution obtained in Step 8, 8.9 parts of V-65 and 79 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of dropping, 0.9 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer AU-11.

<Synthesis Example 22> (Synthesis of Copolymer (A) Mixture Copolymer AU-12)
MEK 419 parts were charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, and then 169 parts of benzyl methacrylate, 34 parts of methacrylic acid, 101 parts of Blemmer PME-1000, 30 parts of Plaxel FM-5 from a dropping device, synthesis example A mixture of 130 parts of the M-2 solution obtained in 2 above, 10.1 parts of V-65 and 139 parts of MEK was added dropwise over 2 hours and 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of the dropping, 1.7 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of copolymer AU-12.

<Comparative Synthesis Example 1> (Synthesis of (meth) acrylic copolymer HA-1)
MEK (278 parts) was charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature in the reaction vessel to 80 ° C. while maintaining a nitrogen atmosphere, 60 parts of benzyl methacrylate, 20 parts of methacrylic acid, 240 parts of Blemmer PME-1000, Blemmer PP-800 (NOF Corporation) Ltd. polypropylene glycol _{monomethacrylate,} -C _{3 H} 7 O-unit number of about 13) 80 parts, was added dropwise a V-65 10.0 parts of MEK340 parts mixture of 2 hours 30 minutes. After completion of dropping, the reaction was further continued for 11 hours at the same temperature. After 3 hours and 6 hours from the end of dropping, 0.9 parts of perbutyl O was added. After completion of the reaction, a part of the solvent was distilled off under reduced pressure to obtain a 45% solution of (meth) acrylic copolymer HA-1 having a weight average molecular weight of 20,500.

<Comparative Synthesis Example 2> (Synthesis of (meth) acrylic copolymer HA-2)
45% solution of (meth) acrylic copolymer HA-2 with a weight average molecular weight of 13,700 in the same manner as in Comparative Example 1 except that 80 parts of Blemmer PP-800 is changed to 80 parts of Plaxel FM-5. Got.

  Table 2 shows the values calculated from Formula (1) and Formula (2) of AU-1 to AU-12, and HA-1, HA-2, and the weight average molecular weight. The weight average molecular weight was measured by gel permeation chromatography and expressed as a value in terms of polystyrene.

Symbols in the formulas (1) and (2) are as follows.
W: Charge amount (parts by weight) of the polymerizable unsaturated monomer (c) having a hydroxyl group, which is a raw material of the mixture containing the polymerizable unsaturated monomer (b) having a polyurethane structure. However, the mixture containing a polymerizable unsaturated monomer (b) having a polyurethane structure is reacted with a polymerizable unsaturated monomer (c) having a hydroxyl group and a polyurethane having an isocyanate group to convert an excess isocyanate group to a hydroxyl group or A mixture sealed with a compound having an active hydrogen group such as an amino group.
X: A polymerizable unsaturated monomer (c) having a hydroxyl group in W, which is a charged amount (part by weight) of a polymerizable unsaturated monomer containing a hydroxyl group and a polyoxyalkylene group or a polylactone group
Y: Charge amount (parts by weight) of the polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure
Z: Charge amount of polymerizable unsaturated monomer (t) (parts by weight)
V: Charge amount (parts by weight) of the mixture containing the polymerizable unsaturated monomer (b) having a polyurethane structure. However, the mixture containing a polymerizable unsaturated monomer (b) having a polyurethane structure is reacted with a polymerizable unsaturated monomer (c) having a hydroxyl group and a polyurethane having an isocyanate group to convert an excess isocyanate group to a hydroxyl group or A mixture sealed with a compound having an active hydrogen group such as an amino group.

<Example 1> (Production of water-based pigment dispersion-containing composition C1 for inkjet recording)
Fast Gen Blue TGR [DIC type β-type copper phthalocyanine pigment C.I. I. Pigment Blue 15: 3], 4.00 parts, 3.09 parts of the AU-1 solution obtained in Synthesis Example 11, 0.25 parts of 20% potassium hydroxide, 0.30 parts of MEK, and 12.36 parts of water, It was dispersed for 2 hours with a paint conditioner (using zirconia beads having a diameter of 0.5 mm). After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water yielded an aqueous pigment dispersion-containing composition C1 for inkjet recording having a non-volatile content of 20.3% (pigment content of 15.0%).

<Example 2> (Production of water-based pigment dispersion-containing composition C2 for inkjet recording)
First Gen Blue TGR 4.00 parts, 3.66 parts of the AU-2 solution obtained in Synthesis Example 12, 0.31 part of 20% potassium hydroxide and 12.04 parts of water were charged, and a paint conditioner (with a diameter of 0.5 mm) was prepared. (Using zirconia beads) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water yielded an aqueous pigment dispersion-containing composition C2 for inkjet recording having a nonvolatile content of 21.3% (pigment content of 15.0%).

<Example 3> (Production of water-based pigment dispersion-containing composition C3 for inkjet recording)
The dispersion and preparation were carried out in the same manner as in Example 12 except that 3.09 parts of the AU-1 solution of Example 1 was changed to 3.09 parts of the AU-3 solution obtained in Synthesis Example 13, and the non-volatile content was 20.3. % (Pigment content 15.0%) of an aqueous pigment dispersion-containing composition C3 for inkjet recording was obtained.

<Example 4> (Production of water-based pigment dispersion-containing composition C4 for inkjet recording)
First Gen Blue TGR 4.00 parts, 3.16 parts of the AU-4 solution obtained in Synthesis Example 14, 0.24 part of 20% potassium hydroxide, 0.26 part of MEK and 12.33 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water was performed to obtain an aqueous pigment dispersion-containing composition C4 for inkjet recording having a nonvolatile content of 20.5% (pigment content of 15.0%).

<Example 5> (Production of water-based pigment dispersion-containing composition C5 for inkjet recording)
First Gen Blue TGR (4.00 parts), 2.87 parts of the AU-5 solution obtained in Synthesis Example 15, 0.27 parts of 20% potassium hydroxide, 0.56 parts of MEK and 12.29 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water was performed to obtain an aqueous pigment dispersion-containing composition C5 for inkjet recording having a nonvolatile content of 20.0% (pigment content of 15.0%).

<Example 6> (Production of water-based pigment dispersion-containing composition C6 for inkjet recording)
First Gen Blue TGR 4.00 parts, 2.99 parts of the AU-6 solution obtained in Synthesis Example 16, 0.22 parts of 20% potassium hydroxide, 0.36 parts of MEK, and 12.43 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water was performed to obtain an aqueous pigment dispersion-containing composition C6 for inkjet recording having a nonvolatile content of 20.1% (pigment content of 15.0%).

<Example 7> (Production of water-based pigment dispersion-containing composition C7 for inkjet recording)
First Gen Blue TGR 4.00 parts, 2.88 parts of the AU-7 solution obtained in Synthesis Example 17, 0.22 part of 20% potassium hydroxide, 0.42 part of MEK and 12.48 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water was carried out to obtain an aqueous pigment dispersion-containing composition C7 for inkjet recording having a nonvolatile content of 20.0% (pigment content of 15.0%).

<Example 8> (Production of water-based pigment dispersion-containing composition C8 for inkjet recording)
First Gen Blue TGR 4.00 parts, 2.77 parts of the AU-8 solution obtained in Synthesis Example 18, 0.26 parts of 20% potassium hydroxide, 0.62 parts of MEK, and 12.36 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water was carried out to obtain an aqueous pigment dispersion-containing composition C8 for inkjet recording having a nonvolatile content of 20.3% (pigment content: 15.0%).

<Example 9> (Production of water-based pigment dispersion-containing composition C9 for inkjet recording)
First Gen Blue TGR (4.00 parts), 2.58 parts of the AU-9 solution obtained in Synthesis Example 19, 0.24 parts of 20% potassium hydroxide, 0.71 part of MEK, and 12.47 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water was carried out to obtain an aqueous pigment dispersion-containing composition C9 for inkjet recording having a nonvolatile content of 20.3% (pigment content: 15.0%).

<Example 10> (Production of water-based pigment dispersion-containing composition C10 for inkjet recording)
First Gen Blue TGR (4.00 parts), 3.15 parts of the AU-10 solution obtained in Synthesis Example 20, 0.31 part of 20% potassium hydroxide, 0.42 parts of MEK and 12.11 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water yielded an aqueous pigment dispersion-containing composition C10 for inkjet recording having a non-volatile content of 21.1% (pigment content of 15.0%).

<Example 11> (Production of water-based pigment dispersion-containing composition C11 for inkjet recording)
First Gen Blue TGR 4.00 parts, 3.26 parts of the AU-11 solution obtained in Synthesis Example 21, 0.32 parts of 20% potassium hydroxide, 0.37 parts of MEK and 12.05 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water yielded an aqueous pigment dispersion-containing composition C11 for inkjet recording having a non-volatile content of 21.3% (pigment content of 15.0%).

<Example 12> (Production of aqueous pigment dispersion-containing composition M1 for inkjet recording)
First Gen Blue TGR of Example 1 was prepared as Fast Gen Super Magenta RY [Dai Nippon Ink Chemical Co., Ltd. C.I. I. Pigment Red 122] is dispersed and prepared in the same manner as in Example 1 except that the AU-1 solution is changed to the AU-3 solution, and for inkjet recording with a non-volatile content of 20.3% (pigment content of 15.0%). An aqueous pigment dispersion-containing composition M1 was obtained.

<Example 13> (Production of aqueous pigment dispersion-containing composition Y1 for inkjet recording)
Except that Fast Gen Blue TGR of Example 4 was Fast Yellow 7413 (manufactured by Sanyo Dye Co., Ltd.), dispersion and preparation were performed in the same manner as in Example 4 to obtain a non-volatile content of 20.5% (pigment content of 15.0). %) An aqueous pigment dispersion-containing composition Y1 for inkjet recording.

<Example 14> (Production of water-based pigment dispersion-containing composition C14 for inkjet recording)
First Gen Blue TGR 4.00 parts, 2.85 parts of the AU-12 solution obtained in Synthesis Example 22, 0.44 part of 20% potassium hydroxide, 0.58 part of MEK, and 12.14 parts of water were added to a paint conditioner ( (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation with water was carried out to obtain an aqueous pigment dispersion-containing composition C14 for inkjet recording having a non-volatile content of 20.6% (pigment content of 15.0%).

<Comparative example 1> (Production of water-based pigment dispersion-containing composition C12 for inkjet recording)
First condition blue TGR 4.00 parts, 2.67 parts of the HA-1 solution obtained in Comparative Synthesis Example 1, 0.19 parts of 20% potassium hydroxide, 0.53 parts of MEK and 12.60 parts of water, and paint conditioner (Using zirconia beads having a diameter of 0.5 mm) for 2 hours. After the completion of dispersion, MEK was distilled off from the liquid obtained by removing the zirconia beads with an evaporator, and then coarse particles were removed by centrifugation. Preparation was carried out with water to obtain an aqueous pigment dispersion-containing composition C12 for inkjet recording having a non-volatile content of 19.6% (pigment content of 15.0%).

<Comparative example 2> (Production of water-based pigment dispersion-containing composition C13 for inkjet recording)
The HA-1 solution of Comparative Example 1 was dispersed and prepared in the same manner as in Comparative Example 4 except that the HA-2 solution obtained in Comparative Synthesis Example 2 was changed to a non-volatile content of 19.6% (pigment content of 15.0). %) An aqueous pigment dispersion-containing composition C13 for inkjet recording.

(Creation and evaluation of water-based pigment ink for inkjet recording)
<Example 15>
An aqueous pigment ink for inkjet recording was prepared using the aqueous pigment dispersion-containing composition C1 for inkjet recording produced in Example 1. The ink composition is shown below.
Inkjet recording aqueous pigment dispersion-containing composition C1 26.7 parts urethane resin aqueous solution U1 (Synthesis Example 9) 1.1 parts triethylene glycol monobutyl ether 10.0 parts diethylene glycol 15.0 parts Surfynol 465 (manufactured by Air Products) ) 0.8 part water 46.4 parts

(Performance evaluation of water-based pigment ink for inkjet recording)
The aqueous pigment ink for inkjet recording prepared in Example 15 was filled in a cartridge of a commercially available piezo inkjet printer (PX-G930, manufactured by Seiko Epson Corporation), and printed on various recording media.

(Exclusive paper gloss evaluation)
Solid printing was performed on photographic paper (glossy) (manufactured by Seiko Epson Corporation) having an ink receiving layer, which is a special paper. Using a BYK Gardner haze gloss meter, the 20 ° gloss value of the surface of the obtained printed matter was measured, and glossiness was determined as a dedicated paper characteristic. Displayed as gross in the table.
○: (Gross value) ≧ 65
×: (Gross value) <65

(Abrasion)
Evaluation was performed using photographic paper (glossy) [manufactured by Seiko Epson Corporation], which is a special paper. Solid printing was carried out on the same photographic paper. Immediately after printing, the printed part was rubbed with a finger after drying for 10 minutes, and the rubbing condition was visually evaluated. It was displayed in the table as a scratch resistance evaluation. The evaluation criteria are described below.
A: Printing is not taken at all B: Printing is hardly taken and the ground is not soiled C: Printing is scraped, but the ground is not soiled D: Printing is scraped and ground is soiled E: Printing is scraped remarkably Immediately after printing, which is taken and the ground is also dirty ○: A, B, C
X: D, E
10 minutes later: A, B
X: C, D, E

(Gloss change (hereinafter abbreviated as GC))
Evaluation was performed using photographic paper (glossy) [manufactured by Seiko Epson Corporation], which is a special paper. Solid printing was performed on the photographic paper, and the printed portion was rubbed with a finger after drying for one day, and the degree of change in gloss on the printed surface was visually evaluated. It displayed as GC evaluation in the table | surface. The evaluation criteria are described below.
A: There is no change in gloss on the printed matter. B: A slight change in gloss is seen on the printed matter.
C: A change in gloss is observed on the printed matter.
D: The printed part is rubbed.
○: A, B
X: C, D

<Example 16>
In the same manner as in Example 15, except that 1.1 parts of the urethane resin aqueous solution U1 of Example 15 was changed to 3.2 parts and 46.4 parts of water was changed to 44.3 parts, an aqueous pigment ink for inkjet recording was used. Prepared and evaluated.

<Example 17>
Example 15 is the same as Example 15 except that 1.1 parts of the urethane resin aqueous solution U1 of Example 15 is changed to 3.2 parts of the urethane resin aqueous solution U2 obtained in Synthesis Example 10, and 46.4 parts of water is changed to 44.3 parts. Similarly, an aqueous pigment ink for inkjet recording was prepared and evaluated.

<Example 18>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C2 for inkjet recording prepared in Example 2, and 1.1 parts of the urethane resin aqueous solution U1 was changed to 2.0 parts. An aqueous pigment ink for inkjet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 45.5 parts.

<Example 19>
Inkjet recording aqueous solution in the same manner as in Example 15, except that the aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was changed to the aqueous pigment dispersion-containing composition C3 for inkjet recording produced in Example 3. Pigment inks were prepared and evaluated.

<Example 20>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C4 for inkjet recording prepared in Example 4, and 1.1 parts of the urethane resin aqueous solution U1 was changed to 0.9 parts. A water-based pigment ink for inkjet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 46.6 parts.

<Example 21>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C5 for inkjet recording prepared in Example 5, and 1.1 parts of the urethane resin aqueous solution U1 was 2.7 parts. A water-based pigment ink for inkjet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 44.8 parts.

<Example 22>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C6 for inkjet recording prepared in Example 6, and 1.1 parts of the urethane resin aqueous solution U1 was changed to 1.3 parts. An aqueous pigment ink for ink-jet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 46.2 parts.

<Example 23>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C7 for inkjet recording prepared in Example 7, and 1.1 parts of the urethane resin aqueous solution U1 was changed to 1.6 parts. A water-based pigment ink for inkjet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 45.9 parts.

<Example 24>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C8 for inkjet recording prepared in Example 8, and 1.1 parts of the urethane resin aqueous solution U1 was changed to 3.0 parts. A water-based pigment ink for inkjet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 44.5 parts.

<Example 25>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C9 for inkjet recording prepared in Example 9, and 1.1 parts of the urethane resin aqueous solution U1 was changed to 3.4 parts. A water-based pigment ink for inkjet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 44.1 parts.

<Example 26>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C10 for inkjet recording prepared in Example 10, and 1.1 parts of the urethane resin aqueous solution U1 was changed to 2.0 parts. An aqueous pigment ink for inkjet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 45.5 parts.

<Example 27>
The aqueous pigment dispersion-containing composition C1 for inkjet recording of Example 15 was added to the aqueous pigment dispersion-containing composition C11 for inkjet recording prepared in Example 11, and 1.1 parts of the urethane resin aqueous solution U1 was changed to 1.8 parts. A water-based pigment ink for inkjet recording was prepared and evaluated in the same manner as in Example 15 except that 46.4 parts of water was changed to 45.7 parts.

<Example 28>
Using the aqueous pigment dispersion-containing composition M1 for inkjet recording produced in Example 12, an aqueous pigment ink for inkjet recording was prepared with the following composition and evaluated in the same manner as in Example 15.
Inkjet recording aqueous pigment dispersion-containing composition M1 40.0 parts Urethane resin aqueous solution U1 1.6 parts Triethylene glycol monobutyl ether 10.0 parts diethylene glycol 15.0 parts Surfinol 465 0.8 parts Water 32.6 parts

<Example 29>
Using the aqueous pigment dispersion-containing composition Y1 for inkjet recording produced in Example 13, an aqueous pigment ink for inkjet recording was prepared with the following composition and evaluated in the same manner as in Example 15.
Inkjet recording aqueous pigment dispersion-containing composition Y1 39.9 parts Urethane resin aqueous solution U1 1.4 parts Triethylene glycol monobutyl ether 10.0 parts diethylene glycol 15.0 parts Surfinol 465 0.8 parts Water 32.9 parts

<Example 30>
Using the aqueous pigment dispersion-containing composition C14 for inkjet recording produced in Example 14, an aqueous pigment ink for inkjet recording was prepared with the following composition and evaluated in the same manner as in Example 15.
Inkjet recording aqueous pigment dispersion-containing composition C14 26.6 parts Urethane resin aqueous solution U1 2.8 parts Triethylene glycol monobutyl ether 10.0 parts diethylene glycol 15.0 parts Surfinol 465 0.8 parts Water 44.8 parts

<Comparative Example 3>
Using the aqueous pigment dispersion-containing composition C12 for inkjet recording produced in Comparative Example 1, an aqueous pigment ink for inkjet recording was prepared with the following composition and evaluated in the same manner as in Example 15.
Aqueous pigment dispersion-containing composition C12 for inkjet recording 26.7 parts Urethane resin aqueous solution U1 2.1 parts Triethylene glycol monobutyl ether 10.0 parts diethylene glycol 15.0 parts Surfinol 465 0.8 parts Water 45.4 parts

<Comparative Example 4>
A water-based pigment ink for inkjet recording was prepared and evaluated in the same manner as in Comparative Example 3 except that the urethane resin aqueous solution U1 of Comparative Example 2 was changed to the urethane resin aqueous solution U2.

<Comparative Example 5>
Inkjet recording aqueous solution in the same manner as in Comparative Example 3, except that the aqueous pigment dispersion-containing composition C12 for inkjet recording in Comparative Example 3 was changed to the aqueous pigment dispersion-containing composition C13 for inkjet recording produced in Comparative Example 2. A pigment ink was prepared and evaluated.
The measurement results for each of these evaluation items are collectively shown in Table 3.

*) 擦過性の０の列は印字直後における試験結果、１０の列は印字１０分後の試験結果
を表わす。

*) The scratch-free column 0 indicates the test result immediately after printing, and the column 10 indicates the test result 10 minutes after printing.

As a result, the aqueous pigment ink for ink-jet recording using the aqueous pigment dispersion-containing composition for ink-jet recording of the present invention had an acceptable value for the gloss change and scratch resistance. Further, a high introduction ratio of polyoxyalkylene structure or polylactone structure has a high urethane 20 ° GLOSS value of 65 or more.
On the other hand, in Comparative Examples 3 to 5 using the aqueous pigment dispersion-containing composition for inkjet recording that does not contain a copolymer having a polymerizable unsaturated monomer (b) having a polyurethane structure as an essential constituent component, The gloss change was bad and the fretting property was not balanced.

Claims (3)

(1) A pigment, and (2) a polymerizable unsaturated monomer (a) having a polyoxyalkylene structure or a polylactone structure and a polymerizable unsaturated monomer (b) having a polyurethane structure are essential components. A composition containing an aqueous pigment dispersion for ink jet recording, comprising the copolymer (A). The aqueous pigment dispersion-containing composition for inkjet recording according to claim 1, wherein the polyurethane structure in the polymerizable unsaturated monomer (b) having the polyurethane structure contains an acid group. An aqueous ink for inkjet recording, comprising the aqueous pigment dispersion-containing composition for inkjet recording according to claim 1.