JP5438467B2 - Method for producing aqueous dispersion for ink jet recording - Google Patents

Description

  The present invention relates to a method for producing an aqueous dispersion for ink jet recording, and an aqueous ink for ink jet recording containing an aqueous dispersion obtained by the method.

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.
In recent years, inks using pigments as colorants have been widely used in order to impart weather resistance and water resistance to printed matter.

Patent Document 1 discloses an aqueous pigment ink comprising a pigment, an anionic dispersant, a cationic water-soluble polymer compound such as polyethyleneimine, and an aqueous medium for the purpose of improving saturation, density, etc. in plain paper printing. ing.
Patent Document 2 discloses an aqueous pigment ink containing a pigment, a polymer dispersant, polyethyleneimine, a water-soluble solvent, and water for the purpose of improving the fixability of the pigment to an OHP sheet or the like.
Patent Document 3 discloses a surface potential adjusting step in which a polymer compound is modified on the surface of fine particles to adjust the surface potential of the fine particles, a fluid containing fine particles having a positive surface potential, and fine particles having a negative surface potential. A method for producing composite particles having a mixing step of mixing a contained fluid with a microchannel or the like is disclosed.
In Patent Document 4, for the purpose of obtaining pigment fine particles having a uniform particle size, two or more kinds of solutions including a particle forming material solution and a poor solvent solution are brought into contact with each other in a mixing unit such as a microreactor to form fine particles. A method of forming microparticles, a step of forming an aggregate by bringing a flocculant into contact with the microparticles in a flow path, a filtration step, and a step of redispersing the aggregate by pH adjustment to form microparticles. It is disclosed.

JP 2004-123865 A Japanese Patent Laid-Open No. 10-60352 JP 2006-82073 A JP 2009-197097 A

When a dispersible color material such as a pigment is used as a colorant for a water-based ink for ink jet recording, there is a problem that a sufficient print density is not obtained because paper fibers are not dyed unlike water-soluble dyes. In addition, since dispersed particles such as pigments have a particle size distribution, the coarse particles cause poor filterability of the ink or the aqueous dispersion used therein, which causes clogging of filters and discharge nozzles installed in the printer. There is.
An object of the present invention is to provide a method for producing an aqueous dispersion for inkjet recording excellent in print density and filterability, and an aqueous ink for inkjet recording containing the aqueous dispersion obtained by the method.

The present inventor considered that the reason why it is difficult to obtain a sufficient print density with an ink using a dispersible color material such as a pigment is that the color material is fine particles and easily penetrates into paper. It was. As a result, an aqueous dispersion containing an anionic colored particle and an aqueous solution containing a water-soluble cationic polymer are mixed at a specific ratio within a flow path having a specific flow path cross-sectional area and flow path length. By mixing at a speed, the generation of coarse particles is suppressed, and chain-like particles are obtained by ionic interaction between the colored particles and the polymer having a uniform particle size, and the ink remains on the surface of the printing paper. Thus, it has been found that the print density can be improved.
That is, the present invention relates to an aqueous dispersion (A) containing anionic colored particles and an aqueous solution (B) containing a water-soluble cationic polymer with a flow passage cross-sectional area of 0.001 to 0.5 mm ² . A method for producing an aqueous dispersion comprising a step of mixing in a channel having a length of 0.1 to 10 mm, wherein the line in the hole at the position where the aqueous dispersion (A) and the aqueous solution (B) join together An aqueous dispersion for inkjet recording, wherein the speed is 1 m / sec or more, and the amount of the cationic group of the water-soluble cationic polymer is 5 to 50 mol% with respect to the amount of the anionic group of the anionic colored particles And a water-based ink for ink-jet recording containing an aqueous dispersion obtained by the method.

  ADVANTAGE OF THE INVENTION According to this invention, the water-based ink for inkjet recording containing the water dispersion obtained by the efficient manufacturing method of the inkjet recording water dispersion excellent in printing density | concentration and filterability, and the method can be provided.

(A-1), (a-2), (a-3) is a schematic diagram showing an example of a T-type microchannel, and (b) is an example of a Y-type microchannel. It is a schematic diagram of the T-type microchannel used in Examples 1 to 6, 8 and Comparative Examples 3 and 4.

The method for producing an aqueous dispersion for ink-jet recording of the present invention comprises an aqueous dispersion containing an anionic colored particle (A) and an aqueous solution containing a water-soluble cationic polymer (B) having a cross-sectional area of 0.001 to 0.001. A method for producing an aqueous dispersion comprising a step of mixing in a flow path having a flow path length of 0.1 to 10 mm at 0.5 mm ² , wherein the aqueous dispersion (A) and the aqueous solution (B) are merged The linear velocity in the pores at the position (hereinafter also referred to as “in-pore linear velocity”) is 1 m / second or more, and the amount of the cationic group of the water-soluble cationic polymer is the anionic group of the anionic colored particle. It is characterized by being 5 to 50 mol% with respect to the amount.
Hereinafter, each component and process used in the present invention will be described.

[Anionic colored particles]
In the present invention, the anionic colored particles (hereinafter also simply referred to as “colored particles”) are “containing a colorant from the viewpoint of dispersion stability of the colored particles in the ink and improving the printing density of the ink. Preferably, the anionic polymer particles are From the viewpoint of storage stability of the anionic polymer particles, the anionic polymer particles are preferably anionic crosslinked polymer particles. As will be described later, the crosslinked polymer particles may be formed, for example, by adding a crosslinking agent to an aqueous dispersion of anionic polymer particles containing a colorant to form an aqueous dispersion of an anionic crosslinked polymer particle containing a colorant. Can be obtained as
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 anionic colored particles is preferably from 10 to 300 nm, more preferably from 40 to 200 nm, more preferably from 50 to 150 nm, still more preferably from 60 to 100 nm, and even more preferably from 60 to 300 nm, from the viewpoint of the printing density of the ink. 90 nm. The average particle size is measured by the method described in the examples.

[Colorant]
The colorant used in the present invention is not particularly limited, and pigments, hydrophobic dyes, water-soluble dyes (acidic dyes, reactive dyes, direct dyes, etc.) can be used, but water resistance, dispersion stability and From the viewpoint of scratch resistance, pigments and hydrophobic dyes are preferable, and pigments are more preferable.
When the pigment and the hydrophobic dye are used in the aqueous dispersion, it is preferable to use a surfactant and a polymer to form stable fine particles in the aqueous dispersion. In particular, from the viewpoint of bleeding resistance, water resistance, printing density, 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, and the organic pigment is preferable from the viewpoint of sufficiently exerting the effect of improving the printing density. 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. Among these, carbon black is preferable particularly in a black water dispersion. 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 pigment such as red, yellow, blue, orange, and green can be used.
Specific examples of preferred organic pigments include C.I. I. Pigment yellow, C.I. I. Pigment Red, C.I. I. Pigment orange, 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. The quinacridone solid solution pigment is preferably a solid solution pigment comprising a combination of unsubstituted quinacridone (CI Pigment Violet 19) and 2,9-dichloroquinacridone (CI Pigment Red 202).

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, as another atomic group, a C1-C12 alkanediyl group, a phenylene group, a naphthylene group, etc. are mentioned.
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 per 1 g of the self-dispersing pigment, and preferably 200 to 700 μmol per 1 g of the self-dispersing pigment when the hydrophilic functional group is a carboxy group.
Examples of commercially available anionic self-dispersing pigments include CAB-O-JET200, 300, 352K, 250C, 260M, 270Y, 450C, 465M, 470Y, and 480V (manufactured by Cabot Corporation) BONJET CW-1, CW-2 (made by Orient Chemical Industry Co., Ltd.), Aqua-Black 162 (made by Tokai Carbon Co., Ltd.), etc. are mentioned.

The hydrophobic dye is not particularly limited as long as it can be contained in the polymer particles. The hydrophobic dye is 2 g / L or more, preferably 20 to 500 g / L (25 ° C.) with respect to the organic solvent (preferably methyl ethyl ketone) used in the production of the polymer from the viewpoint of efficiently containing the dye in the polymer. Those that dissolve are 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 Co., etc.
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 printing density of the ink. Here, the water-insoluble polymer refers to a polymer that is dried at 105 ° C. for 2 hours and dissolved in 100 g of water at 25 ° C. and has a dissolution amount of 10 g or less. The amount is preferably 5 g or less, more preferably 1 g or less. In the case of an anionic 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 dispersion stability of the anionic polymer particles, the polymer is obtained by addition polymerization of a vinyl monomer (vinyl compound, vinylidene compound, vinylene compound). Vinyl polymers are preferred.
Anionic vinyl polymers include (a) anionic monomer (hereinafter also referred to as “(a) component”), (b) macromer (hereinafter also referred to as “(b) component”) and / or (c) hydrophobicity. A vinyl polymer obtained by copolymerizing a monomer mixture (hereinafter also simply referred to as “monomer mixture”) containing a monomer (hereinafter also referred to as “component (c)”) 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 anionic polymer particles in the aqueous dispersion and promote ionic interaction with the cationic polymer.
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 in an aqueous dispersion of anionic polymer particles.

[(B) Macromer]
(B) A macromer is a compound having a number average molecular weight of 500 to 100,000 having a polymerizable functional group at one end, and from the viewpoint of storage stability in an aqueous dispersion of anionic polymer 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, from the viewpoint of dispersion stability of the anionic polymer particles in the aqueous dispersion, a styrene macromer, an aromatic group-containing (meth) acrylate macromer, and a silicone macromer are preferable.
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 anionic polymer particles in the aqueous dispersion. 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 anionic polymer particles in the aqueous dispersion. 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 and the ink containing the aqueous dispersion. 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 and an aromatic group-containing (meth) acrylate. Is more preferable, and an aromatic group-containing (meth) acrylate is more preferable. It is also preferable to use a styrene monomer and an aromatic group-containing (meth) acrylate 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 therein: 1-29) (meth) acrylate, phenoxy (ethylene glycol / propylene glycol copolymer) (1 To 30 and ethylene glycol: 1 to 29) (meth) acrylate therein.

Specific examples of the commercially available component (d) include NK Esters M-20G, 40G, 90G, and 230G from Shin-Nakamura Chemical Co., Ltd., Bremer PE-90 and 200 from NOF Corporation. 350, PME-100, 200, 400, 1000, PP-500, 800, 1000, AP-150, 400, 550, 800, 50PEP-300, 50POEP-800B, 43PAPE600B, etc. Is mentioned.
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 weights from the viewpoint of stably dispersing the anionic polymer particles in the aqueous dispersion and promoting the ionic interaction between the anionic polymer particles and the cationic polymer. %, More preferably 4 to 30% by weight, particularly preferably 5 to 25% by 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 anionic polymer particles in the aqueous dispersion.
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 and the ink containing the aqueous dispersion.
In addition, the weight ratio of [(a) component / [(b) component + (c) component]] is such that the dispersion stability of the anionic polymer particles in the water dispersion, and the water dispersion and the water dispersion thereof are determined. From the viewpoint of the printing density of the ink to be contained, 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 5 from the viewpoint of the dispersion stability of the anionic polymer particles in the aqueous dispersion and the printing density of the aqueous dispersion and the ink containing the aqueous dispersion. 000 to 500,000 are preferred, 10,000 to 400,000 are more preferred, 10,000 to 300,000 are more preferred, and 20,000 to 300,000 are even more preferred. In addition, the weight average molecular weight of a polymer is measured by the method as described in an Example.
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.
From the viewpoint of dispersion stability, the neutralization degree of the anionic group of the anionic polymer is preferably 10 to 300%, more preferably 20 to 200%, and still more preferably 30 to 150%.
When the anionic polymer is crosslinked, the degree of neutralization of the anionic group of the polymer before crosslinking is preferably 10 to 90%, more preferably 20 to 80%, from the viewpoint of dispersion stability and crosslinking efficiency. 30 to 70% is more preferable.
Here, the neutralization degree can be obtained by the following equation.
{[Weight of neutralizing agent (g) / equivalent of neutralizing agent] / [acid value of polymer (KOH mg / g) × polymer weight (g) / (56 × 1000)]} × 100
The acid value can be calculated from the structural unit of the polymer. Alternatively, it can also be determined by a method in which a polymer is dissolved in a suitable solvent (for example, methyl ethyl ketone) and titrated.

[Production of water-insoluble anionic polymer particles containing a colorant]
An aqueous dispersion of water-insoluble 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 colorant, water, and, if necessary, a neutralizing agent and a surfactant are added to the obtained organic solvent solution and mixed. A method of obtaining an oil-in-water type dispersion is preferred. Although there is no restriction | limiting in the order added to the organic solvent solution of an anionic polymer, It is preferable to add in order of a neutralizing agent, water, and a coloring agent.
In the mixture, the colorant 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 The amount is preferably 2 to 40% by weight, more preferably 3 to 20% by weight, and water is preferably 10 to 70% by weight, more preferably 20 to 70% by weight.
From the viewpoint of dispersion stability, the weight ratio of the amount of the colorant to the amount of the anionic polymer [colorant / anionic polymer] is preferably 50/50 to 90/10, and 70/30 to 85 / More preferably, it is 15.

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 lithium hydroxide, 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 size of the anionic polymer particles can be atomized only by the main dispersion until the desired particle size is reached, it is preferably predispersed and then subjected to further dispersion by applying shear stress to It is preferable to control the average particle size 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.
As means for giving the shear stress of this dispersion, kneaders such as roll mills, kneaders and extruders, high pressure homogenizers represented by high pressure homogenizers (Izumi Food Machinery Co., Ltd., trade names), microfluidizers (Microfluidics, Product names), Nanomizers (Yoshida Kikai Kogyo Co., Ltd., trade names), chamber type high-pressure homogenizers such as Optimizer, Starburst (Sugino Machine Co., Ltd., trade names), media shakers such as paint shakers and bead mills Can be mentioned. Commercially available media dispersers include Ultra Apex Mill (trade name, manufactured by Kotobuki Industries Co., Ltd.), Picomill (trade name, manufactured by Asada Tekko Co., Ltd.), Dino Mill (trade name, manufactured by Shinmaru Enterprises Co., Ltd.), 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 a colorant.

Process (2)
In the step (2), an aqueous dispersion of anionic polymer particles containing a colorant can be obtained by distilling off the organic solvent from the obtained dispersion by a known method. The organic solvent in the aqueous dispersion containing the obtained polymer particles is preferably substantially removed, but may remain unless the purpose of the present invention is impaired. If necessary, it may be removed again after crosslinking. The amount of the residual organic solvent 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 polymer containing a colorant is dispersed in water as a main medium. Here, the form of the polymer particles is as described above [0009].

(Water-soluble cationic polymer)
In the present invention, a water-soluble cationic polymer (hereinafter simply referred to as “cation”) is used from the viewpoint of efficiently interacting with anionic colored particles and improving the printing density of an aqueous dispersion or an ink containing the aqueous dispersion. Also referred to as “adhesive polymer”).
Here, “water-soluble” means that when the cationic polymer is dried at 105 ° C. for 2 hours and the polymer that has reached a constant weight is dissolved in 100 g of water at 25 ° C., the dissolved amount exceeds 10 g. The dissolution amount is preferably 20 g or more, more preferably 100 g or more.
The term “cationic” means that when an unneutralized polymer is dispersed or dissolved in pure water, the pH is higher than 7, and in the case of a polymer having a quaternary ammonium salt, the counter ion is When dispersed or dissolved in pure water as hydroxide ions, the pH becomes higher than 7, or when the polymer is insoluble in pure water and the pH cannot be measured clearly, it is dispersed in pure water. The zeta potential of the dispersion is positive.
In the aqueous dispersion for inkjet recording of the present invention, the reason why the printing density is improved by using a water-soluble cationic polymer is not clear, but on the medium after printing, anionic polymer particles and ions containing a colorant are printed. It is considered that the print density is improved since the colorant remains on the surface of the medium without causing anionic polymer particles containing the colorant to permeate into the medium, particularly paper. In addition, when the interaction is strong, in the aqueous dispersion, a plurality of polymer particles become chain-like secondary particles, and physical resistance and catching on the paper fiber as the medium increase, and the medium surface It is considered that the printing density is excellent because a large amount of the colorant can remain in the ink.
The number average molecular weight of the water-soluble cationic polymer is preferably 1,000 to 300,000, more preferably 10,000 to 80,000, from the viewpoint of printing density.

As the cationic polymer, cationic groups such as primary to tertiary amino groups, imino groups, quaternary ammonium bases, and hydrazine are used from the viewpoint of improving the printing density of an aqueous dispersion or an ink containing the aqueous dispersion. A polymer having an amino group and / or an imino group is more preferable, and a polymer having an amino group is still more preferable. The polymer is preferably a homopolymer of a monomer having a cationic group, a copolymer with another monomer, or a condensation polymer.
Specific examples of the cationic polymer include polyethyleneimine, polyallylamine, polyvinylamine, polyvinylpyridine, polyethyleneimine-epichlorohydrin reaction product, polyamide-polyamine resin, polyamide-epichlorohydrin resin, chitosans, cationized starch, polyamine sulfone, polyvinylimidazole. , Polyamidine, dicyanamide polyalkylene polyamine condensate, polyalkylene polyamine dicyandiamide ammonium salt condensate, dicyandiamide formalin condensate, diallyldimethylammonium chloride polymer and copolymer, vinylpyrrolidone / vinylimidazole copolymer, vinylbenzyltrimethylammonium Chloride polymer and copolymer, dimethylaminoethyl (meth) acrylate Compounds and copolymers, (meth) acryloyloxyalkyltrialkylammonium chloride polymers and copolymers, (meth) acryloyloxyalkyldialkylbenzylammonium chloride polymers and copolymers, or acid neutralized products thereof. Can be mentioned.
Preferable examples of the cationic polymer having an amino group include polyethyleneimine, polyallylamine, and polyvinylamine, polyethyleneimine and polyallylamine are more preferable, and polyethyleneimine is still more preferable.
The above cationic polymers can be used alone or in combination of two or more.

(Polyethyleneimine)
Polyethyleneimine is a water-soluble polymer compound represented by — (CH ₂ CH ₂ NH) _n —, in which ethyleneimine units are polymerized in a linear, branched or network form. Polyethyleneimine is present as a polycation in the aqueous dispersion, and when the pH of the aqueous dispersion is adjusted to 7 to 9, it interacts with the anionic group of the polymer particles containing the colorant, and a plurality of polymer particles It is considered that the printing density is improved in order to promote the aggregation due to the ionic interaction between them and suppress the permeation of the ink on the paper surface. Furthermore, since it is a polycation, it is thought that the adsorptivity to the polymer particle surface is high and the amount dissolved in the aqueous dispersion is reduced. Therefore, it is considered that the dispersion stability of the aqueous dispersion is high, and the filterability and storage stability are also excellent.
The number average molecular weight of polyethyleneimine is preferably 300 to 300,000, more preferably 1,000 to 300,000, more preferably 1,000 to 100,000, and still more preferably 10,000 to 80,000. When the number average molecular weight is 300 or more, the fixability of the colorant on the surface of the printing paper is improved and the effect of improving the printing density is enhanced. When the number average molecular weight is 300,000 or less, the dispersion stability of the aqueous dispersion is excellent. It will be a thing.

The production method of polyethyleneimine is not particularly limited, and can be produced by a known polymerization method. For example, [1] a method of ring-opening polymerization of ethyleneimine using carbon dioxide, hydrochloric acid, hydrobromic acid or the like as a catalyst, [2] a method of polycondensation of ethylene chloride and ethylenediamine, [3] a method of heating oxazolidone-2 Etc.
Polyethyleneimine can be used individually or in combination of 2 or more types.
The content of the cationic polymer, particularly polyethyleneimine, in the aqueous dispersion is preferably 0 with respect to the anionic polymer particles containing the colorant from the viewpoint of the balance between the basic physical properties of the aqueous dispersion and the improvement in printing density. 0.01 to 10% by weight, more preferably 0.05 to 2% by weight, still more preferably 0.1 to 1% by weight.

[Production of water dispersion for inkjet recording]
The aqueous dispersion for ink-jet recording of the present invention comprises an aqueous dispersion (A) containing anionic colored particles and an aqueous solution (B) containing a water-soluble cationic polymer, with a channel cross-sectional area of 0.001 to 0.5 mm. ² and mixing at a linear velocity of 1 m / second or more in the hole at the position where the aqueous dispersion (A) and the aqueous solution (B) join in the flow path having a flow path length of 0.1 to 10 mm. And is mixed so that the amount of the cationic group of the water-soluble cationic polymer is 5 to 50 mol% with respect to the amount of the anionic group of the anionic colored particles. Accordingly, it can be efficiently produced by a method further including a crosslinking step.
In this step, for example, an aqueous dispersion containing anionic colored particles such as an aqueous dispersion containing water-insoluble anionic polymer particles containing a colorant obtained by the method having the steps (1) and (2). The cationic polymer containing the cationic polymer containing (A) and the aqueous dispersion (B) is mixed in the channel under the above conditions without causing local aggregation of the polymer particles. Can be uniformly dispersed in the aqueous dispersion. As a result, an aqueous dispersion containing particles in a form in which anionic colored particles are linked in a chain can be obtained without generating coarse particles. The obtained aqueous dispersion is considered to be excellent in printing density and filterability.

(Mixing by microchannel)
In the production method of the present invention, the flow cross-sectional area is 0.001 to 0.5 mm ² from the viewpoint of suppressing the formation of aggregates by laminar flow formation and uniform mixing, and improving the print density and filterability. It is preferable to use a microchannel (microchannel) having a channel having a path length of 0.1 to 10 mm.
The flow path cross-sectional area of the microchannel employed is preferably 0.005～0.2Mm ^2, more preferably 0.01 to 0.1 mm ^2, flow channel length is preferably 0.2～8Mm, more Preferably it is 0.5-5 mm. Here, the channel length means the length of the channel in the section where the channel cross-sectional area is in the range of 0.001 to 0.5 mm ² .
Moreover, from the said viewpoint, the linear velocity in the hole in the position where the aqueous dispersion (A) containing an anionic colored particle and the aqueous solution (B) containing a water-soluble cationic polymer merge is 1 m / sec or more. Here, the linear velocity in the hole is an average linear velocity in the hole at the position where the aqueous dispersion (A) and the aqueous solution (B) merge, and the volume of the liquid passing through the mixing position in one second is expressed as follows. It is the value divided by the channel cross-sectional area.
The linear velocity in the hole is 1 m / second or more, and preferably 2 m / second or more, more preferably 4 m / second or more, and still more preferably from the viewpoint of achieving both printing density and filterability, particularly from the viewpoint of improving printing density. Is 10 m / sec or more, and is preferably 1000 m / sec or less, more preferably 100 m / sec or less, and still more preferably 30 m / sec or less, from the viewpoint of operability and improvement in print density.
In addition, the amount of the cationic group of the cationic polymer when mixed in the microchannel is 5 to 50 mol% in terms of the ratio of the anionic group of the anionic colored particles from the viewpoint of improving the printing density. , Preferably 8 to 30 mol%, more preferably 10 to 25 mol%, still more preferably 12 to 20 mol%.

The weight ratio of the anionic colored particles to the cationic polymer [anionic colored particles / cationic polymer] is preferably 40 to 5000, more preferably 80 to 2000, and still more preferably, from the viewpoint of increasing the printing density of the aqueous dispersion. 100 to 1000, particularly preferably 200 to 400.
The concentration of the anionic colored particles in the aqueous dispersion (A) containing the anionic colored particles before mixing in the microchannel is preferably 1 to 40% by weight, more preferably 10 to 35% by weight, still more preferably. Is 20 to 35% by weight.
The concentration of the cationic polymer in the aqueous solution (B) containing the cationic polymer before mixing in the microchannel is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, still more preferably. Is 0.1 to 0.5% by weight.

The reason why an aqueous dispersion excellent in printing density and filterability can be obtained by adding a cationic polymer to the aqueous dispersion (A) containing anionic colored particles using a microchannel is not clear. It is not considered as follows.
Within the microchannel, each liquid becomes a laminar flow with a very small contact area and forms a very close state. An aqueous dispersion (A) containing anionic colored particles and an aqueous solution (B) containing a cationic polymer are uniform due to the dissipation that occurs when this laminar flow is released from a flow path having a small cross-sectional area and ejected. It is considered that the cationic polymer is uniformly attached to each anionic colored particle, and the particles are repeatedly collided with each other and the chaining of the particles proceeds.
In this way, unlike other stirrers and dispersers, microchannels do not contact droplets with a large contact area before mixing, and do not generate a partial shear force. It is thought that polymer particles in a form connected in a chain of diameters can be obtained, and an aqueous dispersion excellent in printing density and filterability can be obtained.
Furthermore, if water-insoluble anionic polymer particles containing a colorant are used, there is no elution of the polymer in the mixing step, so that the cationic polymer works effectively with the particles and is sufficiently homogeneous in the microchannel. It is considered that the particles connected in a chain form become strong atypical particles due to entanglement and fusion of the polymers, and can further suppress the penetration into the paper, so that the printing density and filterability are excellent. .

The microchannel used in the present invention is not particularly limited in the material, the shape of the inner surface, the mixing angle, etc., as long as the position where the two liquids are mixed and the shape of the flow path after mixing satisfy the above conditions. Are preferably used.
The material of the microchannel is preferably a material that can handle an aqueous solution or an aqueous dispersion under high-pressure conditions, and examples thereof include metals and glass, and stainless steel is preferable.
Further, the inner surface shape is preferably such that the friction is reduced from the viewpoint of reducing pressure loss.
The mixing angle in the case of using the microchannel is preferably a structure in which the liquid before mixing can flow in at 0 to 90 ° with respect to the flow direction after mixing. a)), a Y-type structure (see FIG. 1B) and a double-pipe structure. When the T-type structure is used, there are three modes shown by (a-1), (a-2), and (a-3) in FIG. Among these, a Y-type structure is more preferable.

As the microchannel, for example, a commercially available micromixer or microreactor, or a connector or adapter that is a thin tube connecting part can be used. Specifically, a chromatograph joint low dead volume type union tee SS-1F0-3GC (T type, cross-sectional area 0.07 mm ² , flow path length 1.25 mm) manufactured by Swagelok, GL Sciences Micro volume connector MT1XCS6 (T type, channel cross-sectional area 0.018 mm ² , channel length 1.25 mm) and MY1XCS6 (Y type, channel cross-sectional area 0.018 mm ² , channel length 1.25 mm), etc. Or a slit type Micro Mixers SSIMM manufactured by IMM, a micromixer YM-2 manufactured by Yamatake Corporation, or the like can be used.
Moreover, it is preferable to use a pump with little pulsation of liquid feeding into the microchannel, and a syringe pump is preferably used. The syringe pump is preferably one that can supply a high pressure of 1 MPa or more. For example, a syringe pump such as Toray Engineering Co., Ltd., Harvard Apparatus, etc. can be used. Moreover, low pulsation type diaphragm pumps and plunger pumps such as Takumina Co., Ltd. and Fuji Techno Industry Co., Ltd. can also be used.

(Crosslinking)
In the present invention, a crosslinking agent is added to the aqueous dispersion (A) containing anionic colored particles, particularly an aqueous dispersion of anionic polymer particles containing a colorant, and the anionic polymer is subjected to a crosslinking treatment. Thus, an aqueous dispersion containing anionic crosslinked polymer particles containing a colorant can be obtained. The crosslinking treatment of the anionic polymer may be performed before or after removing the organic solvent in the step (2), or may be performed after the cationic polymer mixing step, but is performed after the cationic polymer mixing step. Is preferable from the viewpoint of uniformly performing a crosslinking reaction. By subjecting the polymer to a crosslinking treatment, the storage stability of the aqueous dispersion can be improved.
Here, as a crosslinking agent, the compound which has a functional group which reacts with the anionic group of an anionic 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, more preferably, when dissolved in 100 g of water at 25 ° C. from the viewpoint of efficiently crosslinking the surface of the polymer, particularly the water-insoluble anionic polymer. 40 g or less, more preferably 30 g or less. Moreover, the molecular weight 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 trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and ethylene glycol diglycidyl ether are more preferable.

The amount of the crosslinking agent used is preferably 0.3 / 100 to 50/100, and preferably 1/100 to 40/100, in terms of the weight ratio of [crosslinking agent / anionic polymer], from the viewpoint of storage stability of the aqueous dispersion. More preferably, 2/100 to 30/100 is still more preferable, and 5/100 to 25/100 is particularly preferable.
The amount of the crosslinking agent used is preferably an amount that reacts with 0.1 to 20 mmol of anionic groups of the polymer in terms of anionic group amount per 1 g of the anionic polymer, The amount reacting is more preferable, and the amount reacting with 1 to 10 mmol is more preferable.
The crosslinked polymer obtained by the crosslinking treatment preferably contains 0.5 mmol or more of an anionic group (preferably a carboxy group) neutralized with a base per 1 g of the crosslinked polymer. Such a crosslinked polymer is considered to contribute to the stability of the crosslinked polymer particles containing the colorant by dissociating in the aqueous dispersion and charge repulsion between anions.
Here, the crosslinking rate (mol%) of the crosslinked polymer obtained from the following formula (I) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 30 to 60 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 (I)
In the formula (I), “the number of moles of the reactive group of the crosslinking agent” is a value obtained by dividing the weight of the crosslinking agent used by the equivalent of the reactive group. That is, the number of moles of the crosslinking agent used is multiplied by the number of reactive groups in one molecule of the crosslinking agent.

[Water dispersion for inkjet recording]
A moisturizing agent and an organic solvent can be added to the aqueous dispersion obtained by the present invention to prevent drying, and a wetting agent, a penetrating agent, a dispersing agent, and a surfactant that are usually used in water-based inks. Further, a viscosity modifier, an antifoaming agent, an antiseptic, an antifungal agent, an antirust agent, and the like can be added and 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 aqueous dispersion obtained by the production method of the present invention in the aqueous dispersion is preferably from 2 to 35% by weight, more preferably from 3 to 30% by weight, from the viewpoint of increasing the printing density. More preferably, it is 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.
The average particle size of the particles in the aqueous dispersion of the present invention is preferably 10 to 500 nm, more preferably 60 to 400 nm, more preferably 80 to 250 nm, still more preferably 110 to 230 nm, and particularly preferably 160 to 200 nm. .

[Water-based ink for inkjet recording]
The water-based ink for ink-jet recording of the present invention contains the water dispersion obtained by the production method of the present invention. The wetting agent, penetrant, dispersant, surfactant, viscosity used in water-based inks are usually used. An adjuster, an antifoaming agent, an antiseptic, an antifungal agent, an antirust agent and the like can be added.
The content of each component in the aqueous ink of the present invention is as follows.
The content of the organic pigment contained in the anionic organic pigment particles used in the aqueous ink of the present invention is preferably 1 to 25% by weight, more preferably 2% in the aqueous ink from the viewpoint of increasing the printing density of the aqueous ink. -20% by weight, more preferably 4-15% by weight, still more preferably 5-12% 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 average particle size of the particles in the aqueous ink of the present invention is preferably 10 to 500 nm, more preferably 60 to 400 nm, more preferably 80 to 250 nm, still more preferably 110 to 230 nm, and particularly preferably 160 to 200 nm.
The ink jet method to which the water-based ink of the present invention is applied is not limited, but is particularly suitable for a piezo ink jet printer.

  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 aqueous dispersions obtained in Examples and Comparative Examples are evaluated for filterability. Printing was performed by a printing method, and the printing density was evaluated.

(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 anionic colored particles and water dispersion, particles in water-based ink The measurement was performed 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 are a temperature of 25 ° C., an angle between incident light and a detector of 90 °, and an integration count of 100. The refractive index of water (1.333) is input as the refractive index of the dispersion solvent, and the volume average particle diameter is It was measured.

(3) Filterability 25 mL of an aqueous dispersion was weighed with a 25 mL needleless syringe (manufactured by Terumo Corporation), and a 5 μm pore size filter (Sartorius Stedim Biotech, minisalted syringe filter, filter) was attached to the tip of the syringe. (A diameter: 26 mm, material: cellulose acetate) was attached and filtered, and the amount (weight) of liquid passing until one filter was clogged was measured. The greater the flow rate, the better the filterability.
(4) Printing method The ink was filled into the ink injection port above the black head of an inkjet printer (manufactured by Seiko Epson Corporation, model number: EM-930C, piezo method) via a silicon tube. Next, a solid print pattern (size: 181 mm in width x 257 mm in length) is created by Photoshop (manufactured by Adobe Systems Inc.), and test printing is performed by changing the solid duty (print condition = paper type: plain paper, Mode setting: black, fine, bidirectional), and the duty was adjusted so that the actual discharge amount was 0.80 ± 0.01 mg / cm ² . The discharge amount was measured by changing the weight of the screw tube containing the ink. Printing was performed on commercially available plain paper (trade name: XEROX 4200, manufactured by XEROX, high-quality plain paper) using the adjusted solid image of Duty.
(5) Measurement of printing density After leaving the printed matter at 25 ° C. and 50% relative humidity for 24 hours, the printing density on the printing surface was measured. For the measurement of the print density, a spectrophotometer (manufactured by Kimoto Co., Ltd., product number: Spectro Eye) was used. The measurement conditions were an observation light source of D65, an observation field of view of 2 degrees, a density reference of DIN 16536, and a magenta color density. The numerical value of the component was read. The number of times of measurement was changed, and 5 points were selected at random from the portion printed in the forward path of bidirectional printing, and 5 points were selected from the portion printed on the return path, and an average value of a total of 10 points was obtained. The higher the numerical value, the better the print density.

Preparation Example 1 (Preparation of aqueous dispersion (A-1) of pigment-containing anionic polymer particles)
(1) Synthesis of anionic polymer 142 parts of benzyl acrylate, 38 parts of methacrylic acid, 40 parts of styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6S) (solid content 50%) are mixed, and the monomer mixture is prepared. Prepared. 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 were mixed and sufficiently substituted with nitrogen gas.
Meanwhile, in the dropping funnel, the remaining 90% of the monomer mixture, 0.27 part of the polymerization chain transfer agent, 42 parts of methyl ethyl ketone, and a polymerization initiator (trade name: V-65, 2, manufactured by Wako Pure Chemical Industries, Ltd.) A mixture of 1.2 parts of 2′-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was heated to 75 ° C. while stirring the mixed solution in a reaction vessel in a nitrogen atmosphere. The mixed solution was added dropwise over 3 hours. After 2 hours at 75 ° C. from the end of dropping, a 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 at 80 ° C. for 2 hours. Weight average molecular weight: 90000).
(2) Preparation of aqueous dispersion (A-1) of pigment-containing anionic polymer particles 45 parts of the polymer solution obtained by drying the polymer solution obtained in the above (1) under reduced pressure was dissolved in 300 parts of methyl ethyl ketone, 10 parts of neutralizing agent 5N aqueous sodium hydroxide solution, 12.2 parts of 25% aqueous ammonia and 1150 parts of ion-exchanged water, and a magenta pigment (solid solution pigment composed of unsubstituted quinacridone and 2,9-dichloroquinacridone) After adding 180 parts of Ciba Japan Co., Ltd., trade name: Chromophthaljet Magenta 2BC) and mixing with Disper blade 7000 rpm at 20 ° C. for 1 hour, a bead mill type disperser (manufactured by Kotobuki Kogyo Co., Ltd., Ultra Apex) Mill, model UAM-05, media particles: zirconia beads, particle size: 0.05 mm) at 20 ° C. 0 minutes mixed and dispersed. The obtained dispersion was further subjected to a 5-pass dispersion treatment at a pressure of 180 MPa using a microfluidizer (manufactured by Microfluidics, high-pressure homogenizer, trade name, model M-140K).
Methyl ethyl ketone was removed from the obtained dispersion at 60 ° C. under reduced pressure, a part of water was further removed, the mixture was centrifuged, and the liquid layer was filtered through a filter having a pore size of 5 μm (manufactured by Sartorius Stedim Biotech). An aqueous dispersion (A-1) of anionic polymer particles containing a pigment (solid content concentration: 28.5%, average particle size 77 nm) was obtained.

Example 1 (Production of water dispersion for ink jet recording)
Two syringe pumps PHD-4400 manufactured by Harvard Aparatus, microchannels shown in FIG. 2 (T type, manufactured by Swagelok, low dead volume type union tee SS-1F0-3GC, inner diameter 0. 3 mm, channel cross-sectional area 0.071 mm ² , channel length 1.25 mm, made of stainless steel) were connected using a polyethylene tube. The liquid sent from the two syringe pumps is connected so that the liquid is sent at a minimum angle of 180 degrees in the microchannel and contacted, and the mixed liquid has the minimum angle based on the flow path through which the liquid before mixing passes. The connection was made so that the liquid was fed from the microchannel to the graduated cylinder at 90 degrees. FIG. 1A-1 shows a connection state of this embodiment.
Next, 50.0 g of the aqueous dispersion (A-1) of the pigment-containing anionic polymer particles obtained in Preparation Example 1 was placed in a stainless syringe DCI70-2255 manufactured by Harvard Aparatus, and a syringe pump PHD-4400 manufactured by Harvard Aparatus. Attached to. On the other hand, 50 g of a 0.105 wt% aqueous solution (B-1) of polyethyleneimine (number average molecular weight 70,000, manufactured by Wako Pure Chemical Industries, Ltd.) was similarly attached to another syringe pump PHD-4400.
And the syringe pump was started simultaneously and in FIG. 2, the aqueous dispersion (A-1) was injected from the left side, and the aqueous solution (B-1) was injected from the right side at a rate of 10 mL / min. The in-hole linear velocity in the microchannel was 4.7 m / sec.
Here, the in-hole linear velocity is calculated by using the elapsed time at the time when it reaches 50 mL, starting to receive the liquid in the graduated cylinder after the outflow of the mixed liquid is stabilized, and that time is the start time. In the case of this example, it was 50 mL / 150 seconds / 0.071 mm ² = 4.7 m / second.
To 80 g of the obtained dispersion, 0.4 g of an epoxy-based cross-linking agent (trade name: Denacol EX321, epoxy equivalent 140, manufactured by Nagase ChemteX Corporation) is added and kept in a 90 ° C. warm bath for 1.5 hours with stirring. did. After cooling, it was concentrated until the solid content concentration of the pigment was 16% to obtain an aqueous dispersion. When the filterability evaluation of the obtained water dispersion was performed, the liquid flow rate was 10 g. After the filterability evaluation, all the aqueous dispersions were filtered to obtain an aqueous dispersion for inkjet recording having an average particle diameter of 145 nm.

Example 2 (Production of water dispersion for inkjet recording)
In Example 1, the same operation as in Example 1 was carried out except that the injection speed was changed to 60 mL / min (in-hole linear speed 28.3 m / sec) to obtain an aqueous dispersion for inkjet recording having an average particle size of 224 nm. . The flow rate in the filterability evaluation was 20 g.
Example 3 (Production of water dispersion for inkjet recording)
In Example 1, the injection rate of the aqueous dispersion (A-1) of the pigment-containing anionic polymer particles obtained in Preparation Example 1 was 60 mL / min, and the injection rate of the aqueous polyethyleneimine solution (B-1) was 40 mL / min. The aqueous dispersion for inkjet recording having an average particle diameter of 151 nm was obtained in the same manner as in Example 1 except that the linear velocity in the hole was changed to 23.6 m / sec. In the filterability evaluation, the flow rate was 25 g or more (25 g total flow rate).

Example 4 (Production of water dispersion for inkjet recording)
Using the aqueous dispersion (A-1) of pigment-containing anionic polymer particles obtained in Preparation Example 1 diluted to 15.0% by weight with ion-exchanged water, the concentration of the polyethyleneimine aqueous solution (B-1) A water dispersion for inkjet recording having an average particle size of 130 nm was obtained in the same manner as in Example 1 except that the amount was changed to 0.055% by weight. In the filterability evaluation, the flow rate was 25 g or more (25 g total flow rate).
Example 5 (Production of water dispersion for inkjet recording)
In Example 2, the same operation as in Example 2 was performed except that polyethyleneimine was changed to one having a number average molecular weight (Mn) of 10,000 (manufactured by Wako Pure Chemical Industries, Ltd.), and inkjet recording having an average particle diameter of 192 nm An aqueous dispersion was obtained. In the filterability evaluation, the flow rate was 25 g or more (25 g total flow rate).

Example 6 (Production of water dispersion for inkjet recording)
The polyethyleneimine used in Example 1 was changed to that having a number average molecular weight (Mn) of 1,800 (manufactured by Wako Pure Chemical Industries, Ltd.), and the same as Example 1 except that the concentration was changed to 0.070%. Operation was performed to obtain an aqueous dispersion for inkjet recording having an average particle size of 95 nm. In the filterability evaluation, the flow rate was 25 g or more (25 g total flow rate).
Example 7 (Production of water dispersion for inkjet recording)
The microchannel used in Example 1 was changed to a micro volume connector MY1XCS6 (Y type, channel cross-sectional area 0.018 mm ² , channel length 1.25 mm) manufactured by GL Sciences (in-hole linear velocity 18.9 m / sec) Except for the above, the same operation as in Example 1 was performed to obtain an aqueous dispersion for inkjet recording having an average particle diameter of 175 nm. In the filterability evaluation, the flow rate was 25 g or more (25 g total flow rate).

Example 8 (Production of water dispersion for inkjet recording)
The concentration of the polyethyleneimine aqueous solution (B-1) in Example 1 was 0.210% by weight, and the injection rate was changed to 40 mL / min (in-hole linear velocity 18.9 m / s), respectively, as in Example 1. Operation was performed to obtain an aqueous dispersion for inkjet recording having an average particle size of 440 nm. The flow rate in the filterability evaluation was 5 g.
Example 9 (Production of water dispersion for inkjet recording)
The microchannel used in Example 1 was changed to a micromixer YM-2 manufactured by Yamatake Corporation (channel cross-sectional area 0.126 mm ² , channel length approximately 8 mm, made of stainless steel), and the injection rate was 80 mL / min each. Except for the change (in-hole linear velocity 21.2 m / sec), the same operation as in Example 1 was performed to obtain an aqueous dispersion for inkjet recording having an average particle diameter of 390 nm. The flow rate in the filterability evaluation was 5 g.

Comparative Example 1 (Production of water dispersion for inkjet recording)
The aqueous dispersion (A-1) of the pigment-containing anionic polymer particles obtained in Preparation Example 1 is diluted with ion-exchanged water and mixed using a magnetic stirrer to obtain an aqueous dispersion for inkjet recording having an average particle size of 77 nm. It was. In the filterability evaluation, the flow rate was 25 g or more (25 g total flow rate).
Comparative Example 2 (Production of water dispersion for inkjet recording)
50.0 g of the aqueous dispersion (A-1) of pigment-containing anionic polymer particles obtained in Preparation Example 1 and 50.0 g of a 0.105% by weight aqueous solution of polyethyleneimine were placed in a beaker (the cationic group of polyethyleneimine). ) Was mixed using a magnetic stirrer, but a large amount of coarse aggregates could not be filtered.
Comparative Example 3 (Production of water dispersion for inkjet recording)
The same operation as in Example 1 was performed except that the injection rate in Example 1 was changed to 2 mL / min (in-hole linear velocity: 0.9 m / sec), but many coarse aggregates could not be filtered.
Comparative Example 4 (Production of water dispersion for inkjet recording)
The same operation as in Example 2 was performed except that the polyethyleneimine aqueous solution (B-1) in Example 2 was changed to ion-exchanged water to obtain an aqueous dispersion for inkjet recording having an average particle size of 77 nm. In the filterability evaluation, the flow rate was 25 g or more (25 g total flow rate).
Comparative Example 5 (Production of water dispersion for inkjet recording)
The microchannel of Example 1 was changed to a microchemical chip ICC-SY-10 (channel cross-sectional area 0.004 mm ² , channel length 80 mm) manufactured by Micro Chemical Engineering Co., Ltd., and the injection rate was 0.3 mL / min each. The same operation as in Example 1 was performed except that the flow rate was changed to (in-hole linear velocity 2.0 m / sec), but aggregates were generated in the flow path and the flow path was blocked, so that an aqueous dispersion could be obtained. could not.
Comparative Example 6 (Production of water dispersion for inkjet recording)
The concentration of the polyethyleneimine aqueous solution (B-1) in Example 1 was 0.420% by weight, and the injection rate was changed to 40 mL / min (in-hole linear velocity 18.9 m / sec), respectively, as in Example 1. Operation was performed to obtain an aqueous dispersion for inkjet recording. The particles in the obtained aqueous dispersion immediately settled, and the filterability could not be evaluated.

Example 10 [Production of water-based ink]
1,2-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.0 parts, 2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) 2.0 parts, Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 Part, Olphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 part, 2.0 parts of glycerin (manufactured by Kao Corporation), triethylene glycol monobutyl ether (trade name: butyl triglycol, manufactured by Nippon Emulsifier Co., Ltd.) 10 0.0 part, 0.3 part of Proxel XL2 (manufactured by Avicia Co., Ltd.) and ion-exchanged water were mixed while stirring with a magnetic stirrer, and further stirred at room temperature for 15 minutes 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 water dispersion for inkjet recording obtained in Example 1 is 100 parts.
Next, 62.5 parts of the aqueous dispersion for inkjet recording obtained in Example 1 (10.0 parts in terms of pigment content (in water-based ink)) was stirred with a magnetic stirrer, and the mixed solution was added. Filtration through a filter having a pore diameter of 5 μm gave a water-based ink. The results are shown in Table 1.

Examples 11 to 18 and Comparative Examples 7 to 8 [Production of water-based ink]
A water-based ink was obtained in the same manner as in Example 10 except that the aqueous dispersions for inkjet recording obtained in Examples 2 to 9 and Comparative Examples 1 to 4 were combined as shown in Table 1. The results are shown in Table 1.

  From Table 1, the aqueous dispersions and aqueous inks of the examples are superior in both filterability and print density as compared with the aqueous dispersions and aqueous inks of the comparative examples, and are compatible with these performances. I understand that.

Claims (10)

An aqueous dispersion (A) containing anionic colored particles and an aqueous solution (B) containing a water-soluble cationic polymer have a channel cross-sectional area of 0.001 to 0.5 mm ² and a channel length of 0.1 to 0.1. A method for producing an aqueous dispersion having a step of mixing in a flow path of 10 mm, wherein a linear velocity in a hole at a position where the aqueous dispersion (A) and the aqueous solution (B) merge is 1 m / second or more. The method for producing an aqueous dispersion for inkjet recording, wherein the amount of the cationic group of the water-soluble cationic polymer is 5 to 50 mol% with respect to the amount of the anionic group of the anionic colored particles.   The method for producing an aqueous dispersion for inkjet recording according to claim 1, wherein the anionic colored particles are anionic polymer particles containing a colorant.   The method for producing an aqueous dispersion for inkjet recording according to claim 2, wherein the anionic polymer is a water-insoluble polymer.   The method for producing an aqueous dispersion for inkjet recording according to claim 2 or 3, wherein the colorant is an organic pigment.   The method for producing an aqueous dispersion for inkjet recording according to any one of claims 1 to 4, wherein the water-soluble cationic polymer has a number average molecular weight of 10,000 to 80,000.   The method for producing an aqueous dispersion for inkjet recording according to any one of claims 1 to 5, wherein the water-soluble cationic polymer is polyethyleneimine.   The manufacturing method of the water dispersion for inkjet recording in any one of Claims 1-6 whose flow path length is 0.5-5 mm. In the manufacturing method in any one of Claims 1-7 whose average particle diameter of the particle | grains in the water dispersion obtained by mixing water dispersion (A) and aqueous solution (B) is 110-230 nm. An aqueous dispersion for ink jet recording obtained.   A water-based ink for inkjet recording, comprising the water dispersion according to claim 8.   A water-based ink for ink-jet recording, comprising the water dispersion for ink-jet recording obtained by the production method according to claim 1.

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