JP2011162687A - Ink for inkjet recording, ink cartridge, inkjet printing apparatus, image-forming method and formed image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersion giving high image density and having excellent ejection stability and liquid stability and to provide an ink for inkjet recording produced by using the pigment dispersion. <P>SOLUTION: The ink for inkjet recording at least includes a pigment, a dispersing agent, water, a water-soluble organic solvent and a humectant, wherein the dispersing agent is a compound having a structural formula (1). In the formula, p is an integer of 1-3; q is an integer of 1-3; m is an integer of 2-4; and M1 and M2 are each H, an alkali metal, alkaline earth metal, ammonium or organic amine. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ink jet recording ink which has a high image density, is excellent in image sharpness, and is also excellent in ink storage stability. The present invention relates to an ink jet recording ink that is excellent in the storage stability of a dispersion, and further has excellent ink liquid ejection stability and ink liquid storage stability.

The inkjet recording method is easy to make full color because the process is simpler than other recording methods, and there is an advantage that a high-resolution image can be obtained even with an apparatus having a simple configuration.
As ink-jet recording inks, dye-based inks in which various water-soluble dyes are dissolved in water or a mixture of water and an organic solvent are used, but dye-based inks have excellent color tone clarity. There was a disadvantage of poor light resistance. On the other hand, pigment-based inks in which carbon black and various organic pigments are dispersed are actively studied because they are superior in light resistance compared to dye-based inks. However, pigment-based inks tend to clog nozzles more easily than dye-based inks.

A pigment-based ink is generally prepared by preparing a dispersion in which a coloring material and a dispersant are pre-dispersed in an aqueous solvent such as water or alcohol, and then using a media-type disperser such as a sand mill. It is prepared by carrying out a dispersion step of dispersing to a predetermined concentration and then diluting to a predetermined concentration.
In the pigment-based water-based ink, a surfactant or a water-soluble resin is generally used to disperse the hydrophobic pigment, but the reliability of the obtained image is extremely poor. Therefore, a technology is known to add film-forming resin fine particles to the ink liquid for the purpose of improving image quality. However, it is difficult to disperse a plurality of components finely and stably over a long period of time, and these fine particles are stably dispersed. If a large amount of a dispersing agent such as a surfactant is used for this purpose, problems such as generation of bubbles in the ink tank and the head and deterioration of the image quality may occur. In addition, for the purpose of improving the dispersibility, methods of changing the pigment surface to hydrophilic groups and using resins containing hydrophilic groups are being studied. There is a problem that dispersion becomes unstable and storage stability deteriorates.

  For the purpose of obtaining a high image density, a method of incorporating a water-insoluble colorant and a chargeable resin pseudo fine particle smaller than the colorant in the ink (see, for example, Patent Document 1), self-dispersion with a limited DBP oil absorption amount of the pigment Type carbon containing method (see, for example, Patent Document 2), a water-based carbon containing a non-ionic surfactant having a carbon dispersion of surface-modified carbon black and an HLB value of 7 to 18 and having an acetylene skeleton A method using a black dispersion (see, for example, Patent Document 3) has been proposed. A water-based ink using an acetylene glycol surfactant (for example, see Patent Document 4) has also been proposed.

  Further, for the purpose of stabilizing the dispersion, a method of dispersing a water-dispersible resin having a carboxyl group and a nonionic hydrophilic group in the molecule in water (for example, see Patent Document 5), the same water-soluble polymer and surfactant. A method of making the polarity or adding nonions (for example, see Patent Document 6), a method of making the hydrophilic group of the colored ionicity-containing polyester resin and the colorant the same in the aqueous recording liquid (for example, see Patent Document 7), A method of making the dispersion polarity of the pigment and the resin fine particles the same (for example, see Patent Document 8) has been reported. In addition, a printing ink using a Gemini surfactant as a dispersant (for example, see Patent Document 9) has also been proposed.

  Also, pigment particles having a particle size distribution in which at least 70% of the particles in the dispersion have a diameter of less than 0.1 μm and the other particles in the dispersion have a diameter equal to or less than 0.1 μm. A water-based inkjet ink composition (for example, see Patent Document 10), a pigment, a polymer dispersant, and a nonionic surfactant containing a pigment dispersion containing aldehyde, an aldehyde naphthalene sulfonate dispersant, and / or at least one sulfone solvent A recording liquid (for example, see Patent Document 11), an AB or BAB block copolymer used as a pigment dispersant (for example, see Patent Documents 12 and 13), a specific pigment, a water-soluble The use of a resin or a solvent (see, for example, Patent Document 14) has been proposed.

  On the other hand, as a pigment dispersion method without using a dispersant, a method of introducing a substituent containing a water-solubilizing group into carbon black (for example, see Patent Document 15), a method of polymerizing a water-soluble monomer or the like on the surface of carbon black (for example, Patent Document 16), a method of oxidizing carbon black (for example, see Patent Document 17), and the like have been proposed. Also proposed is a method for ensuring water resistance and ejection stability with an ink containing an oxidized carbon black and a terpolymer composed of acrylic acid, styrene, and α-methylstyrene (see, for example, Patent Document 18). Yes.

  In addition, an ink jet recording liquid (see, for example, Patent Document 19) in which the volume average particle diameter of dispersed particles in the ink jet recording liquid is 30 to 200 nm has been proposed.

  However, although the above-described conventional ink liquid can obtain a high image density with respect to the color pigment ink, the black pigment ink is not yet satisfactory and is not satisfactory. In addition, examples have been proposed in which beads having a diameter of about 0.05 mm to 1.0 mm are used for bead mill dispersion (see, for example, Patent Documents 20, 21, and 22). Is not enough.

In addition, it is also known that an anionic surfactant is used as the dispersant, and the molecular weight is preferably in the range of 1000 ≦ m ≦ 30000 (see, for example, Patent Document 23), but is sufficient in terms of dispersion stability. However, pigment types that are weak against strong impacts during dispersion lack stability after dispersion, and have been problems such as ejection stability with ink liquid.
In addition, it is also known to use a diisobutylene-maleic acid copolymer as a dispersant (see, for example, Patent Documents 24 and 25). However, both of the dispersion stability and the high density image are not sufficient.

  The present inventors previously proposed a pigment dispersion comprising carbon black, sodium naphthalene sulfonate formalin condensate (dispersant), and water (see Patent Document 26). The ink jet recording ink obtained from this pigment dispersion has a high image density and is excellent in ejection stability and liquid stability.

  In addition to these, ink-jet inks using a colorant composed of a compound having a specific structure are also known (see, for example, Patent Documents 27 and 28).

  The object of the present invention has been made in view of the circumstances as described above. The invention described in Patent Document 26 has been developed, and a pigment dispersion having higher image density and excellent ejection stability and liquid stability. And a technique related to an ink jet recording ink using the pigment dispersion.

  As a result of intensive studies, the present inventors have used a compound having the following structural formula (1) as the dispersant in a recording ink containing at least a pigment, a dispersant, water, a water-soluble organic solvent, and a humectant. It has been found that the above-mentioned problems can be solved when it is done. The present invention has been made based on these findings.

(In the formula, p represents an integer of 1 to 3, q represents an integer of 1 to 3, and m represents an integer of 2 to 4. M1 and M2 represent H or an alkali metal, an alkaline earth metal, ammonium, or an organic amine. .)

Therefore, according to the present invention, the following (1) to (12) are provided.
(1) An ink jet recording ink comprising at least a pigment, a dispersant, water, a water-soluble organic solvent, and a humectant, wherein the dispersant is a compound having the structural formula (1).

(In the formula, p represents an integer of 1 to 3, q represents an integer of 1 to 3, and m represents an integer of 2 to 4. M1 and M2 represent H or an alkali metal, an alkaline earth metal, ammonium, or an organic amine. .)
(2) The inkjet recording ink as described in (1) above, wherein the compound having the general formula (1) is a salt of a formalin condensate of sulfonaphthalenecarboxylic acid.
(3) The ink jet recording ink according to (1) or (2), wherein the ratio of the pigment to the dispersant is 0.01 to 2 of the dispersant with respect to the pigment 1 on a weight basis. .
(4) The inkjet recording ink according to any one of (1) to (3), wherein the pigment is carbon black.
(5) The inkjet recording ink as described in (4) above, wherein the carbon black has an average primary particle diameter of 10 to 30 nm and a BET specific surface area of 100 to 400 m ² / g.
(6) The average particle size (D50) of the carbon black is 70 to 180 nm, and the particle size standard deviation in the particle size distribution of the carbon black is 1/2 or less of the average particle size. (4) or recording ink for ink jet recording according to (5).
(7) An ink cartridge characterized in that the inkjet recording ink according to any one of (1) to (6) is contained in a container.
(8) An ink jet printing apparatus that performs recording by discharging the ink jet recording ink according to any one of (1) to (6) above onto an image support.
(9) The inkjet printing apparatus according to (8), wherein the inkjet printing apparatus is a piezo method or a thermal method.
(10) An image forming method wherein printing is performed with an inkjet printing apparatus using the inkjet recording ink according to any one of (1) to (6).
(11) An image formed product in which the inkjet recording ink according to any one of (1) to (6) is printed on an image support by an inkjet printing apparatus.
(12) The image formed article as described in (11) above, wherein the image support is paper.

  By using the compound having the structural formula (1) as a dispersant, it is possible to provide an ink jet recording ink having good image density, ejection stability and storage stability. The reason why the image density is good is unknown, but the reason why the ejection stability and storage stability are good is that the compound (dispersant) having the structural formula (1) is a general surfactant (single-chain one-hydrophilic group). This is considered to be because of its structural stability compared to the type surfactant).

Hereinafter, the present invention will be described in more detail.
The ink jet recording ink of the present invention contains at least a pigment, a dispersant, and water. Usually, a pigment dispersion containing a pigment, a dispersant, and water is first prepared, and an ink jet recording ink is prepared using this. create.

  The dispersant used in the inkjet recording ink of the present invention is a compound having the following structural formula (1).

(In the formula, p represents an integer of 1 to 3, q represents an integer of 1 to 3, and m represents an integer of 2 to 4. M1 and M2 represent H (hydrogen atom), an alkali metal, an alkaline earth metal, ammonium, or Represents an organic amine.)
However, when M1 and M2 are H, after polymerization or copolymerization with other monomers, it is necessary to neutralize with a base to form carboxylic acid and sulfonic acid as a salt.

Examples of salts of carboxylic acid and sulfonic acid in the structural formula (1) include alkali metal salts such as lithium, sodium and potassium, alkaline earth metal salts such as calcium and magnesium, ammonium, mono, di or trimethylamine, mono, Aliphatic amine in which hydrogen atom of ammonia such as di- or triethylamine is substituted with alkyl group, monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, choline, aminoethanepropanediol, monopropanol Hydrogen atoms of ammonia such as amine, dipropanolamine, tripropanolamine, isopropanolamine, trishydroxymethylaminomethane, aminoethylpropanediol Alcohol amines substituted with alkyl groups, morpholine, N- methylmorpholine, N- methyl-2-pyrrolidone, and organic amine salts such as cyclic amines 2-pyrrolidone and the like.
Among them, alkali metal salts such as lithium, sodium and potassium, and diethanolamine and triethanolamine salts are excellent in dispersion stability.

  The compound having the structural formula (1) is preferably a formalin condensate of sulfonaphthalenecarboxylic acid or a salt thereof.

  The condensate or a salt thereof is not particularly limited as long as it is a condensate of sulfonaphthalene sulfonic acid or a salt thereof and formaldehyde. However, the total content of the dimer, trimer and tetramer of sulfonaphthalenesulfonic acid or a salt thereof in the condensate is preferably 20 to 80% by weight. When the total content is less than 20% by weight, the dispersibility is deteriorated, the storage stability of the carbon black dispersion and the ink is inferior, and as a result, nozzle clogging is likely to occur. On the other hand, when the total content exceeds 80% by weight, the viscosity increases and dispersion becomes difficult.

Although the compound which has Structural formula (1) of this invention is obtained by formalin condensation of the following monomers, it is not this limitation.
That is, if the compound is a sodium salt, for example, 2,6-naphthalenedicarboxylic acid is sulfonated, formalin condensed, neutralized with sulfuric acid, desalted, and the dispersant 4-sulfo-1,8- A sodium salt of naphthalenedicarboxylic acid formalin condensate is obtained.

  Examples of the carboxylic acid monomer used in the present invention include 2-naphthoic acid, 1-naphthalenecarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and 2,3-naphthalenedicarboxylic acid. , 6-formyl-2-naphthoic acid, 1-naphthylacetic acid, 1-methoxy-4- (β-carboxyethylcarbonyl) -naphthalene and the like.

  Examples of the naphthalene sulfonic acid monomer used in the present invention include naphthalene sulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, alkyl (C1-14) naphthalene sulfonic acid, dialkyl (C1 to C14) naphthalene sulfonic acid and the like. It is done.

The mixing ratio of the dispersant in the pigment dispersion is preferably 0.01 to 2 (weight ratio) with respect to the pigment 1. More preferably, it is 0.25 to 1 with respect to pigment 1. If the blending ratio is less than 0.01, the dispersion effect is difficult to achieve, and the storage stability of the aqueous pigment dispersion and the ink is poor. As a result, nozzle clogging tends to occur, and the blending ratio is 2 If it is larger, the viscosity of the aqueous pigment dispersion and the ink tends to be too high, and printing by the ink jet method tends to be difficult.
By adopting such a use amount of the dispersant, the average particle size (D50) of the pigment in the dispersion of the present invention is 70 nm or more and 180 nm or less, and the particle size standard deviation in the particle size distribution of the pigment is the average particle size. The pigment dispersion can be provided with a high image density, ejection stability, and liquid stability.

  As the pigment used in the pigment dispersion of the present invention, any of black pigments and colored pigments can be applied.

  For example, as the yellow pigment, Pigment Yellow 1, Pigment Yellow 2, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75 Pigment Yellow 83, Pigment Yellow 93, Pigment Yellow 95, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 114, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 129, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 155, Pigment Yellow 180 And the like.

  Examples of magenta pigments include Pigment Red 5, Pigment Red 7, Pigment Red 12, Pigment Red 48 (Ca), Pigment Red 48 (Mn), Pigment Red 57 (Ca), Pigment Red 57: 1, Pigment Red 112, and Pigment Red. 122, Pigment Red 123, Pigment Red 168, Pigment Red 184, Pigment Red 202, Pigment Violet 19, and the like.

  Examples of cyan pigments include Pigment Blue 1, Pigment Blue 2, Pigment Blue 3, Pigment Blue 15, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 16, Pigment Blue 22, Pigment Blue 60, and Bat Blue 4. , Bat Blue 60 and the like.

In particular, as the pigment, a black pigment such as carbon black produced by a furnace method or a channel method is preferably used as a black pigment.
Specific examples of carbon black include # 10B, # 20B, # 30, # 33, # 40, # 44, # 45, # 45L, # 50, # 55, # 95, # 260, ## manufactured by Mitsubishi Chemical Corporation. 900, # 1000, # 2200B, # 2300, # 2350, # 2400B, # 2650, # 2700, # 4000B, CF9, MA8, MA11, MA77, MA100, MA220, MA230, MA600, MCF88, etc .; Monarch made by Cabot 120, Monarch 700, Monarch 800, Monarch 880, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Mogal L, Legal 99R, Legal 250R, Legal 300R, Legal 330R, Legal 400R, Legal 500R and Legal 660R, etc .; Made of plastic Printex A, Printex G, Printex U, Printex V, Printex 55, Printex 140U, Printex 140V, Special Black 4, Special Black 4A, Special Black 5, Special Black 6, Special Black 100, Special Black 250 Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, and the like.

  The pigment concentration is preferably 5 to 50% by weight based on the total amount of the pigment dispersion. If it is less than 5% by weight, the productivity is inferior, and if it is more than 50% by weight, the viscosity of the pigment dispersion tends to be too high and dispersion tends to be difficult.

Here, the preparation of the carbon black dispersion will be described as follows.
That is, the carbon black dispersion of the present invention contains the above-described carbon black, a dispersant, water, and various additives as necessary, such as a bead mill, for example, Dino mill KDL type (manufactured by Shinmaru Enterprises), agitator mill LMZ (Ashizawa Disperse with a disperser such as Finetech Co., Ltd., SC Mill (Mitsui Mining Co., Ltd.), and bead mill after dispersion of beads mill, for example, high shear rate type CLEARSS5 (manufactured by M Technique Co.), Cavitron CD1010 (Euro Tech), module DR2000 (Shinmaru Enterprises), thin-film swivel type TK Philmix (made by Tokushu Kika Kogyo Co., Ltd.), ultrahigh pressure collision type artemizer (Sugino Machine), Nanomizer (Made by Yoshida Kikai Kogyo Co., Ltd.), etc.
Also, by pre-processing coarse particles with a homogenizer or the like in the pre-process of the disperser, the particle size distribution can be made sharper, leading to improvements in image density, ejection stability, and the like.
The pigment dispersion of the present invention thus obtained can be suitably used particularly as a pigment-based inkjet ink.

The beads used in the present invention are usually ceramic beads, and generally zirconia balls are used. The bead diameter is preferably 0.05 mmφ or less, more preferably 0.03 mmφ or less.
The average primary particle size of the carbon black in 10.0nm~30.0nm, BET surface area is 100m ² / g~400m ² / g. The average primary particle diameter of preferably carbon black in 15.0nm~20.0nm, BET surface area is 150m ² / g~300m ² / g.
Since this carbon black has a small average primary particle size and a high structure, if the beads are weak against impact during dispersion and the bead diameter exceeds 0.05 mm, the collision energy between the beads will be strong and the structure will be destroyed. As a result, the stability of the resulting carbon black dispersion is impaired. Therefore, the bead diameter is preferably 0.05 mm or less.

The pigment-based inkjet recording ink of the present invention is coarsely mixed by a known method, for example, the above pigment dispersion is mixed with various additives (water-soluble organic solvent, humectant, etc.) and stirred and mixed with a filter, a centrifugal separator, or the like. Prepared by filtering the particles and degassing if necessary.
The concentration of the pigment (carbon black) in the ink is preferably 1% by weight or more and 20% by weight or less based on the total amount of the ink. If it is less than 1% by weight, the image density is low, so that the printing is not clear. If it is more than 20% by weight, not only the viscosity of the ink tends to be high but also nozzle clogging tends to occur.

  The water-soluble organic solvent referred to in the present invention has a boiling point of 180 ° C. or higher. When the water-soluble organic solvent is restarted after interruption, nozzle clogging does not occur, and high discharge stability is obtained. Although the following are illustrated as a water-soluble organic solvent used in this invention, It is not limited to these.

For example, ethylene glycol, diethylene glycol, 1,3-butyl glycol, 3-methyl-1,3-butyl glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol , Polyglycerols such as glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol Polyhydric alcohol alkyl ethers such as dimethyl ether ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl- 2-pyrrolidone, 1,3-dimethylimidazolidinone, nitrogen-containing heterocyclic compounds such as ε-caprolactam, γ-butyrolactone, amides such as formamide, N-methylformamide, N, N-dimethylformamide, monoethanolamine, Examples include amines such as diethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane, and thiodiethanol, propylene carbonate, and ethylene carbonate.
Among these, the inclusion of 1,3-butyl glycol, diethylene glycol, triethylene glycol and / or glycerin prevents clogging due to drying of the ink, that is, prevention of poor jetting characteristics due to moisture evaporation, and saturation of the formed image of the present invention. An excellent effect is obtained in the improvement.

  The content of the water-soluble organic solvent is 1% by weight or more and 50% by weight or less, preferably 5% by weight to 40% by weight, and more preferably 10% by weight to 35% by weight with respect to the total amount of the ink.

  The wetting agent is added for the purpose of preventing clogging of the nozzles of the recording head due to drying. Specific examples of the wetting agent include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, polyhydric alcohols such as petriol and glycerin, or 2-pyrrolidone and N-methyl-2-pyrrolidone And water-soluble nitrogen heterocyclic compounds such as 1,3-dimethylimidazolidinone.

  The content of the humectant is 5% by weight or more and 50% by weight or less, preferably 10% by weight to 40% by weight, and more preferably 15% by weight to 35% by weight with respect to the total amount of the ink.

In addition, the pigment-based inkjet recording ink of the present invention preferably contains 2-ethyl-1,3-hexanediol (EHD), thereby increasing the permeability of the ink and at the same time bleeding by keeping the pigment on the surface. Thus, it is possible to obtain a printed image having a high image density and little show-through.
The content of EHD is preferably 0.1% by weight or more and 10.0% by weight or less, more preferably 0.5% by weight or more and 5.0% by weight or less of the total amount of ink. If the amount is less than 0.1% by weight, the effect is small, and if it exceeds 10.0% by weight, the solubility is low, and the reliability is deteriorated.

  The recording ink of the present invention includes, in addition to the above components, various nonionic, anionic, cationic or amphoteric surfactants and preservatives as necessary.

  Specific examples of surfactants include anionic surfactants such as higher fatty acid salts, alkyl sulfates, alkyl ether sulfates, alkyl ester sulfates, alkyl aryl ether sulfates, alkyl sulfonates, sulfosuccinates, alkyls. Examples include allyl and alkyl naphthalene sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphate esters, and alkyl allyl ether phosphates. Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, tetraalkylammonium salts, benzalkonium salts, alkylpyridinium salts, imidazolinium salts, and the like. Examples of amphoteric surfactants include dimethylalkyl lauryl betaine, alkyl glycine, alkyl di (aminoethyl) glycine, and imidazolinium betaine. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan ester Polyoxyethylene ether, polyoxyethylene ether of sorbitol ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, amine oxide, polyoxyethylene alkylamine and the like.

  Specific examples of preservatives include dehydroacetate, sorbate, benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, 2,4-dimethyl-6-acetoxy-m-dioxane, Examples thereof include compounds such as 1,2-benzthiazolin-3-one.

The pigment-based inkjet ink of the present invention thus obtained can be suitably used for an ink cartridge that accommodates it. The pigment-based ink-jet ink of the present invention can be image-formed by an ink-jet printing apparatus that forms an image by discharging (recording) the image on an image support such as paper.
Examples of the printing method include a continuous jet type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not limited to these examples. In addition, the part in an example is a basis of weight.
Moreover, about evaluation using the ink liquid (pigment-type inkjet ink) obtained by the Example and the comparative example, using each ink liquid, the Ricoh company gel jet printer IPSiO GX5000 made PPC paper made from Xerox Corporation. 4024 was printed, and the ejection stability and the printed image were measured with an Xrite densitometer 938. The ink storage stability was also evaluated by the following test method.

Image density:
The color measurement of the solid image of the image sample is measured with an Xrite densitometer.

Image sharpness:
The sharpness of the character part was judged visually.
◎: Extremely good ○: Good △: Normal ×: Poor

Discharge stability:
After printing the printed matter, the printer was left in a 40 ° C. environment for one month with the printer head capped. Whether the discharge state of the printer after being left is restored to the initial discharge state was evaluated by the following number of cleaning operations.
○: Recovered by one action.
Δ: Recovered by 2 to 3 operations.
X: No recovery was observed even after three or more operations.

Ink storage stability:
Each ink was put in a polyethylene container, sealed, stored at 70 ° C. for 3 weeks, and then the particle size, surface tension, and viscosity were measured and evaluated according to the rate of change from the initial physical properties as follows.
A: Change rate is less than 5% in all items of particle size, surface tension, and viscosity.
○: Change rate is less than 10% in all items of particle size, surface tension, and viscosity.
Δ: Change rate is less than 30% in all items of particle size, surface tension, and viscosity.
X: The rate of change is 30% or more in at least one of the particle size, surface tension, and viscosity.

Dispersion (A)
Prescription carbon black NIPEX150-IQ (Degussa, gas black)
20 parts · Sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate (m = 3) 5 parts · Distilled water 75 parts After premixing the above mixture, a bead mill disperser (manufactured by Kotobuki Kogyo Co., UAM) -015) was dispersed with 0.03 mm zirconia beads (density 6.03 × 10 ⁻⁶ g / m ² ) at a peripheral speed of 10 m / s and a liquid temperature of 30 ° C. for 15 minutes, and then a centrifugal separator (manufactured by Kubota Corporation). , Model-3600), the coarse particles were centrifuged to obtain a dispersion (A) shown in Table 1 having an average particle diameter of 121.2 nm and a standard deviation of 41.1 nm of the carbon black dispersion.

Dispersion (B)
Except for changing the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate of dispersion (A) to the potassium salt of 7-sulfo-1,5-naphthalenecarboxylic acid formalin condensate (m = 4). A dispersion (B) was obtained in the same manner as in the preparation of the dispersion (A).

Dispersion (C)
Dispersion except that the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate in dispersion (A) is replaced with the sodium salt of 4-sulfo-2-naphthalenecarboxylic acid formalin condensate (m = 3). A dispersion (C) was obtained in the same manner as in the preparation of the liquid (A).

Dispersion (D)
A dispersion (D) was obtained in the same manner as in the preparation of the dispersion (A), except that 5 parts of the dispersant added to the dispersion (A) was changed to 2 parts.

Dispersion (E)
A dispersion (E) was obtained in the same manner as the preparation of the dispersion (A), except that 10 parts of the dispersant (A) was added in an amount of 5 parts.

Dispersion (F)
Dispersion liquid (A) except that the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate in dispersion liquid (A) is replaced with dilauroyl glutamic acid ricin Na (manufactured by Asahi Kasei Chemicals, Perisea L-30). ) To obtain a dispersion (F).

Dispersion (G)
Dispersion liquid except that the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate of dispersion liquid (A) is replaced with Piionin A-45-PN (manufactured by Takemoto Yushi Co., Ltd., anionic surfactant). A dispersion (G) was obtained in the same manner as in the preparation of (A).

Dispersion (H)
Dispersion as in the preparation of dispersion (A), except that the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate in dispersion (A) is replaced with polyvinylpyrrolidone (average molecular weight 25000). (H) was obtained.

Dispersion (I)
The dispersion liquid (A) except that the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate in the dispersion liquid (A) was replaced with Hytenol 18E (Daiichi Kogyo Seiyaku Co., Ltd., anionic surfactant). A dispersion (I) was obtained in the same manner as in the preparation of A).

[Examples 1 to 5]
Using the dispersions (A) to (E) obtained by the above method, an ink liquid was prepared according to the following ink formulation 1, and after stirring for 30 minutes, filtered with a membrane filter having a pore size of 0.8 μm, vacuum degassed, Ink liquids (ink liquids a to e) of Examples 1 to 5 were obtained.

Ink prescription 1
Ink formulation (ae)
-Pigment dispersion (pigment concentration 20%) 30.0 parts-Glycerol 15.0 parts-Diethylene glycol 15.0 parts-2-ethyl-1,3-hexanediol 3.0 parts-2-pyrrolidone 3.0 parts- Polyoxyethylene (3) alkyl (C13) ether acetate 0.45 parts, distilled water 33.55 parts

[Comparative Examples 1-4]
Ink liquids (ink liquids f to i) of Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that the dispersion liquids (F) to (I) were used.

(Evaluation)
Table 1 shows the evaluation of the ink liquids (a) to (i).

Dispersion (J)
Prescription Pigment Yellow 138
(Toyo Ink Mfg. Co., Ltd., LIONOGEN YELLOW 1010) 15 parts · Sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate (m = 3) 5 parts · Distilled water 80 parts After premixing the above mixture Disperse with 0.03 mm zirconia beads (density 6.03 × 10 ⁻⁶ g / m ² ) at a peripheral speed of 10 m / s and a liquid temperature of 30 ° C. for 40 minutes using a bead mill disperser (manufactured by Kotobuki Kogyo Co., Ltd., UAM-015). After that, the coarse particles were centrifuged with a centrifuge (Model 3600, manufactured by Kubota Shoji Co., Ltd.), and the dispersions shown in Table 2 having an average particle size of 43.2 nm and a standard deviation of 20.8 nm of the carbon black dispersion (J )

Dispersion (K)
Changing the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate in dispersion (J) to the potassium salt of 7-sulfo-1,5-naphthalenecarboxylic acid formalin condensate (m = 4) A dispersion (K) was obtained in the same manner as in the preparation of the dispersion (J) except that Pigment Red 122 (manufactured by Clariant, Toner Magenta E02) was used.

Dispersion (L)
Changing the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate in dispersion (J) to the sodium salt of 4-sulfo-2-naphthalenecarboxylic acid formalin condensate (m = 3), pigment Was obtained in the same manner as the dispersion (J) except that CI Pigment Blue 15: 3 (manufactured by Toyo Ink Manufacturing Co., Ltd., LIONOL BLUE FG-7351) was obtained.

Dispersion (M)
Dispersion (J) except that the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate of dispersion (J) is replaced with dilauroyl glutamate lysine Na (Asahi Kasei Chemicals, Perisea L-30). A dispersion (M) was obtained in the same manner as in the preparation of 1.

Dispersion (N)
When the sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate in dispersion (J) is replaced with Piionin A-45-PN (an anionic surfactant manufactured by Takemoto Yushi Co., Ltd.), the pigment is pigmented. A dispersion (K) was obtained in the same manner as in the preparation of the dispersion (J) except that Red 122 (manufactured by Clariant, Toner Magenta E02) was used.

Dispersion (O)
The sodium salt of 4-sulfo-1,8-naphthalenedicarboxylic acid formalin condensate of dispersion (J) was converted to polyvinylpyrrolidone ((average molecular weight 25000, Plysurf A219B (Daiichi Kogyo Seiyaku Co., Ltd .: polyoxyethylene alkyl ether phosphoric acid)). In the same manner as the dispersion (J) except that the pigment is Pigment Blue 15: 3 (Toyo Ink Manufacturing Co., Ltd., LIONOL BLUE FG-7351). Obtained.

[Examples 6 to 8]
Using the dispersions (J) to (L) obtained by the above method, an ink liquid was prepared according to the following ink formulation 2, and after stirring for 30 minutes, filtered with a membrane filter having a pore size of 0.8 μm, vacuum deaerated, Ink liquids (ink liquids j to l) of Examples 6 to 8 were obtained.

Ink formula 2
Ink formula (j ~ l)
Pigment dispersion (15% pigment concentration) 30.0 parts Glycerol 15.0 parts Diethylene glycol 15.0 parts 2-ethyl-1,3-hexanediol 3.0 parts 2-pyrrolidone 3.0 parts Polyoxyethylene (3) alkyl (C13) ether acetate 0.45 parts, distilled water 33.55 parts

[Comparative Examples 5 to 7]
Ink liquids (ink liquids m to o) of Comparative Examples 5 to 7 were obtained in the same manner as in Example 6 except that the dispersion liquids (M) to (O) were used.

(Evaluation)
Table 2 shows the evaluation of the ink liquids (j) to (o).

  From the results shown in Tables 1 and 2, the inkjet ink using the pigment dispersion of the present invention has a high image density and is superior to the conventional ones in ejection stability and ink liquid storage stability.

JP 2006/08858 A Japanese Patent Laid-Open No. 2002-03767 JP 2002-219854 A JP 2004-123904 A JP 05-239392 A Japanese Patent Laid-Open No. 08-283633 JP 2000-63727 A JP 2001-81366 A Special table 2003-509571 gazette JP-A-08-333531 Japanese Patent Laid-Open No. 56-147871 US Pat. No. 5,085,698 US Pat. No. 5,221,334 US Pat. No. 5,172,133 US Pat. No. 5,571,311 Japanese Patent Laid-Open No. 08-081646 Japanese Patent Laid-Open No. 08-03498 JP 09-194775 A JP 2000-144028 A Japanese Patent Application Laid-Open No. 2005-281691 JP 2005-314528 A JP 2006-188626 A Japanese Patent No. 3625595 Japanese Patent Publication No. 01-015422 Japanese Patent Application Laid-Open No. 08-041394 JP 2008-63573 A JP 2001-342373 A JP 2004-307632 A

Claims (12)

An ink jet recording ink comprising at least a pigment, a dispersant, water, a water-soluble organic solvent, and a humectant, wherein the dispersant is a compound having the following structural formula (1).
Structural formula (1)

(In the formula, p represents an integer of 1 to 3, q represents an integer of 1 to 3, and m represents an integer of 2 to 4. M1 and M2 represent H or an alkali metal, an alkaline earth metal, ammonium, or an organic amine. .)   The inkjet recording ink according to claim 1, wherein the compound having the general formula (1) is a formalin condensate of sulfonaphthalenecarboxylic acid.   The ink jet recording ink according to claim 1 or 2, wherein the ratio of the pigment to the dispersant is 0.01 to 2 of the dispersant relative to the pigment 1 on a weight basis.   The inkjet recording ink according to claim 1, wherein the pigment is carbon black. 5. The inkjet recording ink according to claim 4, wherein the carbon black has an average primary particle diameter of 10 to 30 nm and a BET specific surface area of 100 to 400 m ² / g.   The average particle diameter (D50) of the carbon black is 70 to 180 nm, and the particle diameter standard deviation in the particle size distribution of the carbon black is 1/2 or less of the average particle diameter. 6. An ink jet recording ink according to 5.   An ink cartridge comprising the ink jet recording ink according to claim 1 contained in a container.   An ink jet printing apparatus that performs recording by discharging the ink jet recording ink according to any one of claims 1 to 6 onto an image support.   The inkjet printing apparatus according to claim 8, wherein the inkjet printing apparatus is a piezo method or a thermal method.   7. An image forming method, wherein printing is performed by an ink jet printing apparatus using the ink jet recording ink according to claim 1.   An image-formed product obtained by printing the inkjet recording ink according to claim 1 on an image support with an inkjet printing apparatus.   The image-formed product according to claim 11, wherein the image support is paper.