JP5544081B2 - Water-based ink for inkjet recording - Google Patents

Description

  The present invention relates to an aqueous dispersion for inkjet recording, an aqueous ink containing the same, and a method for producing the aqueous dispersion.

The ink jet recording system is a recording system in which characters and images are obtained by ejecting ink droplets directly from a very fine nozzle and attaching them to a recording member. This method is widely spread because it is easy to make full color and is inexpensive, and has many advantages such as the ability to use plain paper as a recording member and non-contact with the object to be printed.
Recently, in order to impart weather resistance and water resistance to printed matter, ink using a pigment as a color material has been widely used. Furthermore, in order to suppress ink bleeding or to improve the fixability of pigment to paper, a resin emulsion or the like is added.

Patent Document 1 discloses an aqueous pigment dispersion containing a pigment, a hydrophobic group-containing cationic polymer, and a hydrophobic group-containing anionic polymer for the purpose of improving dispersion stability, dischargeability, and gloss.
Patent Document 2 discloses a self-dispersing pigment surface-modified to a cationic type for the purpose of improving optical density, fixability, water resistance, and the like, and anionic resin particles having a zeta potential of -15 mV or less at pH 6 An ink jet recording ink comprising an aqueous medium is disclosed.
Patent Document 3 includes a step of combining an emulsion of an emulsifiable polymer resin in an anionic medium with a pigment and a cationic surfactant, and aggregating the particles in the obtained mixture to a desired particle size. A method of forming an inkjet ink composition is disclosed.
Patent Document 4 discloses an ink-jet ink coloring material comprising composite particle powder in which the surface of extender particles is coated with a paste and the organic pigment forms a uniform adhesion layer on the coating. Yes.
Patent Document 5 discloses (1) a dispersible color material in which a color material and a chargeable resin pseudo fine particle smaller than the color material are fixed or fused, and the color material itself has a surface charge. In a dispersion aqueous solution of a dispersible color material and (2) a water-insoluble color material in which polar groups are bonded and dispersed on the surface, the radical polymerizable monomer is subjected to water-based precipitation polymerization and fixed on the surface of the water-insoluble color material. A method for producing a dispersible color material for forming fused charge resin pseudo fine particles is disclosed.

JP 2008-239961 A JP 2003-306624 A JP-A-9-124985 JP 2003-55591 A JP 2006-37087 A

Conventionally, an ink using a dispersible color material insoluble in water such as a pigment as a color material has a problem that it is difficult to obtain a sufficient print density.
An object of the present invention is to provide an aqueous dispersion for ink jet recording excellent in printing density, an aqueous ink containing the same, and a method for producing the aqueous dispersion.

The present inventor believes that the reason why it is difficult to obtain a sufficient print density with an ink using a dispersible colorant that is insoluble in water, such as a pigment, is that the colorant is fine particles and easily penetrates into paper. As a result, it has been found that the printing density can be improved by using composite particles in which anionic colored particles are attached to cationic polymer particles.
That is, the present invention provides the following (1) to (3).
(1) An aqueous dispersion for inkjet recording containing composite particles in which anionic colored particles are attached to cationic polymer particles.
(2) A water-based ink for ink jet recording containing the water dispersion of (1).
(3) A method for producing an aqueous dispersion for inkjet recording, comprising the following step (a).
Step (a): A step of mixing an aqueous dispersion of anionic colored particles and an aqueous dispersion of cationic polymer particles to obtain an aqueous dispersion of composite particles in which anionic colored particles are attached to the cationic polymer particles.

  The aqueous dispersion for inkjet recording of the present invention and the aqueous ink containing the same are excellent in print density. In addition, according to the method for producing an aqueous dispersion of the present invention, an aqueous dispersion for ink jet recording excellent in printing density can be efficiently produced.

The aqueous dispersion for inkjet recording of the present invention is characterized in that it contains composite particles (hereinafter also simply referred to as “composite particles”) in which anionic colored particles are attached to cationic polymer particles.
The state of adhesion of the anionic colored particles to the cationic polymer particles can be confirmed by observing the aqueous dispersion or aqueous ink with an electron microscope.
As an adhesion state of the anionic coloring particle to the cationic polymer particle, the anionic coloring particle may be adhered to the surface of the cationic polymer particle, or a part thereof may enter the inside of the cationic polymer particle. From the viewpoint of improving the printing density, those attached to the surface are preferable.
The reason why the aqueous dispersion for ink jet recording and the water-based ink of the present invention are excellent in print density is not clear, but the composite particles in which the anionic pigment-colored particles are attached to the cationic polymer particles become uneven particles, so that paper or the like It is considered that the print density of the printed matter is improved.
Usually, water-based inkjet inks are designed to be weakly alkaline. This is to prevent corrosion of the ink flow path and the head member. Also in the aqueous dispersion for inkjet recording and the water-based ink of the present invention, the pH is preferably 7-9.
In the present invention, anionic colored particles are used in order to stably disperse colored particles in an amount necessary for expressing a sufficient printing density in such a weak alkaline solution. In addition, cationic polymer particles are used as polymer particles different from the colored particles from the viewpoint of efficiently adhering to the anionic colored particles and improving the printing density.
Hereinafter, each component used for the aqueous dispersion for inkjet recording of the present invention will be described.

[Cationic polymer particles]
The cationic polymer particles are preferably water-insoluble polymer particles that can be dispersed as a polymer emulsion in a medium containing a continuous phase in an aqueous system in the presence or absence of a surfactant. Among these, (i) polymer particles obtained by emulsion polymerization of an ethylenically unsaturated monomer, and (ii) self-emulsifying polymer particles containing a structural unit derived from a cationic monomer are preferred. Here, the self-emulsifying polymer particle refers to a water-insoluble polymer particle which is emulsified in water by a functional group (preferably a basic group or a salt thereof) of the polymer itself in the absence of a surfactant.
In this specification, the term “cationic” means that when an unneutralized compound or the like is dispersed or dissolved in pure water, the pH becomes higher than 7, or the compound or the like is insoluble in pure water. The zeta potential of the water dispersion dispersed in pure water is positive, and it corresponds to any one of them.
The water-insoluble polymer means a polymer which is dried at 105 ° C. for 2 hours and reaches a constant weight and dissolved in 100 g of water at 25 ° C., and the dissolved amount is 10 g or less. Is preferably 5 g or less, more preferably 1 g or less. When the basic group is contained, the dissolution amount is the dissolution amount when the basic group is neutralized 100%. When the counter ion to be neutralized is not indicated, the dissolution amount of the neutral group neutralized with hydrochloric acid And the counter ion is a chloride ion.
The average particle diameter of the cationic polymer particles is preferably 10 to 1000 nm, more preferably 50 to 500 nm, and still more preferably 80 to 300 nm from the viewpoint of the aqueous dispersion and the printing density of the ink. The average particle size can be measured by the method described in the examples.

Specific examples of the polymer constituting the polymer particles include (meth) acrylic polymers, vinyl acetate polymers, styrene-butadiene polymers, vinyl chloride polymers, styrene- (meth) acrylic polymers, butadiene polymers, styrene polymers. Examples thereof include polymers. Among these, (meth) acrylic polymers, styrene- (meth) acrylic polymers, and styrene polymers are preferable, styrene- (meth) acrylic polymers, and styrene polymers are more preferable, and styrene polymers are more preferable.
These polymer particles can be used alone or in admixture of two or more.

(Cationic monomer)
Cationic polymer particles can be obtained by polymerizing at least one cationic monomer.
As a cationic monomer, an amino group-containing monomer, an acid neutralized product of an amino group-containing monomer, a quaternary ammonium salt obtained by quaternizing the monomer with a quaternizing agent, or a diallyl type Quaternary ammonium salt etc. are mentioned.
Examples of the monomer having an amino group include (meth) acrylic acid esters or (meth) acrylamides having a dialkylamino group, styrenes having a dialkylamino group, vinylpyridines, N-vinyl heterocyclic compounds, and vinyl ethers. One or more selected from the group is preferred.
Examples of (meth) acrylic acid ester having a dialkylamino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl ( Examples include meth) acrylate, diisobutylaminoethyl (meth) acrylate, and di-t-butylaminoethyl (meth) acrylate.
Examples of (meth) acrylamides having a dialkylamino group include dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) ) Acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylaminopropyl (meth) acrylamide and the like.
Examples of styrenes having a dialkylamino group include dimethylaminostyrene and dimethylaminomethylstyrene. Examples of vinylpyridines include 4-vinylpyridine and 2-vinylpyridine. N-vinyl heterocyclic compounds Examples thereof include N-vinylimidazole, and examples of vinyl ethers include aminoethyl vinyl ether and dimethylaminoethyl vinyl ether.

  The acid neutralized product of a monomer having an amino group, a quaternary ammonium salt obtained by quaternizing the monomer with a quaternizing agent, and a diallyl-type quaternary ammonium salt include the following general formula (1) And / or the compound represented by (2) is preferable, and among them, the quaternary ammonium salt type monomer is more preferable because the viscosity stability is good even when the pH of the system is changed.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group or an alkenyl group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or 1 carbon atom. indicates to 4 alkyl groups, Y is -O- group, -NH- group or _{-O-CH 2 CH (OH)} - represents a group, Z is a linear or branched chain having 1 to 4 carbon atoms An alkanediyl group, and X represents an anion.)
In the general formula (1), the alkyl group having 1 to 4 carbon atoms R ^2, R ³ and R ^4, a methyl group, an ethyl group, n- propyl group, an isopropyl group, various butyl groups. Examples of Z include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, and a tetramethylene group.
Examples of the anion of X include a halide ion, an acid conjugate base, or an alkyl sulfate ion having 1 to 4 carbon atoms. Examples of halide ions include chloride ions, bromide ions, iodide ions, etc., and examples of acid conjugate bases include groups obtained by removing a hydrogen atom from preferred acids for obtaining an acid neutralized product (described later). It is done.
Among the compounds represented by the general formula (1), preferred examples include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride. , (Meth) acryloyloxypropyltrimethylammonium chloride, (meth) acryloyloxybutyltrimethylammonium chloride, and the like. Among them, (meth) acryloyloxyethyltrimethylammonium chloride and (meth) acryloyloxypropyltrimethylammonium chloride are preferable.

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents The same.)
Specific examples of the compound represented by the general formula (2) include diallyl-type quaternary ammonium salts such as dimethyldiallylammonium chloride and diethyldiallylammonium chloride, and dimethyldiallylammonium chloride is preferable.

When the compound represented by the general formula (1) or (2) is an acid neutralized product, preferred acids used for obtaining the acid neutralized product include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, maleic acid. , Fumaric acid, citric acid, tartaric acid, adipic acid, sulfamic acid, toluenesulfonic acid, lactic acid, pyrrolidone-2-carboxylic acid, succinic acid and the like.
When the compound represented by the general formula (1) or (2) is a quaternary ammonium salt, preferred quaternizing agents used for obtaining the quaternary ammonium salt include methyl chloride and ethyl chloride. Alkylating agents such as alkyl halides such as methyl bromide and methyl iodide, and dialkyl sulfates such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate.

The cationic polymer particles preferably contain a constituent unit derived from the hydrophobic monomer (c) described later in addition to the constituent unit derived from the cationic monomer. Examples of the hydrophobic monomer (C) include alkyl (meth) acrylates, alkyl (meth) acrylamides and aromatic ring-containing monomers described later, and alkyl (meth) acrylates and styrene monomers are preferred.
Moreover, it is preferable from the viewpoint of the storage stability of an aqueous dispersion and an ink to contain the structural unit derived from a polyfunctional monomer. An example of the polyfunctional monomer is divinylbenzene.
Furthermore, the cationic polymer particles may contain a constituent unit derived from the nonionic monomer (d) described later.

The content of the structural unit derived from the cationic monomer in the cationic polymer is preferably 0.1 to 40% by weight, more preferably 1 to 40% by weight from the viewpoint of dispersion stability of the polymer particles in the aqueous dispersion or ink. 30% by weight, more preferably 2 to 20% by weight, still more preferably 3 to 10% by weight.
In addition, among the cationic monomers, those having a structure that changes due to neutralization, such as a monomer having an amino group, the content is calculated as a neutralized product of an acid used when producing an aqueous dispersion or ink. .
When the cationic polymer contains a structural unit derived from the hydrophobic monomer (c), the content of the structural unit derived from the hydrophobic monomer (c) in the cationic polymer is determined by the aqueous dispersion of polymer particles obtained. Or from the viewpoint of dispersion stability in the ink, it is preferably 50.0 to 99.9% by weight, more preferably 60.0 to 99.5% by weight, still more preferably 70.0 to 99.0% by weight. is there.
The weight ratio of [(constituent unit derived from cationic monomer) / (constituent unit derived from hydrophobic monomer (c))] in the cationic polymer is the dispersion stability of the polymer particles in the aqueous dispersion or ink. From this viewpoint, it is preferably 1/1000 to 1/2, more preferably 1/300 to 1/3, and still more preferably 1/20 to 1/10.
The content of the structural unit derived from the polyfunctional monomer in the cationic polymer is preferably 0.1 to 10% by weight, more preferably 2 to 5% by weight.

(Manufacture of cationic polymer particles)
When the cationic polymer particle used in the present invention is a polymer particle obtained by emulsion polymerization of (i) an ethylenically unsaturated monomer, it can be produced by a known emulsion polymerization method.
Emulsion polymerization is carried out using a surfactant and a monomer, and soap-free polymerization without using a surfactant can be carried out by selecting the amount and type of the cationic monomer to be used, which is preferable.
Although the surfactant used for emulsion polymerization is not particularly limited, a cationic surfactant or a nonionic surfactant is preferably used, and these can be used alone or in admixture of two or more. Of these, cationic surfactants are preferred.
Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, alkylbetaines, and alkylamine oxides.
Examples of the alkylamine salt include laurylamine acetate and stearylamine acetate. Examples of the quaternary ammonium salt include alkyltrimethylammonium chloride such as lauryltrimethylammonium chloride, stearylammonium chloride, cetylammonium chloride, dialkyldimethylammonium chloride such as distearylammonium chloride, alkylbenzyldimethylammonium chloride, and the like.
Examples of the alkyl betaine include lauryl betaine and stearyl betaine, and examples of the alkylamine oxide include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauryldimethylamine oxide.
Nonionic surfactants include polyoxyalkylene alkyl ethers, esters of alcohols and polyhydric fatty acids, polyoxyalkylene aliphatic amines, ester compounds of fatty acids and polyhydric alcohols, and compounds obtained by adding alkylene oxide thereto. .

  As a polymerization initiator used for polymerizing a polymer, known inorganic peroxides, organic initiators, redox polymerization initiators, and the like can be used. Examples of inorganic peroxides include potassium persulfate and ammonium persulfate. Examples of the organic initiator include azo initiators such as organic peroxides, azobisdiisobutyronitrile, and 2,2′-azobis (2-methylpropionamidine) dihydrochloride. Moreover, as a redox polymerization initiator, what uses reducing agents, such as sodium hydrogen sulfite, sodium thiosulfate, ferrous sulfate, sugar, together with a peroxide and an oxidizing agent is mentioned. Among these, 2,2′-azobis (2-methylpropionamidine) dihydrochloride is preferable.

[Anionic colored particles]
In the present invention, anionic colored particles (hereinafter, also simply referred to as “colored particles”) are dispersed dispersions in an aqueous dispersion or ink of composite particles, from the viewpoint of effectively adhering to cationic polymer particles, From the viewpoint of improving the print density of the aqueous dispersion or ink, an anionic polymer particle containing a colorant is preferable. In addition, the anionic polymer particles are preferably anionic crosslinked polymer particles from the viewpoint of storage stability of the aqueous dispersion. As described later, for example, the crosslinked polymer particles are colored by adding a crosslinking agent to an aqueous dispersion of composite particles in which anionic polymer particles containing a colorant are attached to the cationic polymer particles. It can be obtained in the form of an aqueous dispersion of composite particles to which anionic crosslinked polymer particles containing an agent are attached.
In the present specification, anionicity means that when an unneutralized compound or the like is dispersed or dissolved in pure water, the pH is less than 7, or when the compound or the like is insoluble in pure water, It means that the zeta potential of the dispersion dispersed in pure water becomes negative.
Colored particles include particles consisting only of a colorant such as a pigment, particles obtained by dispersing a colorant with an anionic surfactant, particles obtained by dispersing a colorant with an anionic polymer dispersant, and a colorant And anionic polymer particles containing a colorant are preferred.
The average particle diameter of the colored particles is preferably 30 to 300 nm, more preferably 40 to 200 nm, more preferably 50 to 150 nm, and still more preferably 60 to 90 nm, from the viewpoint of the printing density of the ink.
From the viewpoint of effectively attaching the colored particles to the cationic polymer particles, the average particle size of the colored particles is preferably one having an average particle size smaller than the average particle size of the cationic polymer particles. The average particle size can be measured by the method described in the examples.

(Coloring agent)
The colorant used for the anionic colored particles is not particularly limited, and pigments, hydrophobic dyes, water-soluble dyes (acidic dyes, reactive dyes, direct dyes, etc.) can be used, but from the viewpoint of printing density. Pigments and hydrophobic dyes are preferred, and pigments are more preferred.
When the pigment and the hydrophobic dye are used in an aqueous ink, it is preferable to use a surfactant and a polymer to form fine particles that are stable in the ink. In particular, from the viewpoints of bleeding resistance, water resistance, and the like, it is preferable to include a pigment and / or a hydrophobic dye in the polymer particles.
The pigment may be either an inorganic pigment or an organic pigment. If necessary, they can be used in combination with extender pigments.
Examples of the inorganic pigment include carbon black, metal oxide, metal sulfide, and metal chloride. In the black water-based ink, carbon black is preferable. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.

Examples of the organic pigment include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments.
The hue is not particularly limited, and any chromatic color pigment such as a red organic pigment, a yellow organic pigment, a blue organic pigment, an orange organic pigment, or a green organic pigment can be used.
Specific examples of preferred organic pigments include C.I. I. Pigment yellow, C.I. I. Pigment Red, C.I. I. Pigment violet, C.I. I. Pigment blue, and C.I. I. One or more types of products selected from the group consisting of pigment green are listed. Moreover, solid solution pigments, such as a quinacridone solid solution pigment, can be used.
The quinacridone solid solution pigment includes unsubstituted quinacridone such as β-type and γ-type, and dichloroquinacridone such as 2,9-dichloroquinacridone, 3,10-dichloroquinacridone, and 4,11-dichloroquinacridone. As the quinacridone solid solution pigment, a solid solution pigment comprising a combination of unsubstituted quinacridone (CI Pigment Violet 19 and the like) and 2,9-dichloroquinacridone (CI Pigment Red 202 and the like) is preferable.

In the present invention, a self-dispersing pigment can also be used. Self-dispersing pigments are those in which one or more hydrophilic functional groups (anionic hydrophilic groups such as carboxy groups and sulfonic acid groups, or cationic hydrophilic groups such as quaternary ammonium groups) are directly or other atomic groups. It means an inorganic pigment or an organic pigment that can be dispersed in an aqueous medium without using a surfactant or a resin. Here, examples of the other atomic group include an alkanediyl group having 1 to 12 carbon atoms, a phenylene group, or a naphthylene group, and the hydrophilic functional group is an anionic hydrophilic group such as a carboxy group or a sulfonic acid group. It is preferable.
In order to make the pigment a self-dispersing pigment, for example, a necessary amount of the hydrophilic functional group may be chemically bonded to the pigment surface by a conventional method. More specifically, a method of liquid phase oxidation with acids such as nitric acid, sulfuric acid, peroxodisulfuric acid, hypochlorous acid and chromic acid, and a method of bonding a hydrophilic group using a coupling agent are preferred.
The amount of the hydrophilic functional group is not particularly limited, but is preferably 100 to 3,000 μmol / g per gram of the self-dispersing pigment. When the hydrophilic functional group is a carboxy group, 200 to 700 μmol / g per gram of the self-dispersing pigment. Is preferred.
Examples of commercially available anionic self-dispersing pigments include CAB-O-JET 200, 300, 1027R, 250C, 260M, 270Y, 554B (manufactured by Cabot), BONJET CW-1, and CW- 2 (manufactured by Orient Chemical Co., Ltd.), Aqua-Black 162 (manufactured by Tokai Carbon Co., Ltd.), and the like.

The hydrophobic dye is not particularly limited as long as it can be contained in the polymer particles. The hydrophobic dye is dissolved in an amount of 2 g / L or more, preferably 20 to 500 g / L (25 ° C.) with respect to an organic solvent (preferably methyl ethyl ketone) used in the production of the polymer from the viewpoint of efficiently containing the dye in the polymer. What to do is desirable.
Examples of the hydrophobic dye include oil-soluble dyes and disperse dyes. Among these, oil-soluble dyes are preferable. Examples of the oil-soluble dye include C.I. I. Solvent Black, C.I. I. Solvent Yellow, C.I. I. Solvent Red, C.I. I. Solvent Violet, C.I. I. Solvent Blue, C.I. I. Solvent Green, and C.I. I. One or more types of products selected from the group consisting of Solvent Orange are listed, which are commercially available from Orient Chemical Co., Ltd., BASF Corp. and others.
The above colorants can be used alone or in admixture of two or more at any ratio.

[Anionic polymer particles containing colorant]
(Anionic polymer)
The anionic polymer used for the anionic polymer particles containing the colorant is preferably a water-insoluble polymer from the viewpoint of improving the print density of the aqueous dispersion or ink. Here, the water-insoluble polymer has the same definition as in the cationic polymer. The dissolution amount is the dissolution amount when the anionic group of the polymer is neutralized 100% with sodium hydroxide.
Examples of the polymer to be used include polyester, polyurethane, and vinyl polymer. From the viewpoint of storage stability of the aqueous dispersion, vinyl obtained by addition polymerization of a vinyl monomer (vinyl compound, vinylidene compound, vinylene compound). Based polymers are preferred.
Examples of the vinyl polymer include (a) an anionic monomer (hereinafter also referred to as “component (a)”), (b) a macromer (hereinafter also referred to as “component (b)”) and / or (c) a hydrophobic monomer ( A vinyl polymer obtained by copolymerizing a monomer mixture (hereinafter also simply referred to as “monomer mixture”) containing “(c) component” below is preferable. This vinyl polymer has a structural unit derived from the component (a), a structural unit derived from the component (b) and / or a structural unit derived from the component (c). Among these, those containing all of the structural unit derived from the component (a), the structural unit derived from the component (b), and the structural unit derived from the component (c) are preferable.

[(A) Anionic monomer]
(A) The anionic monomer is used as a monomer component of the anionic polymer in order to stably disperse the composite particles in an aqueous dispersion or ink and to effectively attach the pigment colored particles to the cationic polymer particles.
Examples of the anionic monomer include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.
Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid.
Examples of the sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, and bis- (3-sulfopropyl) -itaconate.
Examples of phosphoric acid monomers include vinylphosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, and the like. It is done.
Among the anionic monomers, a carboxylic acid monomer is preferable and acrylic acid and methacrylic acid are more preferable from the viewpoint of dispersion stability of the composite particles in an aqueous dispersion or ink.

[(B) Macromer]
(B) A macromer is a compound having a polymerizable functional group at one end and a number average molecular weight of 500 to 100,000, and from the viewpoint of storage stability in an aqueous dispersion or ink of composite particles, Used as a monomer component. The polymerizable functional group present at one end is preferably an acryloyloxy group or a methacryloyloxy group, and more preferably a methacryloyloxy group. (B) The number average molecular weight of the macromer is preferably from 500 to 100,000, more preferably from 1,000 to 10,000. The number average molecular weight is measured using polystyrene as a standard substance by gel chromatography using chloroform containing 1 mmol / L dodecyldimethylamine as a solvent.
As the (b) macromer, a styrene macromer, an aromatic group-containing (meth) acrylate macromer, and a silicone macromer are preferable from the viewpoint of dispersion stability of the composite particles in an aqueous dispersion or ink.
Examples of the styrenic macromer include a styrene monomer homopolymer or a copolymer of a styrene monomer and another monomer. In the case of a copolymer, the content of the styrenic monomer is preferably 50% by weight or more, and more preferably 70% by weight or more, from the viewpoint of dispersion stability of the composite particles in an aqueous dispersion or ink. Examples of the styrene monomer include styrene, 2-methylstyrene, vinyl toluene, ethyl vinyl benzene, vinyl naphthalene, chlorostyrene, and the like. Other monomers to be copolymerized include aromatic group-containing (meth) acrylates or acrylonitrile. Specific examples of the styrenic macromer include AS-6 (S), AN-6 (S), HS-6 (S) (trade name of Toagosei Co., Ltd.) and the like.

Examples of the aromatic group-containing (meth) acrylate-based macromer include a homopolymer of an aromatic group-containing (meth) acrylate or a copolymer thereof with another monomer. In the case of a copolymer, the content of the aromatic group-containing (meth) acrylate monomer is preferably 50% by weight or more and 70% by weight or more from the viewpoint of dispersion stability of the composite particles in an aqueous dispersion or ink. More preferred.
As an aromatic group-containing (meth) acrylate, an arylalkyl group having 7 to 22 carbon atoms which may have a substituent containing a heteroatom, or a carbon number which may have a substituent containing a heteroatom. Examples include (meth) acrylates having 6 to 22 aryl groups. Specific examples thereof include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, and the like, and benzyl (meth) Acrylate is preferred. Examples of other monomers to be copolymerized include styrene monomers and acrylonitrile.
(B) The macromer may be a silicone-based macromer, and examples of the silicone-based macromer include organopolysiloxane having a polymerizable functional group at one end.

[(C) Hydrophobic monomer]
(C) The hydrophobic monomer is used as a monomer component of the anionic polymer from the viewpoint of improving the print density of the aqueous dispersion or ink. Examples of the hydrophobic monomer include alkyl (meth) acrylates and aromatic group-containing monomers.
As the alkyl (meth) acrylate, those having an alkyl group having 1 to 22 carbon atoms, preferably 6 to 18 carbon atoms are preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meta) ) Acrylate, (iso or tertiary) butyl (meth) acrylate, (iso) amyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) Examples include decyl (meth) acrylate, (iso) dodecyl (meth) acrylate, and (iso) stearyl (meth) acrylate.
In the present specification, “(iso or tertiary)” and “(iso)” mean both the case where these groups are present and the case where these groups are not present. Indicates. “(Meth) acrylate” indicates acrylate and / or methacrylate.

As the aromatic group-containing monomer, a vinyl monomer having an aromatic group having 6 to 22 carbon atoms, which may have a substituent containing a hetero atom, is preferable, and a styrene monomer or an aromatic group-containing (meth) acrylate. Are more preferable, and it is also preferable to use these in combination.
As the styrenic monomer, styrene, 2-methylstyrene, and divinylbenzene are preferable, and styrene is more preferable.
Moreover, as an aromatic group containing (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. are preferable, and benzyl (meth) acrylate is more preferable.

[(D) Nonionic monomer]
The monomer mixture may further contain (d) a nonionic monomer (hereinafter also referred to as “component (d)”).
(D) As a component, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethyleneglycol (n = 2-30, n shows the average addition mole number of an oxyalkylene group. The same hereafter). (Meth) acrylate, polypropylene glycol (n = 2 to 30) (meth) acrylate, poly (ethylene glycol (n = 1 to 15) / propylene glycol (n = 1 to 15)) (meth) acrylate, methoxypolyethylene glycol ( 1-30) (meth) acrylate, methoxypolytetramethylene glycol (1-30) (meth) acrylate, ethoxypolyethylene glycol (1-30) (meth) acrylate, octoxypolyethylene glycol (1-30) (meth) acrylate , Polyethylene grease (1-30) (meth) acrylate 2-ethylhexyl ether, (iso) propoxypolyethylene glycol (1-30) (meth) acrylate, butoxypolyethylene glycol (1-30) (meth) acrylate, methoxypolypropylene glycol (1 -30) (meth) acrylate, methoxy (ethylene glycol / propylene glycol copolymer) (1-30, ethylene glycol: 1 to 29 therein) (meth) acrylate, and the like.

Specific examples of the commercially available component (d) include NK Esters M-40G, 90G, and 230G from Shin-Nakamura Chemical Co., Ltd., Bremer PE-90, 200, and 350 from Nippon Oil & Fats Co., Ltd. PME-100, 200, 400, 1000, PP-500, 800, 1000, AP-150, 400, 550, 800, 50PEP-300, 50POEP-800B, 43PAPE600B, etc. .
The components (a) to (d) can be used alone or in admixture of two or more.

Content (a) to (c) component in the monomer mixture of the above components (a) to (c) at the time of vinyl polymer production (content as an unneutralized amount; the same applies hereinafter) or vinyl polymer The content of the structural unit derived from is as follows.
The content of the component (a) is preferably 3 to 40% by weight from the viewpoint of stably dispersing the composite particles in an aqueous dispersion or ink and effectively attaching the anionic colored particles to the cationic polymer particles. More preferably, it is 4-30 weight%, Most preferably, it is 5-25 weight%.
The content of component (b) is preferably 1 to 25% by weight, more preferably 5 to 20% by weight, from the viewpoint of dispersion stability of the composite particles in an aqueous dispersion or ink.
The content of the component (c) is preferably 5 to 98% by weight, more preferably 10 to 80% by weight, from the viewpoint of improving the print density of the aqueous dispersion or ink.
Further, the weight ratio of [(a) component / [(b) component + (c) component]] is a viewpoint of dispersion stability of the composite particles in the aqueous dispersion or ink and the print density of the aqueous dispersion or ink. Therefore, it is preferably 0.01 to 1, more preferably 0.02 to 0.67, and still more preferably 0.03 to 0.50.

(Production of anionic polymer)
The anionic polymer is produced by copolymerizing a monomer mixture by a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method. Among these polymerization methods, the solution polymerization method is preferable.
As the solvent used in the solution polymerization method, a polar organic solvent is preferable. When the polar organic solvent is miscible with water, it can be used by mixing with water. Examples of the polar organic solvent include aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and the like. Among these, methanol, ethanol, acetone, methyl ethyl ketone, or a mixed solvent of one or more of these and water is preferable.
In the polymerization, azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), t-butyl peroxyoctate, dibenzoyl oxide, etc. Known radical polymerization initiators such as organic peroxides can be used. The amount of the radical polymerization initiator is preferably 0.001 to 5 mol, more preferably 0.01 to 2 mol per 1 mol of the monomer mixture (1 mol of the total molar amount of each monomer).
In the polymerization, a known polymerization chain transfer agent such as mercaptans such as octyl mercaptan and 2-mercaptoethanol and thiuram disulfide may be further added.
Although the polymerization conditions of the monomer mixture vary depending on the type of radical polymerization initiator, monomer, solvent, etc. to be used and cannot be determined unconditionally, the polymerization temperature is usually preferably 30 to 100 ° C., more preferably 50 The polymerization time is preferably 1 to 20 hours. The polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.
After completion of the polymerization reaction, the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation or solvent distillation. In addition, unreacted monomers and the like can be removed from the obtained polymer by reprecipitation, membrane separation, chromatographic methods, extraction methods and the like.

The weight average molecular weight of the anionic polymer used in the present invention is preferably 5,000 to 500,000 from the viewpoint of the dispersion stability of the composite particles in the aqueous dispersion or ink and the printing density of the aqueous dispersion or ink. 10,000 to 400,000 are more preferable, 10,000 to 300,000 are more preferable, and 20,000 to 300,000 are more preferable. The weight average molecular weight of the anionic polymer was measured by the method shown in the examples.
The anionic polymer used in the present invention is preferably used by neutralizing an anionic group derived from (a) an anionic monomer with a neutralizing agent. Examples of the neutralizing agent include bases such as sodium hydroxide, potassium hydroxide, and various amines.
The degree of neutralization of the anionic group of the anionic polymer is preferably 10 to 300%, more preferably 20 to 200%, from the viewpoint of dispersion stability of the composite particles in the aqueous dispersion or ink. More preferably, ˜150%.
When the anionic polymer is crosslinked, the degree of neutralization of the anionic group of the polymer before crosslinking is 10 to 90% from the viewpoint of dispersion stability and crosslinking efficiency in the aqueous dispersion or ink of the composite particles. It is preferably 20 to 80%, more preferably 30 to 70%.
Here, the neutralization degree can be obtained by the following equation.
{[Weight of neutralizing agent (g) / equivalent of neutralizing agent] / [acid value of anionic polymer (KOH mg / g) × weight of anionic polymer (g) / (56 × 1000)]} × 100
The acid value can be calculated from the structural unit of the anionic polymer. Alternatively, it can also be determined by a method in which an anionic polymer is dissolved in a suitable solvent (for example, methyl ethyl ketone) and titrated.

[Production of Anionic Polymer Particles Containing Colorant]
An aqueous dispersion of anionic polymer particles containing a colorant can be efficiently produced by a method having the following steps (1) and (2).
Step (1): A step of dispersing a mixture containing an anionic polymer, an organic solvent, a colorant, and water to obtain a dispersion of anionic polymer particles containing a colorant Step (2): Step (1) The organic solvent is removed from the dispersion obtained in step 1) to obtain an aqueous dispersion of anionic polymer particles containing a colorant.

Process (1)
In step (1), an anionic polymer is first dissolved in an organic solvent, and then a pigment, water, and if necessary, a neutralizing agent, a surfactant and the like are added to the obtained organic solvent solution and mixed. A method for obtaining an oil-in-water type dispersion is preferred. In the mixture, the pigment is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, the organic solvent is preferably 10 to 70% by weight, more preferably 10 to 50% by weight, and the anionic polymer is 2%. -40% by weight is preferred, 3-20% by weight is more preferred, and water is preferably 10-70% by weight, more preferably 20-70% by weight.
The weight ratio of the amount of the colorant to the total amount of the anionic polymer and the colorant [colorant / (anionic polymer + colorant)] is from the viewpoint of dispersion stability of the composite particles in the aqueous dispersion or ink. 50/100 to 90/100 are preferable, and 70/100 to 85/100 are more preferable.

When neutralizing with a neutralizing agent, it is preferable to neutralize so that the finally obtained aqueous dispersion has a pH of 7-11. Examples of the neutralizing agent include bases such as sodium hydroxide, potassium hydroxide, and various amines. Further, the anionic polymer may be neutralized in advance.
Examples of the organic solvent include alcohol solvents such as ethanol, isopropanol and isobutanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone, and ether solvents such as dibutyl ether, tetrahydrofuran and dioxane. You may use these individually or in combination of 2 or more types.
The amount of the organic solvent dissolved in 100 g of water is preferably 5 g or more, more preferably 10 g or more at 20 ° C., and methyl ethyl ketone and methyl isobutyl ketone are preferred.

There is no restriction | limiting in particular in the dispersion method of the mixture in process (1). Although the average particle diameter of the anionic polymer particles containing the colorant can be atomized only by the main dispersion until the desired particle diameter is reached, preferably after pre-dispersion, the main dispersion is further subjected to shear stress. It is preferable to control the average particle size of the anionic polymer particles containing the colorant to a desired particle size. The temperature in the dispersion in the step (1) is preferably 5 to 50 ° C, more preferably 10 to 35 ° C, and the dispersion time is preferably 1 to 30 hours, more preferably 2 to 25 hours.
When pre-dispersing the mixture, commonly used mixing and stirring devices such as anchor blades and disper blades, such as Ultra Disper, Desperm (Asada Tekko Co., Ltd., trade name), Milder (Ebara Manufacturing Co., Ltd.) High-speed agitation and mixing devices such as TK Homomixer, TK Pipeline Mixer, TK Homojetter, TK Homomic Line Flow, and Fillmix (hereinafter, Primix Co., Ltd., trade name) are preferred.
Examples of means for applying the shear stress of this dispersion include, for example, a kneader such as a roll mill, a kneader, and an extruder, a high pressure homogenizer represented by a high pressure homogenizer (Izumi Food Machinery Co., Ltd., trade name), and a microfluidizer (Microfluidics). Company name, Nanomizer (Yoshida Kikai Kogyo Co., Ltd., trade name), Optimizer, Starburst (Sugino Machine Co., Ltd., trade name) and other chamber type high-pressure homogenizers, paint shakers, bead mills and other media-type dispersers Is mentioned. Commercially available media-type dispersers include Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd., trade name), Picomill (manufactured by Asada Tekko Co., Ltd., trade name), Dino Mill (manufactured by Shinmaru Enterprises Co., Ltd., trade name), etc. Is mentioned. A plurality of these devices can be combined. Among these, it is preferable to use a media type disperser and a high-pressure homogenizer from the viewpoint of reducing the particle size of the anionic polymer particles containing the colorant.

Step (2)
In step (2), an aqueous dispersion of anionic polymer particles containing a colorant is obtained by distilling off the organic solvent from the dispersion obtained in step (1) by a known method to form an aqueous system. be able to. The organic solvent in the aqueous dispersion of the obtained anionic polymer particles is preferably substantially removed, but may remain as long as the object of the present invention is not impaired, and the crosslinking step is performed later. May be additionally removed after crosslinking, if necessary. The amount of the residual organic solvent in the aqueous dispersion of the finally obtained anionic polymer particles is preferably 0.1% by weight or less, and more preferably 0.01% by weight or less.
If necessary, the dispersion can be heated and stirred before the organic solvent is distilled off.
The obtained aqueous dispersion of anionic polymer particles containing a colorant is one in which the solid content of the anionic polymer containing a colorant is dispersed in water as a main medium. Here, the form of the anionic polymer particles is not particularly limited as long as the particles are formed of at least a colorant and an anionic polymer. For example, a particle form in which a colorant is encapsulated in the anionic polymer, a particle form in which the colorant is uniformly dispersed in the anionic polymer, a particle form in which the colorant is exposed on the surface of the anionic polymer particle, etc. included.

[Production of water dispersion for inkjet recording]
The aqueous dispersion for inkjet recording of the present invention can be produced by a method having the following step (a).
Step (a): A step of mixing an aqueous dispersion of anionic colored particles and an aqueous dispersion of cationic polymer particles to obtain an aqueous dispersion of composite particles in which anionic colored particles are attached to the cationic polymer particles. Furthermore, when the anionic colored particles are anionic polymer particles containing a pigment, it is preferably produced by a method having a step (b) after the step (a).
Step (b): Water of composite particles in which a crosslinking agent is added to the aqueous dispersion of composite particles obtained in step (a), and anionic crosslinked polymer particles containing a colorant are attached to the cationic polymer particles. Step of obtaining a dispersion

Step (a)
In the step (a), an aqueous dispersion of anionic colored particles and an aqueous dispersion of cationic polymer particles are mixed. The aqueous dispersion of anionic colored particles used here is preferably an aqueous dispersion of anionic polymer particles containing a colorant obtained by the step (2).
By mixing the two, an aqueous dispersion for ink jet recording containing composite particles in which both are electrically bonded and anionic polymer particles containing a pigment adhere to the surface of the cationic polymer particles can be obtained. . Preferably, after both are mixed, further dispersion processing is performed. By carrying out the dispersion treatment, composite particles having a uniform particle size can be obtained.
The dispersion treatment can be performed using the disperser described in the step (1). For example, kneading machines such as roll mills, homovalve type high pressure homogenizers such as high pressure homogenizers, chamber type high pressure homogenizers such as microfluidizers, nanomizers, optimizers, starbursts, media type dispersers such as paint shakers and bead mills. . Examples of commercially available media type dispersers include Ultra Apex Mill, Pico Mill, and Dyno Mill. Further, the dispersion treatment can be carried out using an ultrasonic disperser, preferably an ultrasonic homogenizer. As the ultrasonic homogenizer, one having a frequency of 20 to 2000 kHz and a wattage per liter of the total reaction volume is preferably 20 to 1000 W, more preferably 50 to 800 W. Such an ultrasonic disperser is commercially available from Nippon Seiki Seisakusho, Alex Co., Ltd. A plurality of these devices can be combined.
The temperature in the dispersion treatment is preferably 0 to 50 ° C, more preferably 0 to 30 ° C.

Step (b)
In the step (b), a cross-linking agent is added to the aqueous dispersion of the composite particles obtained in the step (a), and the anionic cross-linked polymer particles containing a colorant are attached to the cationic polymer particles. This is a step of obtaining an aqueous dispersion. The step (b) is preferably performed from the viewpoint of enhancing the storage stability of the aqueous dispersion.
Crosslinking of the anionic polymer can also be carried out by mixing a dispersion of anionic polymer particles containing the colorant obtained in step (1) and a crosslinking agent. In this case, the aqueous dispersion of the present invention can be obtained by performing the step of removing the organic solvent from the dispersion of the anionic crosslinked polymer particles obtained in the crosslinking step in the same manner as in the step (2). it can.
Here, as a crosslinking agent, the compound which has a functional group which reacts with the anionic group of a polymer is preferable, and the compound which has this functional group in 2 or more, Preferably 2-6 in a molecule | numerator is more preferable.
The crosslinking agent used in the present invention has a dissolution amount of preferably 50 g or less when dissolved in 100 g of water at 25 ° C. from the viewpoint of efficiently crosslinking the surface of an anionic polymer, particularly an anionic water-insoluble polymer. Preferably it is 40 g or less, More preferably, it is 30 g or less. Further, the molecular weight of the crosslinking agent is preferably 120 to 2000, more preferably 150 to 1500, and still more preferably 150 to 1000, from the viewpoint of easy reaction and storage stability of the aqueous dispersion.

(Crosslinking agent)
Preferable examples of the crosslinking agent include the following (a) to (c).
(A) Compound having two or more epoxy groups in the molecule: for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether Polyglycidyl ethers such as trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A type diglycidyl ether.
(B) Compounds having two or more oxazoline groups in the molecule: for example, bisoxazoline compounds such as 2,2′-bis (2-oxazoline), 1,3-phenylenebisoxazoline, 1,3-benzobisoxazoline, A compound having a terminal oxazoline group obtained by reacting the compound with a polybasic carboxylic acid.
(C) Compound having two or more isocyanate groups in the molecule: for example, organic polyisocyanate or isocyanate group-terminated prepolymer.
Among these, (a) a compound having two or more epoxy groups in the molecule is preferable, and ethylene glycol diglycidyl ether and trimethylolpropane polyglycidyl ether are particularly preferable.

The amount of the crosslinking agent used is preferably 0.1 / 100 to 50/100 in terms of the weight ratio of [crosslinking agent / anionic polymer] from the viewpoint of storage stability of the aqueous dispersion, and 0.5 / 100 to 40 / 100 is more preferable, 1/100 to 30/100 is more preferable, and 2/100 to 25/100 is still more preferable.
The amount of the crosslinking agent used is preferably an amount that reacts with 0.01 to 10 mmol / g as the number of moles of reactive groups of the crosslinking agent relative to the anionic polymer (per 1 g). The amount is more preferably 0.05 to 5 mmol / g, and still more preferably 0.1 to 2 mmol / g.
The anionic crosslinked polymer in the aqueous dispersion of composite particles obtained in the step (b) contains 0.5 mmol / g or more of an anionic group (preferably a carboxy group) neutralized with a base per 1 g of the crosslinked polymer. It is preferable. Such a crosslinked polymer is considered to contribute to the stability of the anionic crosslinked polymer particles containing the pigment by dissociating in the aqueous dispersion and charge repulsion between the anions.
Here, the crosslinking rate (mol%) of the crosslinked polymer obtained from the following formula (3) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and still more preferably 30 to 70 mol%. The crosslinking rate can be determined by calculation from the amount of the crosslinking agent used and the number of moles of the reactive group, the amount of polymer used and the number of moles of the reactive group of the polymer that can react with the reactive group of the crosslinking agent.
Crosslinking rate (mol%) = [number of moles of reactive group of crosslinking agent / number of moles of reactive group capable of reacting with crosslinking agent of polymer] × 100 (3)
In the formula (3), “the number of moles of the reactive group of the crosslinking agent” is obtained by multiplying the number of moles of the crosslinking agent to be used by the number of reactive groups in one molecule of the crosslinking agent.

The average particle size of the composite particles obtained by the step (a) or the steps (a) and (b) is preferably 40 to 1000 nm, more preferably 60 to 600 nm, from the viewpoint of the print density of the aqueous dispersion or ink. More preferably, it is 80-300 nm.
The average particle size can be measured by the method described in the examples.

[Water dispersion for inkjet recording]
The aqueous dispersion of the present invention can also be used as an aqueous ink as it is.
The content of each component in the aqueous dispersion of the present invention is as follows.
The content of the colorant contained in the anionic colored particles in the composite particles used in the aqueous dispersion of the present invention in the aqueous dispersion is preferably from 2 to 35% by weight from the viewpoint of increasing the printing density of the aqueous dispersion. More preferably, it is 3 to 30% by weight, and further preferably 5 to 25% by weight. The water content is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, and still more preferably 40 to 70% by weight.
The preferred surface tension (20 ° C.) of the aqueous dispersion of the present invention is 30 to 70 mN / m, more preferably 35 to 65 mN / m.
The viscosity (20 ° C.) of 20% by weight (solid content) of the aqueous dispersion of the present invention is preferably 1 to 12 mPa · s, more preferably 1 to 9 mPa · s, more preferably 2 to 6 mPa · s, and still more preferably. Is 2 to 5 mPa · s.

[Water-based ink for inkjet recording]
The aqueous ink for inkjet recording of the present invention includes a wetting agent, a penetrating agent, a dispersant, a surfactant, a viscosity modifier, an antifoaming agent, an antiseptic, an antifungal agent, a rust preventive agent and the like that are usually used for aqueous inks. Can be added.
The content of each component in the aqueous ink of the present invention is as follows.
The content of the colorant contained in the anionic colored particles in the composite particles used in the aqueous ink of the present invention in the aqueous ink is preferably 1 to 25% by weight, more preferably from the viewpoint of increasing the printing density of the aqueous ink. Is 2 to 20% by weight, more preferably 4 to 15% by weight, still more preferably 5 to 12% by weight. The water content is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, and still more preferably 40 to 70% by weight.
The preferred surface tension (20 ° C.) of the water-based ink of the present invention is 23 to 50 mN / m, more preferably 23 to 45 mN / m, and still more preferably 25 to 40 mN / m.
In order to maintain good ejection reliability, the viscosity (20 ° C.) of the aqueous ink of the present invention is preferably 2 to 20 mPa · s, more preferably 2.5 to 16 mPa · s, and still more preferably 2. 5 to 12 mPa · s.
The ink jet system to which the water-based ink of the present invention is applied is not limited, but is suitable for a piezo ink jet printer suitable for discharging a dispersion liquid containing a dispersible colorant such as a pigment or particles such as polymer particles.

In the following production examples, examples and comparative examples, “parts” and “%” are “parts by weight” and “% by weight” unless otherwise specified. The weight average molecular weight of the polymer and the average particle diameter of the polymer particles are measured by the following method, the storage stability is measured for the aqueous dispersion, and the printing density is evaluated by printing the aqueous ink by the following printing method. did.
(1) Measurement of weight average molecular weight of anionic polymer Gel chromatography using a solution obtained by dissolving phosphoric acid and lithium bromide in N, N-dimethylformamide so as to have concentrations of 60 mmol / L and 50 mmol / L, respectively. It was measured using polystyrene as a standard substance by the method [GPC apparatus (HLC-8120GPC) manufactured by Tosoh Corporation, column (TSK-GEL, α-M × 2), manufactured by Tosoh Corporation, flow rate: 1 mL / min].
(2) Measurement of average particle diameter of cationic polymer particle, anionic polymer particle containing pigment, composite particle or mixed particle The particle size was measured using a laser particle analysis system ELS-8000 (cumulant analysis) manufactured by Otsuka Electronics Co., Ltd. A dispersion diluted with water so that the concentration of particles to be measured was about 5 × 10 ⁻³ wt% was used. The measurement conditions were a temperature of 25 ° C., an angle between incident light and a detector of 90 °, and the number of integrations of 100. The refractive index of water (1.333) was input as the refractive index of the dispersion solvent.

(3) Storage stability of aqueous dispersion The aqueous dispersion is filled into a glass sealed container, and the viscosity after storage at 30 ° C. for 7 days is 20 ° C. using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80L). The viscosity change rate was obtained from the following formula. The smaller the absolute value of the change rate, the better the storage stability.
Storage stability (Viscosity change rate) (%) = (([viscosity after storage] − [viscosity before storage]) / [viscosity before storage]) × 100
(4) Printing method Ink is filled into the ink injection port at the upper part of the black head of an ink jet printer (manufactured by Seiko Epson Corporation, model number: EM-930C, piezo method) through a silicon tube. Next, a solid print pattern (size: horizontal 204 mm × length 275 mm) is created using image editing software Photoshop (manufactured by Adobe), and trial printing is performed by changing the solid duty (printing condition = paper type: normal) Paper, mode setting: black, fine, bidirectional), and the duty was adjusted so that the actual discharge amount was 0.75 ± 0.01 mg / cm ² . The discharge amount was determined from the change in the weight of the screw tube containing the ink. Printing was performed on commercially available plain paper (trade name: XEROX4200, manufactured by XEROX, high-quality plain paper) using the adjusted solid solid image.
(5) Measurement of printing density After the printed matter was left at 25 ° C. and 50% humidity for 24 hours, the printing density on the printing surface was measured. The print density was measured by reading the numerical value of the color density component of magenta using a Macbeth densitometer (Gretag Macbeth, product number: RD914) under the following measurement conditions. Observation light source: D65, observation visual field: 2 degrees, concentration standard: DIN 16536. The measurement place was changed, and 5 points were randomly selected from the printed portions in the forward and return passes of bidirectional printing, and an average value of a total of 10 points was obtained.

Synthesis Example 1 (Synthesis of aqueous dispersion of cationic polymer particles (1))
To a 500 ml Separa flask, 300 g of ion exchange water, 45 g of styrene, 2.5 g of divinylbenzene, and 2.5 g of methacryloyloxyethyltrimethylammonium chloride were added, and the temperature was raised to 70 ° C. while stirring at 300 rpm. Polymerization initiator (trade name: V-50, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 5 g of ion exchange water after stirring for 20 minutes. 5 g was added and reacted for 3 hours under stirring at 70 ° C. and 200 rpm. Thereafter, the temperature was raised to 75 ° C., and the mixture was further reacted for 3 hours (soap-free emulsion polymerization).
The obtained emulsion was filtered through a 200-mesh stainless steel mesh and concentrated with an evaporator until the solid content was 25%. The concentrated emulsion is applied to a centrifuge (treated at 6000 rpm for 15 minutes), decanted to remove the liquid layer, and filtered with a filter (manufactured by Sartorius, mini-Salto syringe filter, pore size: 5 μm, material: cellulose acetate). After removing the coarse particles, the pH is adjusted to 7 with 1N sodium hydroxide, diluted with ion-exchanged water so that the solid content concentration becomes 20%, and the aqueous dispersion of the cationic polymer particles (1) having an average particle diameter of 119 nm is obtained. Got the body.
Synthesis Example 2 (Synthesis of aqueous dispersion of cationic polymer particles (2))
The monomer of Synthesis Example 1 was prepared in the same manner except that 46.25 g of styrene, 2.5 g of divinylbenzene, and 1.25 g of methacryloyloxyethyltrimethylammonium chloride were prepared, and the cationic content was 20% solid content and the average particle size was 195 nm. An aqueous dispersion of polymer particles (2) was obtained.

Comparative Synthesis Example 1 (Synthesis of an aqueous dispersion of anionic polymer particles)
(1) Synthesis of anionic polymer 14 parts of methacrylic acid, 30 parts of styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6S) (solid content 50%), 46 parts of styrene, 25 parts of polypropylene glycol monomethacrylate are mixed. Then, a monomer mixed solution was prepared.
In a reaction vessel, 3 parts of methyl ethyl ketone, 0.03 part of a polymerization chain transfer agent (2-mercaptoethanol) and 10% of the monomer mixture are mixed to obtain an initial charge monomer solution, and nitrogen in the reaction vessel Gas replacement was performed sufficiently.
On the other hand, the balance (90%) of the monomer mixture, 0.27 parts of the polymerization chain transfer agent, 21 parts of methyl ethyl ketone, and a polymerization initiator (trade name: V-65, 2, 2 manufactured by Wako Pure Chemical Industries, Ltd.) 1.0 part of '-azobis (2,4-dimethylvaleronitrile)) was mixed to obtain a dropping monomer solution. This was put into a dropping funnel, and the temperature of the initially charged monomer solution in the reaction vessel was raised to 75 ° C. with stirring under a nitrogen atmosphere, and the dropped monomer solution was dropped over 3 hours. After 2 hours at 75 ° C. from the end of dropping, a polymerization initiator solution in which 0.9 part of the polymerization initiator was dissolved in 45 parts of methyl ethyl ketone was added, and further aged at 75 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a polymer solution. (Weight average molecular weight of polymer: 57000) was obtained.
(2) Preparation of aqueous dispersion of anionic polymer particles 7.9 parts of the polymer obtained by drying the polymer solution obtained in (1) above under reduced pressure was dissolved in 22.7 parts of methyl ethyl ketone, and neutralized therein. After adding 2.4 parts of 5N aqueous sodium hydroxide solution, 0.2 parts of 25% aqueous ammonia, and 66.7 parts of ion-exchanged water, the mixture was mixed at 8000 rpm for 1 hour at 15 ° C. with a microfluidizer (Microfluidics, Inc.). Made by high pressure homogenizer, trade name, model M-140K), and further subjected to 19-pass dispersion treatment at a pressure of 180 MPa. Methyl ethyl ketone and a part of water were removed from the obtained dispersion at 60 ° C. under reduced pressure. The obtained concentrated liquid is centrifuged, and the liquid layer portion is filtered through a filter (manufactured by Sartorius, mini-Salto syringe filter, pore size: 1.2 μm, material: cellulose acetate) to remove coarse particles, and anionic polymer particles An aqueous dispersion (solid concentration: 19.56%, average particle size: 159 nm) was obtained.

Preparation Example 1 (Preparation of aqueous dispersion of anionic polymer particles containing pigment)
(1) Synthesis of anionic polymer 142 parts of benzyl acrylate (c), 38 parts of methacrylic acid (a), and styrene macromer (b) (manufactured by Toagosei Co., Ltd., trade name: AS-6S) (solid content 50%) Forty parts were mixed to prepare a monomer mixture.
In a reaction vessel, 18 parts of methyl ethyl ketone, 0.03 part of a polymerization chain transfer agent (2-mercaptoethanol) and 10% of the monomer mixture are mixed to obtain an initial charge monomer solution, and nitrogen in the reaction vessel Gas replacement was performed sufficiently.
On the other hand, the remainder (90%) of the monomer mixture, 0.27 parts of the polymerization chain transfer agent, 42 parts of methyl ethyl ketone, and 1.2 parts of the polymerization initiator (V-65) are mixed to obtain a dropped monomer solution. It was. This was put into a dropping funnel, and the temperature of the initially charged monomer solution in the reaction vessel was raised to 75 ° C. with stirring under a nitrogen atmosphere, and the dropped monomer solution was dropped over 3 hours. After 2 hours at 75 ° C. from the end of the dropwise addition, a polymerization initiator solution in which 0.3 part of the polymerization initiator was dissolved in 5 parts of methyl ethyl ketone was added, and further aged at 75 ° C. for 2 hours and 80 ° C. for 2 hours. A methyl ethyl ketone solution of the polymer (weight average molecular weight of the polymer: 90000) was obtained.
(2) Preparation of aqueous dispersion of anionic polymer particles containing pigment Dissolve 45 parts of anionic polymer obtained by drying under reduced pressure the methyl ethyl ketone solution of the anionic polymer obtained in (1) above in 300 parts of methyl ethyl ketone. Further, 10.2 parts of a neutralizing agent 5N aqueous sodium hydroxide solution, 12.2 parts of 25% aqueous ammonia, and 1150 parts of ion-exchanged water are added, and a magenta pigment (from unsubstituted quinacridone and 2,9-dichloroquinacridone) is added. After adding 180 parts of a solid solution pigment, manufactured by Ciba Japan Co., Ltd., trade name: Chromophthaljet Magenta 2BC), mixing at 20 ° C. with a disperser blade at 7000 rpm for 1 hour, a bead mill type disperser (manufactured by Kotobuki Industries Co., Ltd., Ultra) Apex mill, model UAM-05, media particles: zirconia beads, Diameter: 0.05 mm) were mixed and dispersed at 20 ° C. 40 minutes using a. The obtained dispersion was further subjected to a 5-pass dispersion treatment at a pressure of 180 MPa using the microfluidizer (M-140K).
Methyl ethyl ketone and a part of water were removed from the obtained dispersion at 60 ° C. under reduced pressure. The obtained concentrated liquid is centrifuged, and the liquid layer portion is filtered through the filter (manufactured by Sartorius, pore size: 5 μm) to remove coarse particles, and an aqueous dispersion of anionic polymer particles containing a pigment [solid content concentration : 30.0%, average particle size 74 nm].

Preparation Example 2 (Preparation of an aqueous dispersion of anionic crosslinked polymer particles containing a pigment)
40 g of an aqueous dispersion of anionic polymer particles containing the pigment obtained in Preparation Example 1 was ion-exchanged with 0.42 g of an epoxy-based crosslinking agent (trade name: Denacol EX321, epoxy equivalent 140, manufactured by Nagase ChemteX Corporation). 0.98 g of water was added, and the mixture was kept in a 90 ° C. warm bath with stirring for 1 hour. After cooling, the mixture is filtered through the filter (manufactured by Sartorius, pore size: 5 μm) to remove coarse particles, and anionic crosslinked polymer particles containing a pigment [solid content concentration: 30.0%, average particle size of 77 nm, the above formula ( An aqueous dispersion having a crosslinking ratio of the crosslinked polymer of 3) of 56.8 mol%] was obtained.

Production Example 1 (Production of aqueous dispersion containing composite particles (1))
While stirring 10 g of the aqueous dispersion of anionic polymer particles containing the pigment obtained in Preparation Example 1, the cationic polymer particles obtained in Synthesis Example 1 adjusted to a solid concentration of 6% with ion-exchanged water (1 20 g of the aqueous dispersion was dropped, and then dispersed for 3 minutes with an ultrasonic disperser (300 μA) to obtain an aqueous dispersion containing composite particles (1) having an average particle diameter of 138 nm.
1 and 2 show electron micrographs of the obtained composite particles 1 (manufactured by JEOL Ltd., transmission electron microscope “JEM-2100 type”, using acceleration voltage of 80 KV).

Production Example 2 (Production of aqueous dispersion containing composite particles (2))
While stirring 40 g of an aqueous dispersion of anionic polymer particles containing the pigment obtained in Preparation Example 1, the cationic polymer particles (1 18.46 g of the aqueous dispersion was dropped and then dispersed for 5 minutes with an ultrasonic disperser (300 μA). Further, 0.47 g of the epoxy crosslinking agent (Denacol EX321) and 1.07 g of ion-exchanged water were added. And kept in a 90 ° C. warm bath with stirring for 1 hour. After cooling, the mixture is filtered through the filter (manufactured by Sartorius, pore size: 5 μm) to remove coarse particles, and composite particles (2) having an average particle size of 147 nm (crosslinking rate of the crosslinked polymer according to the formula (3): 56.8 mol) %) Was obtained.
Comparative Production Example 1 (Production of aqueous dispersion containing mixed particles)
While stirring 10 g of the aqueous dispersion of anionic polymer particles containing the pigment obtained in Preparation Example 1, the solid content concentration was adjusted to 6% with ion-exchanged water. After 20 g of the aqueous dispersion was dropped, the mixture was dispersed for 3 minutes with an ultrasonic disperser (300 μA) to obtain an aqueous dispersion containing mixed particles.
Production Example 3 (Production of aqueous dispersion containing composite particles (3))
While stirring 10 g of the aqueous dispersion of anionic polymer particles containing the pigment obtained in Preparation Example 1, the cationic polymer particles obtained in Synthesis Example 2 adjusted to a solid content concentration of 6% with ion-exchanged water (2 20 g of the aqueous dispersion was dropped, and then dispersed for 3 minutes with an ultrasonic disperser (300 μA) to obtain an aqueous dispersion containing composite particles (3) having an average particle size of 138 nm.

Formulation example (production of water-based ink)
An aqueous dispersion containing any of the composite particles (1) to (3) obtained in Production Examples 1 to 3, an aqueous dispersion containing the mixed particles obtained in Comparative Production Example 1, and obtained in Preparation Example 1. The aqueous dispersion of the anionic polymer particles containing the obtained pigment or the aqueous dispersion of the anionic crosslinked polymer particles containing the pigment obtained in Preparation Example 2 is 10.0 parts in terms of pigment content. Prepared.
2.0 parts of 1,2-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.0 parts of 2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.), Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd., nonionic surfactant) Agent) 0.5 part, Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd., nonionic surfactant) 0.5 part, glycerin (manufactured by Kao Corporation) 2.0 parts, triethylene glycol monobutyl ether (trade name: butyl) Triglycol (manufactured by Nippon Emulsifier Co., Ltd.) 10.0 parts, Proxel XL2 (manufactured by Avicia Co., Ltd., preservative) 0.3 parts, and ion-exchanged water are mixed while stirring with a magnetic stirrer, and further 15 at room temperature. The mixture was stirred for a minute to obtain a mixed solution. Here, the blending amount of the ion-exchanged water is an amount adjusted so that the total amount of the mixed solution and the aqueous dispersion added becomes 100 parts.
Next, stirring the aqueous dispersion prepared in advance with a magnetic stirrer, the mixed solution was added, and the mixture was filtered through a 1.2 μm filter (cellulose acetate film, manufactured by Sartorius) to obtain an aqueous ink.

  From Table 1, the aqueous inks of Examples 1 to 3 are superior in print density to the aqueous inks of Comparative Examples 1 to 3, and Example 2 using a crosslinked polymer as an anionic polymer is Example 1. It can be seen that the storage stability is better than that.

4 is an electron micrograph of composite particles obtained in Production Example 1. FIG. 4 is another electron micrograph of the composite particles obtained in Production Example 1.

Claims (7)

Containing composite particles with anionic colored particles attached to the cationic polymer particles ;
The anionic colored particles are anionic polymer particles containing a colorant;
An aqueous dispersion for ink jet recording , wherein the anionic colored particles have an average particle size smaller than the average particle size of the cationic polymer particles . The anionic polymer used for the anionic colored particles is a vinyl polymer obtained by copolymerizing a monomer mixture containing (a) an anionic monomer and (b) a macromer and / or (c) a hydrophobic monomer. The aqueous dispersion for inkjet recording according to claim 1. The aqueous dispersion for inkjet recording according to claim 1 or 2, wherein the anionic polymer particles containing a colorant are anionic crosslinked polymer particles containing a colorant. The anionic crosslinked polymer particles are formed from an anionic polymer particle containing the colorant and a crosslinking agent,
The said crosslinking agent is a compound which has a functional group which reacts with the anionic group of the anionic polymer used for the said anionic colored particle, and is a compound which has 2 or more of this functional group in a molecule | numerator . Water dispersion for inkjet recording. The aqueous dispersion for inkjet recording according to claim 4, wherein the crosslinking agent is a compound having two or more epoxy groups in a molecule . The water dispersion for ink-jet printing according to claim 1, obtained by granulation process made that have a following step (a).
Step (a): A step of mixing an aqueous dispersion of anionic colored particles and an aqueous dispersion of cationic polymer particles to obtain an aqueous dispersion of composite particles in which anionic colored particles are attached to the cationic polymer particles. The aqueous dispersion for inkjet recording according to claim 1, which is obtained by a production method having the following steps (a) and (b) .
Step (a): A step of mixing an aqueous dispersion of anionic colored particles and an aqueous dispersion of cationic polymer particles to obtain an aqueous dispersion of composite particles in which anionic colored particles are attached to the cationic polymer particles. Step (b): Water of composite particles in which a crosslinking agent is added to the aqueous dispersion of composite particles obtained in step (a), and anionic crosslinked polymer particles containing a colorant are attached to the cationic polymer particles. Step of obtaining a dispersion