JP6128377B2 - Aqueous pigment dispersion composition, recording method and recorded matter - Google Patents

Description

  The present invention relates to an aqueous pigment dispersion composition, a recording method, and a recorded matter.

In recent years, water-based inks have been replaced by organic solvent-based inks in a wide range of fields because of their safety and low environmental impact.
Especially for business use, water-based coloring materials that do not smell are essential as inks used for various types of printing in offices, and in industrial use, they are organic due to problems in the working environment, safety of ink and paint handling, and waste liquid treatment. There is an increasing tendency to use as little solvent as possible. In addition, water-based colorants are also more popular than organic solvent-type colorants because they do not require special equipment such as explosion-proof equipment, exhaust equipment, and organic solvent recovery equipment during production. .

  As water-based colorants, two types of dyes and pigments are used depending on the application. Dyes are excellent in gradation and easy to form high-resolution images, but they have poor light resistance compared to pigments and have practical problems. There is. In contrast, pigments are inferior in dispersibility to dyes, but are extremely excellent in water resistance and light resistance, and many pigment inks have been provided by the advancement of dispersion technology.

  Gravure inks that are printed through printing plate making and aqueous liquid inks for offset printing have been developed, but inkjet recording methods are becoming popular as industrial recording methods that use aqueous inks.

The ink jet recording method is a method in which ink droplets are ejected from a fine nozzle head to record characters and images on the surface of a recording medium such as paper. Since printing can be easily performed on demand without producing a printing plate, it is becoming widespread.
In recent years, in particular, with the improvement of the printing speed of inkjet recording apparatuses, printing on film, coated paper, metal foil, etc., which has been conventionally performed by a roll-to-roll method such as gravure printing or flexographic printing, is inkjet recording. It is being considered to carry out by the method.

  As an ink-jet ink composition used in such an ink-jet recording system, a composition containing pigment particles and a styrene-acrylic copolymer resin has been proposed (for example, Japanese Patent Application Laid-Open No. 2004-35716). In the inkjet ink composition, the styrene-acrylic copolymer resin is constituted by a main chain composed of carbon-carbon bonds. It is difficult to be affected by hydrolysis and the like, is excellent in water solubility and is inexpensive, and can be suitably coated with pigment particles to be microencapsulated.

JP 2004-35716 A JP 2004-35718 A

  However, as a result of studies by the present inventors, the inkjet ink composition using the styrene-acrylic copolymer resin is prone to sedimentation, separation, agglomeration, and the like, particularly when self-dispersing carbon black is used as a pigment. It has been found that not only it is difficult to exhibit sufficient dispersibility, but it cannot always exhibit sufficient compatibility and wettability with respect to a high boiling point organic solvent used as a wetting agent.

In addition, printing on film, coated paper, metal foil, etc., which has been performed by the roll-to-roll method in the past (unlike printing on paper, etc.) cannot be expected to be fixed by penetration of the ink composition. However, a material having sufficient adhesion to the surface of a film to be printed, coated paper, metal foil or the like is required, but the conventional inkjet ink composition has not always exhibited sufficient adhesion.
Furthermore, what can form the ink coating film which has sufficient glossiness is desired as an inkjet ink composition.

  Accordingly, the present invention provides an aqueous pigment dispersion composition capable of forming a coating film exhibiting excellent gloss, adhesion, and color density as well as excellent pigment dispersibility, and also provides a recording method and recorded matter. It is intended to do.

  In order to achieve the above object, the present inventors have conducted intensive studies and found that the aqueous medium-dispersible pigment (A), the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, an amide group, morpholine. A resin particle (B) obtained by copolymerizing an acrylate (b2) having one or more groups selected from a group and an imide group, and a monomer (b3) copolymerizable therewith, and an aqueous medium (C). The present inventors have found that the above technical problems can be solved by using an aqueous pigment dispersion composition, and have completed the present invention based on this finding.

That is, the present invention
(1) Aqueous medium-dispersible pigment (A) and an acrylate having at least one group selected from a phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, an amide group, a morpholine group, and an imide group ( and b2) and which like copolymerizable with the monomer (b3) a copolymer to become resin particles (B), see contains an aqueous medium (C),
An aqueous pigment dispersion composition, wherein the resin particles (B) have an average particle size of 50 to 200 nm ,
(2) The aqueous pigment dispersion composition according to (1), wherein the aqueous medium-dispersible pigment (A) is self-dispersing carbon black,
(3) Phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end is represented by the following general formula (I)
(Wherein, _{R 1} is methyl group or a hydrogen atom, n is an integer of 0 to 3, a is an integer from 1 to 3, b is an integer of 0 to 2, it is a + b = 3, When a is 2 or more, a plurality of R ₁ may be the same or different from each other. When a is 2 or more and n is present, the plurality of n are the same as each other. Or an aqueous pigment dispersion composition according to (1) or (2) above, which is a compound represented by :
(4 ) The resin particle (B) contains 0.1 to 2% by mass of a phosphorus atom derived from a phosphate ester (b1) having a (meth) acryloyloxy group at a molecular end, an amide group, a morpholine group, and an imide The aqueous pigment dispersion composition according to any one of the above (1) to ( 3 ), comprising 0.2 to 5% by mass of a nitrogen atom derived from an acrylate (b2) having one or more groups selected from the group,
( 5 ) The composition according to any one of (1) to ( 4 ), comprising 10 to 300 parts by mass of the resin particles (B) with respect to 100 parts by mass of the aqueous medium-dispersible pigment (A) in terms of solid content. An aqueous pigment dispersion composition,
( 6 ) The aqueous pigment dispersion composition according to any one of the above (1) to ( 5 ), wherein the aqueous pigment dispersion composition is an inkjet ink composition,
( 7 ) A recording method comprising recording by an ink jet recording method using the aqueous pigment dispersion composition described in ( 6 ) above,
( 8 ) A recorded matter that is recorded by an ink jet recording method using the aqueous pigment dispersion composition according to ( 6 ) above,
Is to provide.

  According to the present invention, it is possible to provide an aqueous pigment dispersion composition that is excellent in pigment dispersibility and can form a coating film that exhibits excellent gloss, adhesion, and color density, and provides a recording method and recorded matter. can do.

First, the aqueous pigment dispersion composition of the present invention will be described.
The aqueous pigment dispersion composition of the present invention is a kind selected from an aqueous medium-dispersible pigment (A), a phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, an amide group, a morpholine group, and an imide group. The resin particle (B) obtained by copolymerizing the acrylate (b2) having the above group and the monomer (b3) copolymerizable therewith, and an aqueous medium (C) are characterized in that .

  In the aqueous pigment dispersion composition of the present invention, the pigment constituting the aqueous medium-dispersible pigment (A) is not particularly limited, and examples thereof include black pigments such as carbon black, metals such as titanium oxide, zinc oxide, and iron oxide. Inorganic pigments such as oxides, aluminum flakes, barium sulfate, calcium carbonate, silicates, insoluble azo pigments, soluble azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, isoindoline pigments, benzimidazolone pigments, pyranthrone pigments, One or more selected from organic pigments such as thioindigo pigments and quinophthalone pigments can be mentioned.

  Specific examples of the black pigment include ivory black, peach black, lamp black, mars black, bitumen, titanium black, and carbon black. Among these, carbon black has a carbon content. High, high blackness derived from amorphous structure, excellent jetness and coloring power when used as a black pigment for inkjet recording, faster drying speed and storage stability than peach black, lamp black, etc. Since it is high and inexpensive, it can be suitably used.

  Carbon black manufactured by contact method called channel black, roller black, disc black, manufactured by furnace method called furnace black such as gas furnace black, oil furnace black, etc. And those produced by a thermal method called thermal black or acetylene black.

  Among the above carbon blacks, furnace black is excellent in productivity and ultra fine, so when the obtained aqueous pigment dispersion is used in an ink jet ink composition, a high resolution and excellent print quality is obtained. It becomes easy.

As carbon black, those having an average particle diameter of 50 to 250 nm are preferable, those having 60 to 200 nm are more preferable, and those having 70 to 150 nm are more preferable.
In this application document, the average particle size of carbon black is 50% of the average particle size (average particle size) in the volume-based integrated particle size distribution as measured by Nikkiso Microtrac Ultra Particle Analyzer (UPA). Diameter D50).

In the present application documents, the aqueous medium-dispersible pigment (A) can maintain a stable dispersion state without adding a surfactant or a polymer compound when suspended in water to obtain a dispersion. It means a self-dispersing liquid whose surface tension is almost the same as that of water.
As the aqueous medium-dispersible pigment (A), the pigment itself may be self-dispersible. However, since the surface of a pigment is usually oleophilic, the surface of the pigment is made hydrophilic and self-dispersible. Those to which is given are suitable.

As the self-dispersing pigment, a pigment having an acidic surface is preferable, and as a pigment having an acidic surface, various pigments that have been surface-acid-treated by synergists, pigments having an acidic group introduced into the surface by diazo coupling, and appropriate oxidation are used. At least one hydrophilic group containing an acidic group, such as a pigment having an acidic group such as a phenolic hydroxyl group or a carboxyl group introduced to the surface, or a pigment obtained by neutralizing a pigment acidified by a surface treatment with a counter ion. Examples thereof include those in which the group is bonded directly to the surface of the pigment or through another atomic group.
As the self-dispersing pigment, self-dispersing carbon black in which an acidic group is added to the surface of carbon black is preferable.

  The acidic group introduced into the pigment surface is not particularly limited, and examples thereof include one or more selected from a sulfonic acid group, a phosphoric acid group, a carboxyl group, a hydroxyl group, and the like. The introduction amount of these acidic groups can be controlled, for example, by controlling the gas phase oxidation conditions or liquid phase oxidation conditions described below.

  The oxidation treatment for introducing an acidic group onto the pigment surface can be performed by a known method such as a liquid phase method, a gas phase method, or a combination of these.

  When oxidizing by the liquid phase method, various oxidizing agents such as hydrogen peroxide, nitric acid, sulfuric acid, chlorate, persulfate, percarbonate can be used as the oxidizing agent. A pigment having an acidic group on the surface can be obtained by introducing the pigment into an aqueous solution containing and stirring, and by controlling the amount of the oxidant added and the reaction temperature, the pigment such as carbon black can be obtained. Acidic groups can be uniformly introduced on the surface.

  In addition, in the case of oxidation treatment by a vapor phase method, ozone or air is used as an oxidant, and a method of oxidizing by contacting with a pigment such as carbon black can be exemplified. Therefore, it can be easily oxidized compared with the liquid phase method.

  Furthermore, by introducing acidic groups such as sulfonic acid groups, phosphoric acid groups, and carboxyl groups on the surface of pigments such as carbon black by a coupling reaction with a diazonium salt, or by bringing the pigments into contact with free oxygen at high temperatures, the pigments Examples of the method include introducing an acidic group on the surface, or introducing an acidic group on the pigment surface by treating the pigment surface with bromine and water under normal pressure or pressure.

  Specific examples of the self-dispersing carbon black in which an acidic group is added to the surface of the carbon black by an oxidation method such as the liquid phase method or the gas phase method include Aqua Black (registered trademark) 162 and Aqua Black (registered trademark) 164. , Aqua Black (registered trademark) 120 (all manufactured by Tokai Carbon Co., Ltd.), BONJET (registered trademark) BLACK, CW-2, BONJET (registered trademark) BLACK CW-3 (all manufactured by Orient Chemical Industry Co., Ltd.) Etc.

  As a self-dispersing carbon black in which an acidic group is added to the surface of the carbon black by a method other than the oxidation method such as the liquid phase method or the gas phase method, specifically, CAB-O-JET200 manufactured by Cabot Specialty Co., Ltd. CAB-O-JET300, CAB-O-JET400, etc. can be mentioned.

  Further, when the aqueous medium dispersible pigment (A) is a self-dispersing pigment obtained by imparting self-dispersing properties to cyan, magenta, and yellow pigments, these self-dispersing pigments include CAB-O-JET (registered trademark). ) 250C, CAB-O-JET (registered trademark) 260M, CAB-O-JET (registered trademark) 270Y, CAB-O-JET (registered trademark) 450C, CAB-O-JET (registered trademark) 465M, CAB-O -JET (registered trademark) 470Y (both manufactured by Cabot Specialty Chemicals) and the like.

The aqueous medium-dispersible pigment (A) preferably has a carboxyl group amount of 200 to 1200 μmol / g, more preferably 400 to 1000 μmol / g, and still more preferably 600 to 800 μmol / g.
Note that in the present application, a carboxyl group content, the sodium bicarbonate 0.5 dm ³ of 0.976mol / dm ^3, by adding an aqueous medium dispersion pigment (A) 2 g, was 6 hours shaken, the aqueous It means a value when the medium-dispersible pigment (A) is separated from the reaction solution by filtration and neutralized with a 0.05 mol / dm ³ sodium hydroxide aqueous solution.

  The aqueous pigment dispersion composition of the present invention comprises, as resin particles (B), a phosphate ester (b1) having an (meth) acryloyloxy group (acryloyloxy group or methacryloyloxy group) at the molecular end, an amide group, and a morpholine group. And acrylate (b2) having one or more groups selected from imide groups and those obtained by copolymerization with monomers (b3) copolymerizable therewith.

As the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, the following general formula (I)
(Wherein, _{R 1} is methyl group or a hydrogen atom, n is an integer of 0 to 3, a is an integer from 1 to 3, b is an integer of 0 to 2, it is a + b = 3, When a is 2 or more, a plurality of R ₁ may be the same or different from each other. When a is 2 or more and n is present, the plurality of n are the same as each other. And may be different from each other.

  In the compound represented by the general formula (I), a is an integer of 1 to 3, and when a is 1, the compound represented by the general formula (I) has a (meth) acryloyloxy group at the terminal. When the phosphoric acid ester has one molecular chain and a is 2, the compound represented by the general formula (I) is a compound having two molecular chains having a (meth) acryloyloxy group at the terminal. When a is 3, the compound represented by the general formula (I) is a compound having three molecular chains having a (meth) acryloyloxy group at the terminal.

In the aqueous pigment dispersion composition of the present invention, the resin particles (B) may be obtained by copolymerizing a plurality of types of phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end. In this case, those obtained by copolymerizing a plurality of compounds represented by formula (I) can be mentioned.
When the resin particles (B) are obtained by copolymerizing a plurality of compounds represented by the general formula (I), the average value of a in all the compounds represented by the general formula (I) is a number of 1 to 2 It is preferable that

In the compound represented by the general formula (I), when R ₁ is a methyl group or a hydrogen atom, and R ₁ is a methyl group, the compound represented by the general formula (I) has a methacryloyloxy group at the terminal. When R ₁ is a hydrogen atom, the compound represented by the general formula (I) is a phosphate ester having a molecular chain having an acryloyloxy group at the terminal. is there.
In the compound represented by the general formula (I), when a is 2 or 3, a plurality of R ₁ may be the same or different from each other, and when R ₁ is different, The compound represented by (I) becomes a phosphate ester having a molecular chain having an acryloyloxy group at the terminal and a molecular chain having a methacryloyloxy group at the terminal.

  In the compound represented by the general formula (I), n is an integer of 0 to 3. In the compound represented by the general formula (I), when a is 2 or more and a plurality of n are present, a plurality is present. n may be the same as or different from each other.

  As described above, when the resin particles (B) are obtained by copolymerizing a plurality of compounds represented by the general formula (I), the average value of n in all the compounds represented by the general formula (I) is A number of 0 to 2 is preferred.

In the compound represented by the general formula (I), b is an integer of 0 to 2.
In the compound represented by the general formula (I), a + b = 3.

  In the compound represented by the general formula (I), when b is 0, a is 3, and the compound represented by the general formula (I) is a molecular chain having an acryloyloxy group at the terminal or methacryloyl at the terminal. The phosphoric acid ester having a total of three molecular chains having an oxy group, when b is 1, a is 2, and the compound represented by the general formula (I) has one hydroxyl group and a terminal. Is a phosphate ester having a total of two molecular chains having an acryloyloxy group or a molecular chain having a methacryloyloxy group at the end, and when b is 2, a is 1, and is represented by the general formula (I). The resulting compound is a phosphate ester having two hydroxyl groups and a molecular chain having an acryloyloxy group at the terminal or a molecular chain having a methacryloyloxy group at the terminal. .

  As described above, when the resin particles (B) are obtained by copolymerizing a plurality of compounds represented by the general formula (I), the average value of b in all the compounds represented by the general formula (I) is A number of 0 to 2 is preferred.

Specifically, as a compound represented by the general formula (I), Kayamar PM21 manufactured by Nippon Kayaku Co., Ltd. (in the general formula (I), R ₁ = CH ₃ , n = 1, a = 1, b = 2 and a compound in which R ₁ = CH ₃ , n = 1, a = 2, b = 1 (one average of n is 1, the average of a is 1.5, b And the like having an average value of 1.5).

As the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, in addition to the compound represented by the above general formula (I), the following general formula (II)
(Wherein, _{R 2} is a methyl group or a hydrogen atom, p is an integer of 0 to 3, c is an integer from 1 to 3, d is an integer of 0 to 2, a c + d = 3, When c is 2 or more, a plurality of R ₂ may be the same or different from each other. When c is 2 or more and there are a plurality of p, the plurality of p are the same as each other. Or may be different.) Or a compound represented by the following general formula (III)
(Wherein, _{R 3} is a methyl group or a hydrogen atom, q is an integer of 0 to 3, e is an integer from 1 to 3, f is an integer of 0 to 2, is e + f = 3, When e is 2 or more, a plurality of R ₃ may be the same or different from each other. When e is 2 or more and there are a plurality of q, the plurality of qs are the same as each other. Or may be different.) And the like.

In the compound represented by the general formula (II) and the compound represented by the general formula (III), each of c and e is an integer of 1 to 3.
The resin particles (B) may be obtained by copolymerizing a plurality of compounds represented by the general formula (II). In this case, the average value of c in all the compounds represented by the general formula (II) is The number is preferably 1 or 2.
The resin particles (B) may be obtained by copolymerizing a plurality of compounds represented by the general formula (III). In this case, the average value of e in all the compounds represented by the general formula (III) is also The number is preferably 1 or 2.

In the compound represented by the general formula (II) and the compound represented by the general formula (III), R ₂ and R ₃ are a methyl group or a hydrogen atom.
In the compound represented by the general formula (II), when c is 2 or 3, a plurality of R ₂ may be the same or different from each other, and when R ₂ is different, The compound represented by (II) becomes a phosphate ester having a molecular chain having an acryloyloxy group at the terminal and a molecular chain having a methacryloyloxy group at the terminal.
Also in the compound represented by the general formula (III), when e is 2 or 3, a plurality of R ₃ may be the same or different from each other, and when R ₃ is different, The compound represented by the formula (III) is a phosphate ester having a molecular chain having an acryloyloxy group at the terminal and a molecular chain having a methacryloyloxy group at the terminal.

In the compound represented by the general formula (II), p is an integer of 0 to 3, and in the compound represented by the general formula (II), when c is 2 or more and a plurality of p are present, a plurality of them are present. p may be the same as or different from each other.
In the compound represented by the general formula (III), q is an integer of 0 to 3. In the compound represented by the general formula (III), when e is 2 or more and a plurality of q are present, a plurality is present. q may be the same as or different from each other.

When the resin particles (B) are obtained by copolymerizing a plurality of compounds represented by the general formula (II), the average value of p in all the compounds represented by the general formula (II) is 0 to 2 It is preferable that
When the resin particles (B) are obtained by copolymerizing a plurality of compounds represented by the general formula (III), the average value of q in all the compounds represented by the general formula (III) is a number of 0-2. It is preferable that

In the compound represented by the general formula (II), d is an integer of 0 to 2, and in the compound represented by the general formula (II), c + d = 3.
In the compound represented by the general formula (III), f is an integer of 0 to 2, and in the compound represented by the general formula (III), e + f = 3.

When the resin particles (B) are obtained by copolymerizing a plurality of compounds represented by the general formula (II), the average value of d in all the compounds represented by the general formula (II) is 0 to 2 It is preferable that
When the resin particles (B) are obtained by copolymerizing a plurality of compounds represented by the general formula (III), the average value of f in all the compounds represented by the general formula (III) is also a number from 0 to 2. It is preferable that

  In the present application documents, the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular terminal does not include an acrylate having one or more groups selected from an amide group, a morpholine group, and an imide group. And

  In the aqueous pigment dispersion composition of the present invention, the resin particle (B) contains a structural unit derived from the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, and the phosphorous ester constituting this phosphate ester. The aqueous pigment dispersion composition of the present invention is an inkjet ink composition because the acid group can form a hydrogen bond with the surface-treated surface of a film or coated paper that is a substrate to be printed, or the surface of a metal foil or the like. It can be suitably used as an object.

The resin particles (B) preferably contain 0.1 to 3% by mass of phosphorus atoms derived from the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, and 0.2 to 2. It is more preferable to contain 5% by mass, and it is even more preferable to include 0.3 to 2% by mass.
In addition, in this application document, the content rate of the phosphorus atom derived from the phosphate ester (b1) which has a (meth) acryloyloxy group in the molecular terminal in the resin particle (B) is the said phosphate ester added at the time of copolymerization. The resin particle (B) can be calculated from the mass of (b1) and the molecular weight of the phosphate ester (b1), from the acid value (mgKOH / g) of the phosphate ester (b1) measured in advance. It can also be confirmed by measuring the acid value.

  From the content ratio of the phosphorus atom, the content ratio of the structural unit derived from the phosphate ester (b1) in the resin particle (B) can also be calculated.

  Resin particles (B) include an acrylate (b2) having at least one group selected from an amide group, a morpholine group, and an imide group, together with the phosphoric ester (b1) having a (meth) acryloyloxy group at the molecular end described above. These (phosphoric ester (b1) and acrylate (b2)) and a copolymerizable monomer (b3) are copolymerized.

  Examples of the acrylate (b2) having at least one group selected from an amide group, a morpholine group, and an imide group include (meth) acrylic acid amide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N, N-dimethyl. Acrylate having an amide group such as aminopropylacrylamide, N, N-dimethylmethacrylamide, N-isopropylacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, acryloylmorpholine, methacryl Acrylates having a morpholine group such as morpholine, N-alkylmaleimides such as N-butylmaleimide, (meth) acryloyloxyethylhexahydrophthalimide, (meth) acryloyloxyethyltetrahydrophthalimide, (meth) Reaction products of phthalic anhydrides such as acryloyloxyethylphthalimide, (meth) acryloyloxypropylhexahydrophthalimide, (meth) acryloyloxypropyltetrahydrophthalimide, (meth) acryloyloxypropylphthalimide, and alkanolamine with (meth) acrylic Examples include (meth) acryloyloxyalkylphthalimides which are acid reactants.

The resin particles (B) preferably contain 0.2 to 5.0% by mass of nitrogen atoms derived from the acrylate (b2) having one or more groups selected from amide groups, morpholine groups and imide groups. More preferably, the content is from 3 to 4.0% by mass, and further preferably from 0.4 to 3.0% by mass.
In addition, in this application document, the content rate of the nitrogen atom derived from the acrylate (b2) which has 1 or more types of groups chosen from an amide group, a morpholine group, and an imide group in the resin particle (B) was added at the time of copolymerization. It can be calculated from the mass of the acrylate (b2) and the molecular weight of the acrylate (b2).

  From the content ratio of the nitrogen atom, the content ratio of the structural unit derived from the acrylate (b2) having one or more groups selected from the amide group, morpholine group, and imide group in the resin particles (B) may be calculated. it can.

  In the aqueous pigment dispersion composition of the present invention, the resin particle (B) contains a structural unit derived from an acrylate (b2) having one or more groups selected from an amide group, a morpholine group, and an imide group. The amide group, morpholine group, and imide group that constitutes ()) can improve the compatibility and wettability with the aqueous medium-dispersible pigment (A) and the high-boiling organic solvent used as a wetting agent. Therefore, the water-based pigment dispersion composition of the present invention can be suitably used as an inkjet ink composition or the like.

  The resin particles (B) are prepared together with the acrylate (b2) having one or more groups selected from the above-described phosphate ester (b1) having a molecular end (meth) acryloyloxy group, an amide group, a morpholine group, and an imide group. And a monomer (b3) copolymerizable with the above.

  The monomer (b3) is copolymerized with a phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end and an acrylate (b2) having one or more groups selected from an amide group, a morpholine group and an imide group. There is no particular limitation as long as it is possible.

  As the monomer (b3), methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) Acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, docosanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl ( Alkyl (meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cycloalkyl (meth) acrylate, and the like; styrene, p-ter -Aromatic vinyl monomers such as butyl styrene, α-methyl styrene, vinyl toluene, etc .; product name Veova 9 (neonanoic acid vinyl ester), product name Veova 10 (neodecanoic acid vinyl ester), etc. One or more selected from vinyl monomers and the like can be mentioned.

  Examples of the monomer (b3) include 2-methoxyethyl (meth) acrylate, 4-butoxy (meth) acrylate, (meth) acrylate, ω-alkoxyalkyl (meth) acrylate, and N, N-dimethylamino (meth) ) Monomers having tertiary amino acids such as acrylate and N, N-diethylamino (meth) acrylate; amino group-containing monomers such as acryloyl morpholine and N, N-dimethyl (meth) acrylamide; and 2-hydroxyethyl (meth) Hydroxyl group-containing compounds such as acrylate, (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, etc. Monomers and hydroxyl group-containing monomers obtained by adding ε-caprolactone to these hydroxyl group-containing monomers; monomers having an active methylene group such as vinyl acetoacetate and 2-acetoacetoxyethyl (meth) acrylate; vinyltrimethoxysilane, 3- ( Monomers having a silyl group such as (meth) acryloyloxypropyltrimethoxysilane; epoxy groups such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4 epoxycyclohexyl (meth) acrylate, glycidyl vinyl ether, allyl glycidyl ether 2-isocyanate propene, 2-isocyanate ethyl vinyl ether, 2-isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethyl One or more selected from monomers having an isocyanate group, such as benzyl isocyanate, and the like.

  Furthermore, as the monomer (b3), polyoxyalkylene ether (meth) such as polyoxyethylene ether glycol mono (meth) acrylate, polyoxypropylene ether glycol mono (meth) acrylate, polyoxybutylene ether glycol (meth) acrylate, etc. Acrylate; Monovinyl ether of polyoxyalkylene ether diol, etc. One terminal group is a vinyl group and the opposite molecular terminal is a hydroxyl group monomer; Opposite to the above-mentioned polyoxyalkylene ether (meth) acrylate, vinyl group of polyoxyalkylene vinyl ether And a polyoxyalkylene ether having a terminal hydroxyl group such as methoxy, ethoxy, propyloxy, butoxy, lauryloxy, stearyloxy, etc. Meth) acrylate, the molecular terminal hydroxyl groups of opposite vinyl group of the polyoxyalkylene ether is phenyl, one or more can be mentioned selected from monomers such nonylphenyl terminated.

  In each compound constituting the monomer (b3), the polyoxyalkylene ether chain is obtained by block copolymerization with one or more selected from oxyethylene ether, oxypropylene ether, oxybutylene ether, and the like, or is randomly copolymerized. It may be formed by copolymerization with lactones such as polycaprolactone.

  The monomer (b3) may be an acid vinyl monomer having a vinyl group and an acid in order to increase the dispersion stability in an aqueous medium such as water, if necessary. Examples of the acid vinyl monomer include acrylic acid, Methacrylic acid, itaconic acid, maleic acid, fumaric acid and dibasic acids itaconic acid, maleic acid, half ester vinyl monomer in which only one carboxyl group of fumaric acid is alkyl ester, β hydroxyethyl (meth) Carboxyl groups in the molecule obtained by reaction of hydroxyl groups of hydroxyalkyl (meth) acrylates such as acrylates with acid anhydrides such as succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. And (meth) acryloyl group-containing acid vinyl monomer, acrylic acid dimer, ( Data) vinyl acid obtained by adding caprolactone such as acrylic acid and ε-caprolactone monomer, and a hydroxyl group of a hydroxyalkyl (meth) acrylic acid ester, and the like acid vinyl monomers consisting of monoesters of phosphoric acid.

In order to stably disperse the resin particles (B) in the aqueous medium, the resin particles (B) may be neutralized with a counter ion as necessary.
Examples of the counter ion include various basic compounds. Examples of the basic compound include trimethylamine, triethylamine, 2-aminoethanol, 2-dimethylaminoethanol, ammonia, sodium hydroxide, potassium hydroxide, One or more selected from tetraammonium hydroxide, trimethylbenzylammonium hydroxide, and the like can be given.
When the aqueous pigment dispersion composition of the present invention contains the counter ion as the resin particle (B), the counter ion evaporates from the coating film when used in an ink composition or a coating material, whereby the water resistance of the coating film is increased. In order to express the effect, it is preferable to employ a volatile basic compound as the counter ion, specifically, selected from ammonia, triethylamine, 2-dimethylaminoethanol, and the like. One or more of these may be mentioned.

  The amount of the counter ion used is equivalent to 0.3 to 1.2 equivalents with respect to the phosphate group of the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end and 1 equivalent of the acid vinyl monomer. The amount is preferably an amount corresponding to 0.6 to 1.1 equivalents.

The content ratio of the structural unit derived from the monomer (b3) in the resin particle (B) is derived from the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end in the resin particle (B). Is appropriately adjusted according to the content ratio of the structural unit to be formed and the content ratio of the acrylate (b2) having one or more groups selected from the amide group, morpholine group and imide group.
The content rate of the structural unit derived from the said monomer (b3) in the resin particle (B) was calculated | required by the method mentioned above from 100 mass%, and the phosphate ester ((meth) acryloyloxy group at the molecular terminal ( The content (mass%) of the structural unit derived from b1) and the content (mass%) of the structural unit derived from the acrylate (b2) having one or more groups selected from amide group, morpholine group and imide group Can be obtained by subtracting.

  In the aqueous pigment dispersion composition of the present invention, the resin particles (B) are structural units derived from the phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, an amide group, a morpholine group, and an imide group. In addition to the structural unit derived from the acrylate (b2) having one or more groups selected from the above, the structural unit derived from the monomer (b3) copolymerizable therewith, and the structural unit derived from this monomer (b3) , Hydrophilicity (dispersibility in an aqueous medium) and lipophilicity (affinity to pigment) can be easily controlled.

The resin particles (B) may contain a polymerization initiator used when forming the resin particles (B).
Resin particles (B) are composed of a phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, an acrylate (b2) having one or more groups selected from an amide group, a morpholine group, and an imide group, and When the total amount of the copolymerizable monomer (b3) is 100 parts by mass, it is appropriate to contain 0.1 to 10 parts by mass of a polymerization initiator, and 0.2 to 5 parts by mass. It is more suitable, and what contains 0.3-3 mass parts is further suitable.

The resin particles (B) preferably have an acid value of 10 to 200 mgKOH / g, more preferably 15 to 150 mgKOH / g, and still more preferably 20 to 100 mgKOH / g.
The acid value of the resin particles (B) is an acrylate (b2) having one or more groups selected from a phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, an amide group, a morpholine group, and an imide group. Moreover, it can control by adjusting the kind and compounding quantity of the monomer (b3) copolymerizable with these.

The resin particles (B) preferably have an average particle size of 20 to 150 nm, more preferably 30 to 100 nm, and still more preferably 40 to 80 nm.
When the average particle diameter of the resin particles (B) is 20 to 150 nm, the resin particles (B) can be suitably used as a vehicle for the inkjet ink composition.
In the present application documents, the average particle size of the resin particles (B) is 50% in terms of the cumulative particle size in the volume-based cumulative particle size distribution, as measured by Nikkiso Co., Ltd. Microtrac Ultra Particle Analyzer (UPA). It means the particle size (average particle size D50).

The resin particle (B) is, for example, the acrylate (b2) having one or more groups selected from the above-described phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, an amide group, a morpholine group, and an imide group. ), And a monomer (b3) copolymerizable therewith, can be prepared by copolymerization by an emulsion polymerization method or a dispersion method.
In consideration of the dispersibility of the obtained resin particles (B) in an aqueous medium, the resin particles (B) are preferably obtained by copolymerizing each component by an emulsion polymerization method.

  When producing the resin particles (B) by an emulsion polymerization method or a dispersion method, it is preferable to copolymerize each component in the presence of a polymerization initiator.

  As said polymerization initiator, 1 or more types chosen from the water-soluble radical initiator whose 1-hour half life of a polymerization initiator is 100 degrees C or less are preferable.

When the resin particles (B) are prepared by copolymerizing each component by the emulsion polymerization method, the polymerization initiator includes inorganic water-soluble initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate; Wako Pure Chemical Industries, Ltd. Azonitrile-based water-soluble initiators such as V-30 and V-501 manufactured by Co., Ltd .; 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (for example, Wako Pure Chemical Industries, Ltd.) VA-086), 2,2′-azobis [2-methyl-N- (1-1′-bis (hydroxymethyl) -2-hydroxyethyl) propionamide] (for example, Wako Pure Chemical Industries, Ltd.) ) Azoamide water-soluble initiators such as VA080)
2,2′-azobis (2-amidinopropane) dihydrochloride (for example, V-50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [N- (2-carboxyethyl) -2-methyl Propionamidine] · 4H ₂ O (for example, Wako Pure Chemical Industries, Ltd. VA-057) and other azoamidine-based water-soluble initiators;
2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) · 2HCl (for example, VA-067 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-] (2 -Imidazolin-2-yl) propane · 2HCl (for example, VA044 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] · 2H ₂ SO ₄ ( For example, VA-046B manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} 2HCl (for example, WA Azo imidazoline series such as VA060 manufactured by Kojun Pharmaceutical Co., Ltd.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (for example, VA-061 manufactured by Wako Pure Chemical Industries, Ltd.) Water-soluble initiator;
Polymer azo polymerization initiator (for example, VPE-0201 manufactured by Wako Pure Chemical Industries, Ltd., VPE-0401 manufactured by Wako Pure Chemical Industries, Ltd., VPE-0601 manufactured by Wako Pure Chemical Industries, Ltd.)
One or more types selected from organic water-soluble initiators such as

  Further, when the resin particles (B) are prepared by copolymerizing each component by an emulsion polymerization method, examples of the polymerization initiator include benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1, Organic peroxide polymerization initiators such as 3,3-tetramethylbutylperoxy-2-ethylhexanoate, or 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4- One or more selected from oil-soluble polymerization initiators such as azo polymerization initiators such as dimethylvaleronitrile) and 2,2′-azobis (2-methylbutyronitrile), and having a (meth) acryloyloxy group at the molecular end The phosphoric acid ester (b1), the acrylate (b2) having one or more groups selected from an amide group, a morpholine group and an imide group, and a monomer (b3) copolymerizable therewith in advance After mixing and dissolving, it can be used in combination with a water-soluble polymerization initiator.

  The amount of the polymerization initiator used is a phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, an acrylate (b2) having one or more groups selected from an amide group, a morpholine group and an imide group, and this When the total amount of the copolymerizable monomer (b3) is 100 parts by mass, it is suitably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass. It is more suitable that it is 0.3-3 mass parts.

When the resin particles (B) are prepared by copolymerizing each component by an emulsion polymerization method, an emulsifier is added to the reaction system to form an emulsion.
Examples of the emulsifier include dodecylbenzene sulfonate, naphthalene sulfonic acid formalin condensate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphate, and the like. Nonionic surfactants such as ionic surfactants, alkylphenol type surfactants, polyoxyethylene styrenated phenyl ethers, polyoxyalkylene alkyl ethers, amphoteric surfactants, (meth) acryloyl groups, propenyl groups, etc. One or more kinds selected from reactive surfactants having a vinyl group can be mentioned.

When the resin particles (B) are prepared by copolymerizing each component by an emulsion polymerization method, a known method can be employed, for example, a phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end. , An acrylate (b2) having one or more groups selected from an amide group, a morpholine group, and an imide group, and a monomer (b3) copolymerizable therewith, mixed and stirred with water and an emulsifier, and obtained. Part of the resulting suspension and part of the polymerization initiator are placed in a reaction vessel, heated to the reaction temperature and polymerized to form a pre-emulsion, and then the pre-emulsion obtained at the above reaction temperature. Examples include a method in which the suspension and the remainder of the polymerization initiator are dropped and reacted.
When the resin particles (B) are prepared by copolymerizing each component by the emulsion polymerization method, the temperature and reaction time for reacting each component can be appropriately selected according to each component to be copolymerized.

  The aqueous pigment dispersion composition of the present invention contains resin particles (B), and the resin particles (B) form hydrogen bonds with the surface of the film to be printed, coated paper, metal foil, etc., and firmly adhere to them. And improve the compatibility and wettability with the aqueous medium-dispersible pigment (A) and the high-boiling organic solvent used as a wetting agent, improve the dispersibility of the pigment, and improve the gloss and color density Therefore, it can be suitably used as an inkjet ink composition or the like.

The aqueous pigment dispersion composition of the present invention contains an aqueous medium (C) together with the aqueous medium-dispersible pigment (A) and the resin particles (B).
Examples of the aqueous medium (C) include water and a mixed solution in which a water-soluble organic solvent is mixed with water, but water is preferable from the viewpoint of economy and safety, and deionized water is particularly preferable. preferable.

  The aqueous pigment dispersion composition of the present invention preferably contains 2 to 20% by mass of the aqueous medium-dispersible pigment (A), more preferably 3 to 12% by mass, and 4 to 10% by mass. More preferred.

  The aqueous pigment dispersion composition of the present invention preferably contains 10 to 300 parts by mass of the resin particles (B) with respect to 100 parts by mass of the aqueous medium-dispersible pigment (A) in terms of solid content. More preferably, it contains 200 parts by mass, and even more preferably 30-150 parts by mass.

When the amount of the resin particles (B) with respect to 100 parts by mass of the aqueous medium-dispersible pigment (A) exceeds 300 parts by mass, the coating film performance such as adhesion is improved, but the pigment concentration is relatively lowered. The color density of the resulting coating film tends to decrease.
The aqueous pigment dispersion composition of the present invention exhibits excellent pigment dispersibility when used as an ink-jet ink composition, etc., because the concentration of the resin particles (B) is within the above range. To improve the adhesion and wettability with high-boiling organic solvents used as aqueous media-dispersible pigments (A) and wetting agents, etc. It is possible to impart excellent gloss to the resulting coating film.

  In the aqueous pigment dispersion composition of the present invention, the concentration of the aqueous medium-dispersible pigment (A) is adjusted to a desired concentration by the aqueous medium (C). Usually, the aqueous medium-dispersible pigment (A) is contained in the aqueous pigment dispersion composition. 2) to 20% by mass of the aqueous medium (C) is adjusted to obtain an aqueous pigment dispersion composition having sufficient color density and viscosity suitable for printing as an inkjet ink composition or the like. Can do.

  The aqueous pigment dispersion composition of the present invention can be obtained by using a residual aqueous medium (C) obtained by subtracting the aqueous medium-dispersible pigment (A) and the resin particles (B). Since the aqueous pigment dispersion composition of the present invention contains the aqueous medium (C) in the above range, an aqueous pigment dispersion composition having excellent dispersibility and a desired solid content concentration can be easily obtained.

  The aqueous pigment dispersion composition of the present invention preferably has a solid content concentration of 2 to 25% by mass, more preferably 3 to 20% by mass, and even more preferably 4 to 15% by mass.

  The aqueous pigment dispersion composition of the present invention comprises, in addition to the aqueous medium-dispersible pigment (A), resin particles (B), and aqueous medium (C), a wax dispersed in water, a resin particle emulsion, a humectant, and a preservative. , An emulsifier, a pH adjuster, an antifoaming agent, an additive such as a coating film surface smoothing agent, and a known component such as a water-soluble resin may be included. By including these components, an aqueous pigment composition was used. It is possible to easily develop paintability, ink applicability, printability, paint scratchability, hardness, flexibility, and the like.

  The resin particle emulsion is not particularly limited, and examples thereof include vinyl monomers having an unsaturated group such as acrylic ester, methacrylic ester, styrene, acrylamide, acryloyl morpholine, acrylonitrile, vinyl vinyl acetate, vinyl acetate, and butadiene. , Acrylic acid, methacrylic acid, crotonic acid, fumaric acid, acid having an unsaturated group such as maleic acid, base monomer such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, or polyoxyethylene ether From self-emulsifying and dispersing emulsions copolymerized with chain oligomers; from emulsion polymerization emulsion resins such as emulsions that are emulsified and dispersed using anionic, cationic or nonionic emulsifiers Mention may be made of one or more of the barrel.

  In addition, as the resin particle emulsion, for example, a self-emulsification dispersion type in which a polyurethane resin having a nonionic molecular chain, an acidic group, or a basic group in the molecule is neutralized with a counter ion and phase-shifted and dispersed in water. Polyurethane resin emulsions; Self-emulsifying and dispersing polyester resin emulsions in which a polyester resin having an acidic group in the molecule is neutralized with a counter ion and phase-reversed and dispersed in water; an alkyd resin having an acidic group in the molecule Is selected from self-emulsifying and dispersing alkyd resin emulsions that are neutralized with a counterion and phase-dispersed in water; and self-emulsifying and dispersing acrylic resin emulsions obtained by copolymerizing the above-mentioned vinyl monomers having unsaturated groups. One or more of these may be mentioned.

  As the resin particle emulsion, those having compatibility with the resin particles (B) are preferable. In general, when different types of resins are mixed, those having better compatibility over a wide range of mixing are blended. The degree of freedom is high, and it becomes easy to obtain a coating film excellent in pigment concentration such as gloss and blackness.

  Since the aqueous pigment dispersion composition of the present invention contains the resin particle emulsion, the average particle diameter of the resin particles and the viscosity can be easily adjusted, and the strength and hardness of the resulting coating film can be adjusted. Can be easily controlled.

  Examples of humectants include polyoxyalkylene ether glycols such as glycerin, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 3-methylpentanediol, 1,2-pentanediol, 1,5-pentanediol, etc. Water-soluble such as polyalkylenediols, monoalkyl ethers of polyoxyalkylene ether glycols, dialkyl ethers, N-methyl-2-pyrrolidone, 2-pyrrolidone, ecamide (manufactured by Idemitsu Kosan Co., Ltd.), BYKEOL (BYK) One or more selected from high-boiling solvents and the like can be mentioned.

  In addition, the aqueous pigment dispersion composition of the present invention has effects such as a known general-purpose antifoaming agent and a wettability improvement aid in order to easily obtain effects such as coating suitability, printability, and smoothness of the coating film. In order to facilitate, additives, auxiliaries and organic solvents may be included.

  The aqueous pigment dispersion composition of the present invention is added to an agitating vessel while adding the aqueous medium-dispersible pigment (A), the resin particles (B) and the aqueous medium (C) with stirring. Addition of water-dispersed wax, resin particle emulsion, moisturizer, preservative, emulsifier, pH adjuster, antifoaming agent, coating surface smoothing agent, water-soluble resin, etc. If necessary, it can be produced by adjusting the viscosity with water or a water-soluble organic solvent and filtering by a known arbitrary filtration method.

  The aqueous pigment dispersion composition of the present invention can be used as various paints and ink compositions, and can be particularly suitably used as an inkjet ink composition.

  According to the aqueous pigment dispersion composition of the present invention, it is possible to provide an aqueous pigment dispersion composition that is excellent in pigment dispersibility and can form a coating film that exhibits excellent gloss, adhesion, and color density. .

Next, the recording method of the present invention will be described.
The recording method of the present invention is characterized by recording by the ink jet recording system using the aqueous pigment dispersion composition of the present invention.

  The details of the aqueous pigment dispersion composition of the present invention are as described above. In addition, as a recording method by the ink jet recording method, a known method can be appropriately employed.

  In the recording method of the present invention, the recording material is suitably at least one selected from a film, coated paper, metal foil and the like.

  Since the recording method of the present invention uses the aqueous pigment dispersion composition of the present invention, it is possible to form a coating film that exhibits excellent gloss, adhesion and color density.

Next, the recorded matter of the present invention will be described.
The recorded matter of the present invention is characterized by being recorded by the ink jet recording method using the aqueous pigment dispersion composition of the present invention.

  The details of the aqueous pigment dispersion composition of the present invention are as described above. In addition, as a recording method by the ink jet recording method, a known method can be appropriately employed.

  The recorded matter of the present invention is suitably formed on one or more base materials selected from films, coated papers, metal foils and the like.

  Since the recorded matter of the present invention uses the aqueous pigment dispersion composition of the present invention, it can exhibit excellent glossiness, adhesion and color density.

  The contents of the present invention will be described below with reference to specific examples together with comparative examples. However, the present invention is not limited to these examples.

The aqueous medium-dispersible pigment (A) (Pigment (A) -1, Pigment (A) -2) used in the following Examples and Comparative Examples has the following physical properties.
(1) Pigment (A) -1
Carbon black aqua black 162 manufactured by Tokai Carbon Co., Ltd. (solid content concentration: 19.2% by mass), which is an aqueous dispersion of acidic carbon black containing carbon black pigment having an acidic functional group introduced as pigment (A) -1. Was used.
Pigment (A) -1 are those acidic functional group is introduced by oxidizing the carbon black DBP oil absorption 115cm ^3/100 g, amount of carboxyl group measured by the following methods 780μmol / g, When measured with a Nikkiso Co., Ltd. Microtrac Ultra Particle Analyzer (UPA), the 50% particle size (average particle size D50) in the volume-based integrated particle size distribution was 110 nm.

(2) Pigment (A) -2
As a pigment (A) -2, Tokai Carbon Co., Ltd. carbon black aqua black 120 (solid content concentration 19.5 mass%) which is an aqueous dispersion of acidic carbon black containing a carbon black pigment having an acidic functional group introduced Was used.
Pigment (A) -2 are those acidic functional group is introduced by oxidizing the carbon black DBP oil absorption of 56cm ^3/100 g, amount of carboxyl group measured by the following methods 600 [mu] mol / g, When measured with a Nikkiso Microtrac Ultra Particle Analyzer (UPA), the 50% particle size (average particle size D50) in the volume-based integrated particle size distribution was 80 nm.

<Method for measuring the amount of carboxyl group>
In 0.976mol / dm ³ of sodium bicarbonate 0.5 dm ^3, with the addition of carbon black 2g, after 6 hours shaken, filtered off the carbon black from the reaction solution, the filtrate of 0.05 mol / dm ³ Neutralization titration with an aqueous sodium hydroxide solution was performed to quantify the amount of carboxyl groups.

  In addition, the acrylate (b2) having at least one group selected from a phosphate ester (b1) having a (meth) acryloyloxy group at a molecular end, an amide group, a morpholine group, and an imide group, used in the following Examples, In addition, resin particles (B) (resin particles (B) -1 to (B) -6) obtained by copolymerizing these and a copolymerizable monomer (b3) were produced as follows. It is.

<Preparation of resin particle (B) -1 (phosphate ester / morpholine group-containing resin particle)>
(1) Preparation of reaction liquid A 1 liter (1 L) reactor (reaction vessel) equipped with a stirring blade, a condenser, a nitrogen blowing tube, a dropping tank a and a dropping tank b was charged with 106 g of ion-exchanged water and NOF Corporation ) 0.52 g of emulsifier Newlex Soft Type 30 was prepared and dissolved by stirring.
On the other hand, in the dropping tank a, 3.5 g of 1,6-hexanediol diacrylate, 17.5 g of acryloylmorpholine (amount corresponding to 10% by mass of all monomers), 78.5 g of styrene monomer, 2-methacryloyl Oxyethyl caproate acid phosphate (Nippon Explosives Co., Ltd. Kayamer PM21, in general formula (I), R ₁ = CH ₃ , n = 1, a = 1, b = 2, and R ₁ = CH ₃ , n = 1, a = 2, b = 1 one-to-one mixture with a compound), 8.7 g, Adeka Co., Ltd. reactive emulsifier Adekaria soap SR-10, ethyl acrylate 61.1 g of water, and while stirring, add an aqueous solution of 0.35 g of NOF's emulsifier Newlex Soft Type 30 dissolved in 153 g of ion-exchanged water in advance. More, a monomer emulsion was prepared in a dropping tank a.
Further, in the dropping tank b, 0.7 g of an aqueous azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 65 g of ion-exchanged water to prepare a polymerization initiator aqueous solution in the dropping tank b.

(2) Synthetic reaction In the above reaction vessel, stirring, nitrogen gas blowing, condenser cooling was started, and after raising the temperature of the reaction vessel to 73 ° C, 1/6 of the total volume of the monomer emulsion was dropped from the dropping tank a. Further, after 1/6 of the total volume of the polymerization initiator aqueous solution was dropped from the dropping tank b, the temperature was raised again to 73 ° C., and the reaction was performed at the same temperature for 1 hour.
Subsequently, the remainder of the monomer emulsion (5/6 of the total volume of the monomer emulsion) is dropped from the dropping tank a over 2 hours, and the remainder of the polymerization initiator aqueous solution (the total volume of the polymerization initiator aqueous solution) is dropped from the dropping tank b. 5/6) was added dropwise over 2 hours to cause the reaction.
The non-volatile content is measured every 2 hours after the completion of the dropping, and the non-volatile content is 34% by mass or more. In two consecutive measurements, the non-volatile content difference is 0.3% by mass. The reaction was carried out until it became less than%.
After completion of the reaction, 1.8 g of triethylamine is added to the reaction vessel while cooling, followed by 200-mesh wire mesh filtration at a temperature of 30 ° C. or lower, whereby resin particles (B) -1 (phosphate ester / morpholine group). Containing resin particles).

(3) the resin particles (B) -1 of physical properties and component amounts obtained resin particles (B) -1 is non volatile content ratio 34.5% by weight, Gardner bubble viscosity of A-A1 ^2, Nikkiso When measured with Microtrac Ultra Particle Analyzer (UPA) manufactured by Co., Ltd., the particle size of 50% (average particle size D50) in terms of the integrated particle size in the volume-based integrated particle size distribution was 178 nm.
The resin particle (B) -1 contains 0.35% by mass of a phosphorus atom derived from a phosphate ester (b1) having a methacryloyloxy group at the molecular end in terms of solid content, and includes an amide group and a morpholine group. And 1% by mass of nitrogen atoms derived from acrylate (b2) having one or more groups selected from imide groups.

<Preparation of resin particle (B) -2 (phosphate ester / amide group-containing resin particle)>
(1) Preparation of reaction liquid 106 g of ion-exchanged water and NOF Emulsifier New Co., Ltd. were added to a reactor (reaction vessel) having a capacity of 1 L equipped with a stirring blade, a condenser, a nitrogen blowing tube and a dropping tank a and a dropping tank b. 0.52 g of Rexsoft type 30 was charged and dissolved by stirring.
On the other hand, in the dropping tank a, 3.5 g of 1,6-hexanediol diacrylate, 17.5 g of diethylacrylamide (amount corresponding to 10% by mass of all monomers), 78.5 g of styrene monomer, 2-methacryloyl 8.7 g of oxyethyl caproate acid phosphate (Kayamar PM21 manufactured by Nippon Explosives Co., Ltd.), 8.7 g of Adeka Reactive Emulsifier manufactured by Adeka Co., Ltd., 57.6 g of ethyl acrylate, While stirring, a monomer emulsion was prepared in the dropping tank a by adding an aqueous solution prepared by dissolving 0.35 g of NOF's emulsifier Newlex Soft Type 30 in 153 g of ion-exchanged water in advance.
Further, in the dropping tank b, 0.7 g of an aqueous azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 65 g of ion-exchanged water to prepare a polymerization initiator aqueous solution in the dropping tank b.

(2) Synthetic reaction Using the monomer emulsion prepared in (1) and the polymerization initiator aqueous solution, the synthetic reaction is performed under the same conditions as "(2) Synthetic reaction" in the preparation example of resin particles (B) -1. Thus, resin particles (B) -2 (phosphate ester / amide group-containing resin particles) were obtained.

(3) the resin particles (B) -2 physical properties and component amounts obtained resin particles (B) -2, the non volatile content ratio 35.0% by weight, Gardner bubble viscosity of A2-A3 ^2, Nikkiso When measured with a Microtrac Ultra Particle Analyzer (UPA) manufactured by Co., Ltd., a 50% particle size (average particle size D50) in the volume-based cumulative particle size distribution was 83.9 nm.
The resin particle (B) -2 contains 0.35% by mass of a phosphorus atom derived from a phosphate ester (b1) having a methacryloyloxy group at the molecular end in terms of solid content, and includes an amide group and a morpholine group. And 1.1% by mass of nitrogen atoms derived from the acrylate (b2) having an imide group.

<Preparation of resin particles (B) -3 (phosphate ester / amide group-containing resin particles)>
(1) Preparation of reaction liquid 106 g of ion-exchanged water and NOF Emulsifier New Co., Ltd. were added to a reactor (reaction vessel) having a capacity of 1 L equipped with a stirring blade, a condenser, a nitrogen blowing tube and a dropping tank a and a dropping tank b. 0.52 g of Rexsoft type 30 was charged and dissolved by stirring.
On the other hand, in the dropping tank a, 3.5 g of 1,6-hexanediol diacrylate, 17.5 g of diethylacrylamide (amount corresponding to 10% by mass of all monomers), 87.2 g of styrene monomer, 2-methacryloyl 8.7 g of oxyethyl caproate acid phosphate (Kayamar PM21 manufactured by Nippon Explosives Co., Ltd.), 8.7 g of reactive emulsifier Adeka Soap SR-10 manufactured by Adeka Co., Ltd., and 48. 2-methoxyethyl acrylate. A monomer emulsion was prepared in the dropping tank a by adding 9 g of an aqueous solution prepared by previously dissolving 0.35 g of NOF's emulsifier Newlex Soft Type 30 in ion-exchanged water 153 g while stirring.
Further, in the dropping tank b, 0.7 g of an aqueous azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 65 g of ion-exchanged water to prepare a polymerization initiator aqueous solution in the dropping tank b.

(2) Synthetic reaction Using the monomer emulsion prepared in (1) and the polymerization initiator aqueous solution, the synthetic reaction is performed under the same conditions as "(2) Synthetic reaction" in the preparation example of resin particles (B) -1. Thus, resin particles (B) -3 (phosphate ester / amide group-containing resin particles) were obtained.

(3) Physical properties and component amounts of resin particle (B) -3 The obtained resin particle (B) -3 has a non-volatile content of 34.6% by mass, a Gardner cell viscosity of A2-A3 ² , and Nikkiso When measured with Microtrac Ultra Particle Analyzer (UPA) manufactured by Co., Ltd., the 50% particle size (average particle size D50) in the volume-based cumulative particle size distribution was 81.6 nm.
The resin particles (B) -3 contain 0.35% by mass of a phosphorus atom derived from a phosphate ester (b1) having a methacryloyloxy group at the molecular end in terms of solid content, and include an amide group and a morpholine group. And 1.1% by mass of nitrogen atoms derived from acrylate (b2) having one or more groups selected from imide groups.

<Preparation of resin particles (B) -4 (phosphate ester / amide group-containing resin particles)>
(1) Preparation of reaction liquid 106 g of ion-exchanged water and NOF Emulsifier New Co., Ltd. were added to a reactor (reaction vessel) having a capacity of 1 L equipped with a stirring blade, a condenser, a nitrogen blowing tube and a dropping tank a and a dropping tank b. 0.52 g of Rexsoft type 30 was charged and dissolved by stirring.
On the other hand, in the dropping tank a, 3.5 g of 1,6-hexanediol diacrylate, 26.2 g of diethylacrylamide (amount corresponding to 15% by mass of all monomers), 69.8 g of styrene monomer, 2-methacryloyl 8.7 g of oxyethyl caproate acid phosphate (Kayamar PM21 manufactured by Nippon Explosives Co., Ltd.), 8.7 g of Adeka Reactive Emulsifier manufactured by Adeka Co., Ltd., 57.6 g of ethyl acrylate, While stirring, a monomer emulsion was prepared in the dropping tank a by adding an aqueous solution prepared by dissolving 0.35 g of NOF's emulsifier Newlex Soft Type 30 in 153 g of ion-exchanged water in advance.
Further, in the dropping tank b, 0.7 g of an aqueous azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 65 g of ion-exchanged water to prepare a polymerization initiator aqueous solution in the dropping tank b.

(2) Synthetic reaction Using the monomer emulsion prepared in (1) and the polymerization initiator aqueous solution, the synthetic reaction is performed under the same conditions as "(2) Synthetic reaction" in the preparation example of resin particles (B) -1. Thus, resin particles (B) -4 (phosphate ester / amide group-containing resin particles) were obtained.

(3) Physical properties and amount of components of resin particle (B) -4 The obtained resin particle (B) -4 has a non-volatile content ratio of 35.0% by mass and a Gardner cell viscosity of A2-A3 ^2. When measured with Microtrac Ultra Particle Analyzer (UPA) manufactured by Co., Ltd., the 50% particle size (average particle size D50) in the volume-based cumulative particle size distribution was 87.0 nm.
The resin particle (B) -4 contains 0.35% by mass of a phosphorus atom derived from a phosphate ester (b1) having a methacryloyloxy group at the molecular end in terms of solid content, and includes an amide group and a morpholine group. And 1.1% by mass of nitrogen atoms derived from acrylate (b2) having one or more groups selected from imide groups.

<Preparation of resin particles (B) -5 (phosphate ester / amide group-containing resin particles)>
(1) Preparation of reaction liquid 106 g of ion-exchanged water and NOF Emulsifier New Co., Ltd. were added to a reactor (reaction vessel) having a capacity of 1 L equipped with a stirring blade, a condenser, a nitrogen blowing tube and a dropping tank a and a dropping tank b. 0.52 g of Rexsoft type 30 was charged and dissolved by stirring.
On the other hand, in the dropping tank a, 3.5 g of 1,6-hexanediol diacrylate, 14.0 g of N-isopropylacrylamide (manufactured by Kojin Co., Ltd.) (an amount corresponding to 8% by mass of all monomers), styrene 78.5 g of monomer, 8.7 g of 2-methacryloyloxyethyl caproate acid phosphate (Kayamar PM21 manufactured by Nippon Explosives Co., Ltd.), and 8.7 g of reactive emulsifier Adeka Soap SR-10 manufactured by Adeka Corporation Then, 61.6 g of ethyl acrylate was charged, and while stirring, an aqueous solution in which 0.35 g of an oil emulsifier Newlex Soft Type 30 made by NOF Corporation was dissolved in 153 g of ion-exchanged water in advance was added. A monomer emulsion was prepared.
Further, in the dropping tank b, 0.7 g of an aqueous azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 65 g of ion-exchanged water to prepare a polymerization initiator aqueous solution in the dropping tank b.

(2) Synthetic reaction Using the monomer emulsion prepared in (1) and the polymerization initiator aqueous solution, the synthetic reaction is performed under the same conditions as "(2) Synthetic reaction" in the preparation example of resin particles (B) -1. Thus, resin particles (B) -5 (phosphate ester / amide group-containing resin particles) were obtained.

(3) Physical properties and component amounts of resin particle (B) -5 The obtained resin particle (B) -5 has a non-volatile content of 34.7% by mass and a Gardner cell viscosity of A3 ² -A4. When measured with Microtrac Ultra Particle Analyzer (UPA) manufactured by Co., Ltd., the 50% particle size (average particle size D50) in the volume-based integrated particle size distribution was 110 nm.
The resin particles (B) -5 contain 0.35% by mass of phosphorus atoms derived from the phosphate ester (b1) having a methacryloyloxy group at the molecular end in terms of solid content, and include amide groups and morpholine groups. And 1% by mass of nitrogen atoms derived from acrylate (b2) having one or more groups selected from imide groups.

<Preparation of resin particles (B) -6 (phosphate ester / imide group-containing resin particles)>
(1) Preparation of reaction liquid 106 g of ion-exchanged water and NOF Emulsifier New Co., Ltd. were added to a reactor (reaction vessel) having a capacity of 1 L equipped with a stirring blade, a condenser, a nitrogen blowing tube and a dropping tank a and a dropping tank b. 0.52 g of Rexsoft type 30 was charged and dissolved by stirring.
On the other hand, in the dropping tank a, 3.5 g of 1,6-hexanediol diacrylate and 17.5 g of acryloyloxyethyl tetrahydrophthalimide (Aronix M-145 manufactured by Toagosei Co., Ltd.) (corresponding to 10% by mass of the total monomers) Styrene monomer, 78.5 g, 2-methacryloyloxyethylcaproate acid phosphate (Nippon Explosives Co., Ltd. Kayamer PM21), Adeka Co., Ltd. reactive emulsifier Adekaria soap SR- By adding an aqueous solution prepared by previously dissolving 0.35 g of NOF's emulsifier Newlex Soft Type 30 in 153 g of ion-exchanged water while stirring and charging 8.7 g of 10 and 57.6 g of ethyl acrylate, A monomer emulsion was prepared in the dropping tank a.
Further, in the dropping tank b, 0.7 g of an aqueous azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 65 g of ion-exchanged water to prepare a polymerization initiator aqueous solution in the dropping tank b.

(2) Synthetic reaction Using the monomer emulsion prepared in (1) and the polymerization initiator aqueous solution, the synthetic reaction is performed under the same conditions as "(2) Synthetic reaction" in the preparation example of resin particles (B) -1. Thus, resin particles (B) -6 (phosphate ester / imide group-containing resin particles) were obtained.

(3) Physical Properties and Component Amounts of Resin Particle (B) -6 The obtained resin particle (B) -6 has a non-volatile content of 34.8% by mass and a Gardner cell viscosity of A2 ² -A3. When measured with a Microtrac Ultra Particle Analyzer (UPA) manufactured by Co., Ltd., the 50% particle size (average particle size D50) in the volume-based integrated particle size distribution was 78.0 nm.
The resin particles (B) -6 contain 0.35% by mass of phosphorus atoms derived from the phosphate ester (b1) having a methacryloyloxy group at the molecular end in terms of solid content, and include amide groups and morpholine groups. And 0.56% by mass of nitrogen atoms derived from acrylate (b2) having one or more groups selected from imide groups.

(Example 1 to Example 6)
As shown in Table 1, the pigment (A) -1 and the resin particles (B) -1 to resin particles (B) -6 prepared as described above were used, and the wetting agent A (N-methylpyrrolidone). , Wetting agent B (diethylene glycol diethyl ether (DEDG)) and wetting agent C (BYKET-PC manufactured by BYK), BYK manufactured by BYK as a leveling agent, and DYNOL manufactured by Air Products as a wetting aid Using 604, Nissin Chemical Industry Co., Ltd. Olphine AK02, which is an antifoaming agent, and ion-exchanged water, the compositions shown in Table 1 were blended and stirred to obtain pigment dispersion compositions. A liquid ink having a pigment concentration of 5% by mass was prepared.

(Example 7 to Example 12)
As shown in Table 2, using the pigment (A) -2 and the resin particles (B) -1 to resin particles (B) -6 prepared as described above, a wetting agent A (N-methylpyrrolidone) , Wetting agent B (diethylene glycol diethyl ether (DEDG)) and wetting agent C (BYKET-PC manufactured by BYK), BYK manufactured by BYK as a leveling agent, and DYNOL manufactured by Air Products as a wetting aid Using 604, Nissin Chemical Industry Co., Ltd. Orphine AK02, which is an antifoaming agent, and ion-exchanged water, the compositions shown in Table 2 were blended and stirred to obtain pigment dispersion compositions. A liquid ink having a pigment concentration of 5% by mass was prepared.

(Comparative Examples 1 to 6)
As shown in Table 3, Pigment (A) -1 and Pigment (A) -2, an acrylic styrene resin emulsion 1 (Voncoat EC-740EF manufactured by DIC, solid content concentration 39.8% by mass), an acrylic styrene resin Emulsion 2 (Toyo Ink Co., Ltd. W-168, solid content concentration 49.2 mass%) and acrylic styrene resin emulsion 3 (BASF Co., Ltd. John Krill 61J, solid content concentration 30.0 mass%), and Wetting agent A (N-methylpyrrolidone), wetting agent B (diethylene glycol diethyl ether (DEDG)) and wetting agent C (BYKETOL-PC manufactured by BYK), a leveling agent BYK manufactured by BYK-333, and wetting Dynor 604 manufactured by Air Products, which is an auxiliary agent, and Olfin AK manufactured by Nissin Chemical Industry Co., Ltd., which is an antifoaming agent. 2, using the ion-exchanged water, were blended to obtain the composition shown in Table 3, by stirring, are each pigment concentration as the pigment dispersion composition and the liquid ink was prepared is a 5% by weight.

  The liquid inks prepared in Examples 1 to 12 and Comparative Examples 1 to 6 were each drawn on a draw down rod # 6 using a PET film (an ACL75TACX 75 μm surface-treated polyester film manufactured by Panac Co., Ltd.), coated cardboard ( Each test piece was coated on an Oji Paper Co., Ltd. OK coated cardboard) and an aluminum sheet (thickness 0.3 mm, Al plate for untreated name plate) and dried at 120 ° C. for 10 minutes by a blow dryer. Got.

  Using each of the above test pieces, gloss, adhesion, and color density (OD value) were measured by the following methods. The results are shown in Tables 4-6.

<Gloss measurement method>
Each liquid ink was applied to OK coated cardboard manufactured by Oji Paper Co., Ltd. with a draw down rod # 6, dried at 120 ° C. for 10 minutes, and allowed to stand at room temperature for 1 hour, and then a gloss meter manufactured by BYK Gardner. The 60 ° gloss was measured by (micro gloss 60 °) and evaluated according to the following evaluation criteria.
The 60 ° gloss measured value of OK-coated cardboard manufactured by Oji Paper Co., Ltd. before application of liquid ink was 11.
◎: The measured value of 60 ° gloss is 50 or more ○: The measured value of 60 ° gloss is 40 or more and less than 50 Δ: The measured value of 60 ° gloss is 30 or more and less than 40 ×: The measured value of 60 ° gloss is less than 30

<Adhesion (a) measurement method>
After each liquid ink is applied to OK coated cardboard made by Oji Paper Co., Ltd. with a draw down rod # 6, dried at 120 ° C. for 10 minutes, and allowed to stand at room temperature for 1 hour to form an ink coating film. Apply a cut (scratch) in the shape of a cross (cross cut) about 2 cm in length and width to the surface of the ink coating film using a cutter knife, and attach 24 mm wide Nichibansello tape (registered trademark) to the cross part and adhere it sufficiently. The film was slowly peeled off and evaluated according to the following evaluation criteria.
○: There is no peeling of the ink at the crosscut portion.
Δ: Some peeling of ink at the crosscut portion is observed.
X: The ink of the crosscut part and the coated cardboard are peeled off.

<Adhesion (b) measurement method>
Each liquid ink is applied to a PET film and an aluminum sheet with a draw down rod # 6, dried at 120 ° C. for 10 minutes, and allowed to stand at room temperature for 1 hour to form an ink coating film. Make 11 centimeters (scratches) vertically and horizontally with a cutter knife on 1 cm square of the film, and divide it into 100 mm, and apply 24 mm wide Nichibansero tape (registered trademark) to the above-mentioned 100 mm section, and make sure that it is in close contact. It peeled off well and the 100-mm part peeling was evaluated on the following evaluation criteria.
○: The number of peeled pieces of the 100 升 portion is less than 1. Δ: The number of peeled pieces of the 100 枡 portion is 1 to less than 5. ×: The number of peeled pieces of the 100 枡 portion is 5 or more.

<Color density measurement method>
After each liquid ink is applied to OK coated cardboard made by Oji Paper Co., Ltd. with a draw down rod # 6, dried at 120 ° C. for 10 minutes, and allowed to stand at room temperature for 1 hour to form an ink coating film. The ink film was evaluated by evaluating the OD value measured with a reflective optical color densitometer (X-Rite Inc. X-Rite 504) according to the following criteria.
○: OD value: 1.7 or more Δ: OD value: 1.5 or more and less than 1.7 ×: OD value: less than 1.5

  From the results of Tables 4 and 5, the liquid inks obtained in Examples 1 to 12 (aqueous pigment dispersion composition) use specific resin particles (B) as the pigment dispersion composition containing the polyurethane resin-added pigment. Since the aqueous medium-dispersible pigment (A) is dispersed, the pigment is excellent in dispersibility and can form an ink coating film that exhibits excellent gloss, adhesion and color density. I understand that there is.

  On the other hand, from the results of Table 6, the liquid inks (aqueous pigment dispersion compositions) obtained in Comparative Examples 1 to 6 dispersed the aqueous medium-dispersible pigment (A) using a conventional acrylic styrene resin. As a result, the dispersibility of the pigment is inferior, and the glossiness, adhesion and color density of the resulting ink coating film are inferior.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the dispersibility of a pigment, the aqueous pigment dispersion composition, recording method, and recorded matter which can form the coating film which exhibits the outstanding glossiness, adhesiveness, and color density can be provided. .

Claims (8)

An aqueous medium-dispersible pigment (A), an acrylate (b2) having one or more groups selected from a phosphate ester (b1) having a (meth) acryloyloxy group at a molecular end, an amide group, a morpholine group, and an imide group; see contains thereto such copolymerizable with the monomer (b3) a copolymer to become resin particles (B), an aqueous medium (C),
The aqueous pigment dispersion composition, wherein the resin particles (B) have an average particle size of 50 to 200 nm .   The aqueous pigment dispersion composition according to claim 1, wherein the aqueous medium-dispersible pigment (A) is self-dispersing carbon black. The phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end is represented by the following general formula (I)
(Wherein, _{R 1} is methyl group or a hydrogen atom, n is an integer of 0 to 3, a is an integer from 1 to 3, b is an integer of 0 to 2, it is a + b = 3, When a is 2 or more, a plurality of R ₁ may be the same or different from each other. When a is 2 or more and n is present, the plurality of n are the same as each other. and may be different may be.) is a compound represented by claim 1 or an aqueous pigment dispersion composition according to claim 2. The resin particle (B) contains 0.1 to 2% by mass of a phosphorus atom derived from a phosphate ester (b1) having a (meth) acryloyloxy group at the molecular end, and is selected from an amide group, a morpholine group, and an imide group. The aqueous pigment dispersion composition according to any one of claims 1 to 3 , comprising 0.2 to 5% by mass of a nitrogen atom derived from an acrylate (b2) having one or more groups. The aqueous pigment dispersion composition according to any one of claims 1 to 4 , comprising 10 to 300 parts by mass of the resin particles (B) with respect to 100 parts by mass of the aqueous medium-dispersible pigment (A) in terms of solid content. object. The aqueous pigment dispersion composition according to any one of claims 1 to 5 , wherein the aqueous pigment dispersion composition is an inkjet ink composition. 7. A recording method, wherein the aqueous pigment dispersion composition according to claim 6 is used for recording by an ink jet recording method. 7. A recorded matter recorded by the ink jet recording method using the aqueous pigment dispersion composition according to claim 6 .