JPH10114865A - Aqueous fine particle dispersion of disperse dye, disperse dye ink for inkjet recording using the same, and fabric dyeing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous microdispersion in which a disperse dye is effectively dispersed in the form of microparticles and which, even when it has a high solid content, is lowly viscous and stable and which is highly adaptable for a dyeing step by specifying the acid value of the constituent water-soluble polyester and specifying the mean particle diameter of the microparticles. SOLUTION: This microdispersion consists essentially of water, a water-soluble organic solvent, a disperse dye and a water-soluble polyester having an acid value of 100-250. The mean particle diameter of the dispersed microparticles should be 0.25μm or below. The polyester used is an anionic water-soluble polyester obtained by using a sulfonated diol or a carboxylated diol as a component of the diol component. The disperse dye is dispersed in this polyester to obtain a stable dispersion. The materials for synthesizing the polyester is a sulfonated diol or a carboxylated diol represented by e.g. formula I or II and being a substance in which the functional groups are protected. An aqueous microdispersion of the disperse dye is mixed with a liquid medium comprising water and a humectant solvent such as a polyhydric alcohol, and the pH of the obtained mixture is adjusted to 5-10 to obtain an ink jet recording ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous fine particle dispersion using a disperse dye, and more particularly, to an aqueous fine particle dispersion having a particle size of 0.25 .mu.m or less which is useful as a fabric dyeing liquid or an ink jet printing ink. About the body. Incidentally, the present invention uses a disperse dye of 0.01 to 1 μm
The present invention provides a water-based fine particle dispersion exhibiting efficient and stable dispersibility even with a dispersion having a particle size distribution in the range described above, and is useful for application to uses other than ink jet inks.

[0002]

2. Description of the Related Art In recent years, a system for performing plateless printing using an ink jet recording method has been proposed. The dispersion used in this method is in a fine particle state having an average particle diameter of 0.25 μm or less and has a viscosity of 3 even at a solid content of about 10%, as a basic requirement required by the inkjet system itself. It is required that the dispersion has a low viscosity of not more than centipoise and a stable fine particle dispersion.

On the other hand, a technique for dispersing a disperse dye in an aqueous medium has been conventionally known. First, typical dispersants for aqueous dispersion of disperse dyes include, for example,
Formalin condensates of naphthalene sulfonic acid, lignin sulfonic acid and the like can be mentioned, and examples of the surfactant include JP-A-48-14888 (Hoechst) and JP-A-50-88.
100386 (Nichika Chemical), JP-A-54-248
No. 4 (Toho Kagaku), Japanese Unexamined Patent Publication No. 55-54353 (ICI), and the like are known. These techniques are all used in the dispersion method which is industrially performed in the existing dyeing method. However, these conventional material technologies cannot efficiently and stably obtain a fine particle dispersion having an average particle size of 0.25 μm or less.

On the other hand, a technique for dispersing fine particles of a pigment in an aqueous medium has been put to practical use in the fields of inks for writing implements, inks for ink jet recording, photoresists, and liquid developers for electrophotography. However, these technologies and materials
Even when applied to the dispersion of fine particles in the submicron region of a disperse dye, the desired results are hardly obtained.

[0005] According to the dispersant and dispersion method currently used in aqueous pigment dispersion, very stable dispersions have been produced, and these dispersions are used as inks and paints. When an image is formed by printing or coating, water resistance, abrasion resistance and the like are developed, and an excellent image is formed. This is presumably because the dispersant is strongly adsorbed on the pigment particles as a protective colloid. However, it is not easy to chemically or physically desorb the substance once adsorbed. This contradicts the requirement that the dispersant must be removed after dyeing in the fabric dyeing process. Further, it is important to disperse the particles in a state of stable and fine particle diameter, and to impart stable suitability to a fabric dyeing process. However, it is extremely difficult to obtain a stable dispersion of a disperse dye with high yield and high stability using the above-mentioned conventional materials.

In order to improve the dispersibility of the disperse dye,
First, it is thought that it is necessary that the substance used as a dispersant has an adsorptivity (strong intermolecular attraction) with respect to a disperse dye which is not dissolved in an aqueous medium. However, it is considered that this property is not sufficient in the above-mentioned conventional materials, and as a result, the dispersibility is restricted. A technique of including a sulfonated polyester resin in an aqueous dispersion of a disperse dye is disclosed in Japanese Patent Publication No. 5-62632. However, as described clearly below, the two are completely different technologies.

First, in the invention described in Japanese Patent Publication No. 5-62632 (hereinafter simply referred to as the above invention), although the dispersant is specified as "partially sulfonated polyester resin", The existing sites are not clearly described, and are different from the present invention in the following points. (1) The aqueous fine particle dispersion of the disperse dye of the present invention is produced using a water-soluble polyester as a dispersant. on the other hand,
In the above invention, the polyester dispersion is used by stirring and mixing with the disperse dye. That is, in the above-mentioned invention, the polyester dispersion is prepared in advance as a dispersion, and only the dispersion and the dye are mixed at the time of preparing the ink. (2) As apparent from the formulation in the examples described below, the aqueous fine particle dispersion of the disperse dye of the present invention contains the polyester resin in an amount of 4 to 5 times the amount of the dye. It is presumed that the polyester resin is independently dispersed in particles. On the other hand, the amount of the polyester resin used in the above invention is small, and it is considered that the polyester resin is not independently dispersed in particles. (3) The water-soluble polyester constituting the aqueous fine particle dispersion of the disperse dye of the present invention has a high acid value of 100 to 250, but the sulfonated polyester resin used in the above invention is best exemplified by the following examples. In the possible embodiments, the acid number is <2, which is different from the constituent materials according to the invention. (4) In the present invention, one of the technical problems is various properties such as fine particle dispersion when used in an ink jet ink for fabric dyeing and suitability for the dyeing process. The effects are merely described, and do not disclose the technical problem to be solved by the present invention.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for efficiently dispersing fine particles in a state where the average particle size is 0.25 μm or less based on the above background. And a low-viscosity fine particle dispersion which can maintain a stable state for a long period of time even when a dispersion having a high solid content is used.
Further, an important object of the present invention is to provide a fine particle dispersion imparted with sufficient suitability for a dyeing step, such as reducing washing properties and cotton stainability after dyeing. An object of the present invention is to develop a dispersion having excellent detergency in a dyeing process.

[0009]

The above object is achieved by the present invention described below. That is, the present invention at least water,
In the aqueous fine particle dispersion containing a water-soluble organic solvent, a disperse dye and a water-soluble polyester, the water-soluble polyester is a water-soluble polyester having an acid value of 100 to 250, and the average particle diameter of the fine particles dispersed therein. Is 0.
An aqueous fine particle dispersion of a disperse dye, which is prepared to have a particle size of 25 μm or less, and a disperse dye ink for inkjet recording and a fabric dyeing method using the same. Furthermore, the water-soluble polyester used in the present invention having the above structure is obtained by a generally performed condensation reaction of a polycarboxylic acid and a polyhydric alcohol such as a diol. As one of them, an anionic water-soluble polyester obtained using a sulfonated diol or a carboxylated diol is more preferably used. Further, by adopting such a configuration, a greater effect of the present invention can be obtained.

The aqueous fine particle dispersion according to the present invention having the above-mentioned structure is used for fabrics, recording papers, ink-jet papers, films having water-absorptive ink absorbency, metals, plastics, etc., which have been subjected to a base treatment for improving printability. It is preferably used as an aqueous fine particle-dispersed ink which gives a recorded image having high color quality and excellent fastness. In particular, the aqueous fine particle dispersion of the present invention can provide an ink jet recording ink excellent in particle dispersibility in the submicron region, storage stability, and ejection characteristics in an ink jet recording apparatus. Such an ink jet recording ink using the aqueous fine particle dispersion of the present invention has at least an aqueous fine particle dispersion of a disperse dye, water, and a moisturizing solvent, and more preferably contains a penetrant. . And
The ink jet recording method using the ink for ink jet recording is particularly useful for digital textile printing, and can be used for a fabric dyeing method capable of producing a wide variety of fine patterns.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The aqueous fine particle dispersion of the disperse dye of the present invention contains at least water, a water-soluble organic solvent, a disperse dye and a water-soluble polyester,
The water-soluble polyester is a water-soluble polyester having an acid value of 100 to 250, and the dispersed fine particles have an average particle diameter of 0.25 μm or less.

Hereinafter, the substance constituting the aqueous fine particle dispersion of the disperse dye of the present invention will be described. First, the water-soluble polyester in which the disperse dye is dispersed will be described. As described above, the polyester is obtained by a condensation reaction between a polycarboxylic acid and a polyhydric alcohol such as a diol. In the present invention, the polyester is obtained by using a sulfonated diol or a carboxylated diol as at least one of the diol components. Anionic water-soluble polyesters are more preferably used. That is, by dispersing a disperse dye using an anionic water-soluble polyester, fine particles can be efficiently formed, a stable dispersion can be obtained, and the effects of the present invention can be more effectively obtained. Therefore, in the synthesis, as described below, as a raw material for polyester synthesis, these functional groups in the compound are temporarily protected by a protecting group so that the obtained water-soluble polyester has these functional groups. It is preferred to use a protected (protected so as not to participate in polyester synthesis) substance.

Although various synthetic methods using a protecting group are known, in the present invention, silyl esterification, t
-Butyl esterification, acetal esterification, and by a protection method such as ketal esterification, while suitably protecting a carboxyl group or a sulfone group as a dissociation group,
It is preferred to synthesize a water-soluble polyester. Specific examples of the substance that binds the above-described protecting group for polyester synthesis that can be used in the present invention include the following sulfonated diols and carboxylated diols.

[0014]

Embedded image N, N-Bis (2-hydroxyethyl) -2-aminoethane carb
oxylic acid

[0015]

Embedded image N, N-Bis (2-hydroxyethyl) -2-aminoethane sulf
onic acid

[0016]

Embedded image 3- [N, N-Bis (2-hydroxyethyl) amino] -2-hydroxy
propane sulfonic acid

[0017]

Embedded image 2,7-dihydroxynaphthalene-3,6-disulfonic ac
id

[0018]

Embedded image 1,7-dihydroxynaphthalene-3-sulfonic acid

[0019]

Embedded image 2,3-dihydroxynaphthalene-6-sulfonic acid

[0020]

Embedded image 1,8-dihydroxynaphthalene-3,6-disulfonic ac
id

[0021]

Embedded image 3,5-dihydroxy phenylmethane sulfonic acid

[0022]

Embedded image 3,5-dihydroxy phenylmethane calboxylic aci
d

In the present invention, the following half-ester compounds composed of a polyol and a polycarboxylic acid are also suitably used as a substance that binds a protecting group that can be used in the synthesis of polyester.

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

The structures obtained by bonding various protecting groups to the above-mentioned compounds are shown below by taking the compound (1) as an example below, and are as follows.

[0031]

Embedded image (Trimethylsilyl esterification)

[0032]

Embedded image (t-butyl esterification)

[0033]

Embedded image (Acetal esterification)

[0034]

Embedded image (Ketal esterification)

As described above, silyl esterification, t
By performing butyl esterification, acetal esterification, ketal esterification, or the like, the carboxyl group, which is the dissociating group of the compound (1), is protected from participating in the polyesterification reaction. Other diols containing a dissociating group used in such a method include,
Examples thereof include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid.

The water-soluble polyester used in the present invention is:
According to a conventional method, the skeleton is obtained by esterifying a polycarboxylic acid and a diol. When a polyester is synthesized using the diol having a dissociating group described above as one of the diol components, after esterification of the diol with a polycarboxylic acid for forming a skeleton, the polyester is synthesized for protection of the dissociating group. It is necessary to selectively hydrolyze the dissociated group portion of the diol which has been esterified and restore it to make it water-soluble.
Therefore, in this case, it is necessary to remove the protecting group of the dissociating group under the condition that the hydrolysis of the ester bond forming the main chain is suppressed. In consideration of this point, among the above four protection methods, it is most preferable to use one in which the dissociation group is protected by silyl esterification. It is known that the reaction proceeds by using a protecting group.
No. 269 is used.

The water-soluble polyester used in the present invention is synthesized as described above. Examples of the polycarboxylic acid used in this case include adipic acid, succinic acid, malonic acid, sebacic acid and cyclohexanedicarboxylic acid. The acid is selected from acids, phthalic acid, trimellitic acid, endic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and anhydrides thereof. Among them, carbon 6
Polycarboxylic acid having a membered ring structure and phthalic anhydride as its anhydride, 1,3-cyclopentanedicarboxylic acid,
Anhydrides of 1,4-cyclohexanedicarboxylic acid and their oligoester derivatives are preferred.

Examples of the diol component having no dissociating group that can be used in the synthesis of the water-soluble polyester used in the present invention include ethylene glycol and
Diethylene glycol, triethylene glycol, tripropylene glycol, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,
Examples thereof include compounds such as 2,5-pentanetriol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, bisphenol A, and hydrogenated bisphenol A. These diols having no dissociating group are used for the purpose of adjusting the number of dissociating groups in the molecule of the obtained polyester, and for adjusting the flexibility of the molecular chain, the softening temperature, and the like. Is preferably used in combination with a diol having

In the synthesis of the water-soluble polyester used in the present invention, the esterification reaction between the polycarboxylic acid forming the main chain and the diol can be carried out under conventionally known conditions. It is possible to add an aprotic polar solvent during the synthesis for the purpose of lowering the viscosity of. As the aprotic polar solvent used at that time, for example, tetrahydrofuran, ethers such as dioxane, esters such as ethyl acetate,
Examples include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alkyl ethers of glycol compounds, amides such as N-methylpyrrolidone and dimethylformamide, and halogenated aromatic compounds such as chlorobenzene and dichlorobenzene. In the present invention, a solvent is selected from the solvents belonging to these classes in consideration of the reaction temperature, the solubility of the produced polymer, the vapor pressure, and the removal under reduced pressure after the reaction. Specifically, dioxane, diethylene glycol monobutyl ether, N-methylpyrrolidone, o-dichlorobenzene and the like are preferably used.

The reaction conditions for synthesizing the polyester using the above-mentioned synthetic materials may be the conditions used in a conventional manner. For example, at a temperature of 120 to 180 ° C., the solvent and the solvent are removed while removing water. The reaction is carried out under reflux of the reactants for 3 to 5 hours. After the reaction is completed, the reaction solution is cooled, and a hydrolysis treatment for removing a protecting group for protecting a dissociating group is performed by adding water and a base such as sodium hydroxide and stirring. The generated low molecular alcohol is removed under reduced pressure conditions. In this manner, conversion to an aqueous system is carried out to obtain a water-soluble polyester resin having an acid value of 100 to 250 and having an anionic dissociating group, which is suitably used in an aqueous fine particle dispersion of the disperse dye of the present invention.

When the water-soluble polyester used in the present invention is obtained by the above-described synthesis, the diol or dicarboxylic acid used as the synthesis raw material has a molecular weight of 300 to 300 in which a hydroxyl group or a carboxyl group is previously introduced into a terminal.
It may be 1,500 oligoesters or oligourethane compounds.

The specific procedure of the method for producing the water-soluble polyester used in the present invention obtained as described above will be described. For example, a polycarboxylic acid such as succinic acid or adipic acid is added to a silyl ester compound of a carboxylated diol or a sulfonated diol, and the mixture is placed in a reaction flask equipped with a thermometer and a refluxer, and then heated to a temperature of 120 to 1.
At 80 ° C. under reflux of the solvent and reactants while removing water,
The condensation reaction is performed for 3 to 5 hours. Next, in the resulting solution,
After adding water, sodium hydroxide or the like to hydrolyze the protecting group portion of the dissociating group, the generated trimethylsilanol is removed under reduced pressure. Next, after neutralizing by adding a neutralizing agent to the reactive group, water is added to the aqueous system while removing the solvent under reduced pressure to carry out solvent replacement in an aqueous system to obtain a water-soluble polyester used in the present invention. As described above, the water-soluble polyester used in the present invention requires a neutralizing agent when used as an aqueous solution, and the neutralizing agent used in this case includes inorganic and organic basic compounds. Both can be used. Examples of the neutralizing agent specifically used include, for example, an inorganic base, ammonia, monoethanolamine, diethanolamine, triethanolamine,
Amines such as dimethylamine, triethylamine and aminomethylpropanol are exemplified.

(Disperse Dye) In the aqueous fine particle dispersion of the disperse dye of the present invention, examples of the disperse dye dispersed by the water-soluble polyester having the above constitution include the following dyes. -Yellow disperse dye CIDisperse Yellow 5, CIDisperse Yellow 42,
CIDisperse Yellow54, CIDisperse Yellow 6
4, CIDisperse Yellow 79, CIDisperse Yellow
82, CIDisperse Yellow 83, CIDisperse Yello
w 93, CIDisperse Yellow 99, CIDisperse Yel
low 100, CIDisperse Yellow 119, CIDisper
se Yellow 122, CI Disperse Yellow 124, CI
Disperse Yellow 126, CIDisperse Yellow 16
0, CIDisperse Yellow 184: 1, CIDisperse Y
ellow 186, CIDisperse Yellow 198, CIDisp
erse Yellow 199, CIDisperse Yellow 204, C.
I. Disperse Yellow 224, CIDisperse Yellow 23
7,

Orange disperse dye CIDisperse Orange 13, CIDisperse Orange 2
9, CIDisperse Orange 31: 1, CIDisperse Ora
nge 33, CIDisperse Orange 49, CIDisperse O
range 54, CIDisperse Orange 55, CIDisperse
Orange 66, CIDisperse Orange 73, CIDisper
se Orange 118, CI Disperse Orange 119, CID
isperse Orange 163,

Red disperse dye CI Disperse Red 54, CI Disperse Red 72, CI
Disperse Red 73, CIDisperse Red 86, CIDisp
erse Red 88, CIDisperse Red 91, CIDisperse
Red 92, CIDisperse Red 93, CIDisperse Red
111, CIDisperse Red 126, CIDisperse Red
127, CIDisperse Red 134, CIDisperse Red
135, CIDisperse Red 143, CIDisperse Red
145, CIDisperse Red 152, CIDisperse Red
153, CIDisperse Red 154, CIDisperse Red
159, CIDisperse Red 164, CIDisperse Red
167: 1, CIDisperse Red 177, CIDisperse
Red 181, CIDisperse Red 204, CIDisperse
Red 206, CIDisperse Red 207, CIDisperse
Red 221, CIDisperse Red 239, CIDisperse
Red 240, CIDisperse Red 258, CIDisperse
Red 277, CIDisperse Red 278, CIDisperse
Red 283, CIDisperse Red 311, CIDisperse
Red 323, CIDisperse Red 343, CIDisperse
Red 348, CIDisperse Red 356, CIDisperse R
ed 362,

A purple disperse dye CIDisperse Violet 33, a blue disperse dye CIDisperse Blue 56, CI Disperse Blue 60, C.I.
I. Disperse Blue 73, CI Disperse Blue 87, CI
Disperse Blue 113, CIDisperse Blue 128, C.I.
I. Disperse Blue 143, CIDisperse Blue 148,
CIDisperse Blue 154, CIDisperse Blue 15
8, CIDisperse Blue 165, CIDisperse Blue 1
65: 1, CIDisperse Blue 165: 2, CIDisper
se Blue 176, CIDisperse Blue 183, CIDisp
erse Blue 185, CIDisperse Blue 197, CIDi
sperse Blue 198, CI Disperse Blue 201, CI
Disperse Blue 214, CI Disperse Blue 224, C.I.
I. Disperse Blue 225, CIDisperse Blue 257,
CIDisperse Blue 266, CIDisperse Blue 26
7, CIDisperse Blue 287, CIDisperse Blue 3
54, CIDisperse Blue 358, CIDisperse Blue
365, CIDisperse Blue 368, Green disperse dye CIDisperse Green 6: 1, CIDisperse Green 9

Among the above dyes, more preferred dyes are as follows. -Yellow disperse dye CIDisperse Yellow 5, CIDisperse Yellow 42,
CIDisperse Yellow83, CIDisperse Yellow 9
3, CIDisperse Yellow 99, CIDisperse Yellow
198, CIDisperse Yellow 224 ・ Orange disperse dye CIDisperse Orange 29, CIDisperse Orange 4
9. CIDisperse Orange 73

Red disperse dye CI Disperse Red 92, CI Disperse Red 126, C.I.
I. Disperse Red 145, CI Disperse Red 152, C.
I. Disperse Red 159, CI Disperse Red 177, C.
I. Disperse Red 181, CIDisperse Red 206, C.I.
I. Disperse Red 283-Blue disperse dye CI Disperse Blue 60, CI Disperse Blue 87, C.I.
I. Disperse Blue 128, CIDisperse Blue 154,
CIDisperse Blue 201, CIDisperse Blue 21
4, CIDisperse Blue 224, CIDisperse Blue 2
57, CIDisperse Blue 287, CIDisperse Blue
368

The dyes described above are preferable examples that can be used in the present invention, and the present invention is not limited to the dyes described above, and may be, of course, newly synthesized dyes. . In particular, in the present invention, it is preferable to use a disperse dye product taken out in the form of a wet cake during the production of the dye, since good fine particle dispersion can be achieved. That is, when the product in such a wet cake state is used in the dispersion treatment step, the dispersion can be efficiently made into fine particles. However, the use of a product taken out in the form of a wet cake is basically not a problem of work efficiency and has little effect on the attainable performance, and is not an essential condition in the present invention.

(Production of Dispersion) The aqueous fine particle dispersion of the disperse dye of the present invention can be obtained by subjecting the above-mentioned disperse dye to a dispersion treatment with the above-mentioned water-soluble polyester. At the time of dispersion, the disperse dye and the water-soluble polyester are mixed in a weight ratio of 100: 10 to 100: 200, premixed, and then subjected to dispersion treatment. As a method of the dispersion treatment, it is preferable to use a dispersion method using glass beads, silica-alumina ceramic beads, zirconia beads, natural silica beads such as Ottawa sand or the like as a medium.

The dispersing machine used in the dispersion of the present invention may be any commonly used dispersing machine as long as the average particle size of the disperse dye in the obtained dispersion is within the desired range efficiently. Any device such as a device may be used. For example, a ball mill, a sand mill and the like can be mentioned. Among them, a high-speed sand mill is preferable, and examples thereof include a super mill, a sand glider, a bead mill, an agitator mill, a Glen mill, a Dyno mill, a pearl mill, and a Kobol mill (all trade names). In addition, a roll mill, a jet mill, or the like, which does not use beads but can apply a high shear stress, is also effective to be used in combination, since impurities are less mixed therein.

In the present invention, it is necessary that the average particle diameter of the dispersed fine particles of the disperse dye is adjusted to 0.25 μm or less. When the average particle diameter is larger than 0.25 μm, when the obtained dispersion is used for an application such as an ink for ink jet recording, the ejection property is poor and clogging occurs,
Further, it becomes difficult to obtain a fine high-quality image. Furthermore,
In the present invention, the particle size distribution of the fine particles of the disperse dye is 0.1.
It is preferable to adjust the thickness to be from 01 to 1 μm.
A fine particle dispersion of an aqueous disperse dye having such a particle size distribution and having an average particle size of 0.25 μm or less and having excellent dispersion stability is particularly excellent in ink jet suitability when applied to an ink for ink jet recording. It is possible to stably provide a high quality color image.

In the present invention, a method of obtaining a dispersion having a desired particle size distribution includes, for example, a method of reducing the size of a pulverizing medium of a disperser, a method of dispersing and then classifying by pressure filtration or centrifugation, Techniques such as aging treatment and pressure filtration are mentioned. In the present invention, a dispersion having a desired particle size distribution can be easily obtained by these techniques. For example, coarse particles can be removed by centrifugation, but in the present invention, fine particles can be efficiently formed because a water-soluble polyester is used as a dispersant. Therefore, the desired dispersion can be obtained under low centrifugation conditions without generating a large amount of precipitate by centrifugation. As described above, the aqueous fine particle dispersion of the present invention is produced.

Next, an ink jet recording ink according to the present invention, comprising the aqueous fine particle dispersion of the disperse dye of the present invention having the above-described structure, water and a humectant, will be described. The ink jet recording ink of the present invention is prepared by adjusting the aqueous fine particle dispersion of the present invention to a liquid medium composition according to the purpose of use. In the present invention, water and usually used in an aqueous fine particle dispersion are used. Water-miscible moisturizing solvents such as monohydric alcohols, polyhydric alcohols, and monoalkyl ethers of polyhydric alcohols are used. The water-miscible moisturizing solvents were classified into the following three groups as a result of classification by the present inventors based on their functions. Specific solvents that may belong to these groups are listed below. Group 1: Solvents that have high moisture retention, are difficult to evaporate, and are excellent in hydrophilicity. Group 2: Solvents having a hydrophobic atom group at the end and having good wettability to a hydrophobic surface and also having evaporation and drying properties. : Moderate wettability, low viscosity solvent (monohydric alcohols)

Therefore, it is preferable that the liquid medium used in the ink jet recording ink of the present invention is appropriately selected from these solvents based on the function of these solvents, combined, and used as a liquid medium together with water. In the ink jet recording ink of the present invention, the total amount of the liquid medium comprising the water-soluble solvent as described above is generally 5 to 40% by weight based on the entire aqueous fine particle dispersion of the disperse dye of the present invention.
Is preferably within the range. If the amount is less than 5% by weight, problems such as poor ink ejection properties and clogging occur. On the other hand, if the amount is more than 40% by weight, the viscosity becomes high, and the drivable frequency decreases, which is not preferable. As for the composition of the liquid medium of each group described above, the solvent contained in the first group or the second group should contain at least 5% by weight, preferably about 10% by weight.
The third group of solvents is preferably used in an amount of 5% by weight or less.

As the solvent belonging to the first group, specifically, ethylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, glycerin, 1,2,4-butanetriol, 1,2,6
-Hexanetriol, 1,2,5-pentanetriol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dimethylsulfoxide,
Diacetone alcohol, glycerin monoallyl ether, propylene glycol, butylene glycol, polyethylene glycol 300, thiodiglycol, N-methyl-2-pyrrolidone, 2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone , Sulfolane, trimethylolpropane, trimethylolethane, neopentyl glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, propylene glycol Glycol monomethyl ether, dipropylene glycol monomethyl ether, bis β- hydroxyethyl sulfone, bis β- hydroxyethyl urea, urea, acetonyl acetone, pentaerythritol, and 1,4-cyclohexane diol.

Examples of the solvents belonging to the second group include hexylene glycol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monophenyl ether, diethylene glycol diethyl ether, Diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether,
Dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, glycerin monoacetate, glycerin diacetate, glycerin triacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, cyclohexanol, 1,2-cyclohexanediol , 1-butanol, 3-methyl-1,5-pentanediol, 3-hexene-2,5-diol, 2,3-
Butanediol, 1,5-pentanediol, 2,4-
Pentanediol, 2,5-hexanediol and the like can be mentioned.

Further, examples of the solvents belonging to the third group include ethanol, n-propanol, 2-propanol, 1-methoxy-2-propanol, furfuryl alcohol, tetrahydrofurfuryl alcohol and the like.

The aqueous fine particle dispersion of the disperse dye of the present invention is
When water is mixed with a liquid medium comprising a moisturizing solvent such as the above-mentioned polyhydric alcohol to prepare an ink for inkjet recording, it is preferable to adjust the pH of the ink from a neutral to a basic region. Specifically, the pH of the ink is 5-1.
It is desirably within the range of 0, preferably 7 to 9.
By adjusting the pH to this range, the storage stability of the ink can be obtained. Furthermore, especially when an image is formed on a fabric, the fabric is suitable for dyeing properties, reducing washing after dyeing, washing with water, and the like. Is obtained.

Examples of the pH adjuster for the base species used at this time include inorganic bases such as sodium hydroxide, potassium hydroxide and lithium hydroxide, ethanolamine, diethanolamine, triethanolamine and N-methylethanolamine. , N-ethyldiethanolamine, 2-amino-2-methylpropanol, 2-ethyl-2-amino-1,3-propanediol, 2- (2-aminoethyl) ethanolamine, tris (hydroxymethyl) aminomethane, ammonia And organic bases such as glycine, glycylglycine, histidine, L-lysine, L-arginine, piperidine, morpholine and β-dihydroxyethylurea.

Further, when the aqueous fine particle dispersion of the disperse dye of the present invention is applied to an ink for ink jet recording or the like, it imparts a dyeing property to the cloth and improves the ejection efficiency when used in a bubble jet type ink jet apparatus. For purposes, it may be practically advantageous to add a surfactant as a penetrant. Examples of the surfactant used in this case include nonionic surfactants such as ethylene oxide adduct of acetylene glycol, formalin condensate of naphthalenesulfonic acid, and polyoxyethylene long-chain alkyl ether; polyoxyethylene phosphoric acid, carboxylic acid And a nonionic anionic surfactant such as a polyoxyethylene alkyl ether or a polyoxyethylene alkyl phenyl ether having an anionic dissociation group selected at the terminal of ethylene oxide and having an HLB of 10 or more. The addition of these surfactants in the present invention is preferably appropriately selected and added as necessary in consideration of foaming properties.

When the aqueous fine particle dispersion of the disperse dye of the present invention is used as an ink jet recording ink for dyeing, additives such as a preservative and an antifoaming agent may be required. It is preferable that these additives are appropriately selected from water-soluble preservatives, defoamers having good miscibility with water, and the like.

The ink jet recording ink containing the aqueous fine particle dispersion of the disperse dye according to the present invention having the above-described structure is particularly preferable for a fabric dyeing method using an ink jet recording apparatus using thermal energy as a droplet discharge source. Used. The ink for ink jet recording of the present invention is particularly preferably used in an ink jet system in which recording is performed by discharging droplets by the action of thermal energy, but it goes without saying that it can also be used as a general writing instrument.

As a recording method and apparatus suitable for performing recording using the ink-jet ink of the present invention, a thermal energy corresponding to a recording signal is applied to the ink in the recording head chamber, and droplets are generated by the thermal energy. An ink jet recording method and apparatus are exemplified. Hereinafter, such an ink jet recording apparatus will be described. FIGS. 1, 2 and 3 show examples of the configuration of a head which is a main part of the apparatus. The head 13 includes a glass, ceramic or plastic plate or the like having a groove 14 through which ink passes, and a heating head 15 (a thin film head is shown in the figure, but is not limited to this) used for thermal recording. Are obtained by bonding. The heating head 15 includes a protective film 16 made of silicon oxide or the like, and aluminum electrodes 17-1 and 17-.
2. It is composed of a heating resistor layer 18 made of nichrome or the like, a heat storage layer 19, and a substrate 20 having good heat dissipation such as alumina.

The ink 21 has a discharge orifice (fine hole) 2
2, and a meniscus 23 is formed by a pressure (not shown). Now, aluminum electrodes 17-1 and 17
When electric signal information is added to -2, the area indicated by n of the heating head 15 generates heat rapidly, bubbles are generated in the ink 21 in contact with the area, and the meniscus 23 protrudes due to the pressure, and the ink 21 is ejected. The ink orifices 22 fly toward the recording material 25 from the ejection orifices 22.

FIG. 3 is an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described with reference to FIG. FIG. 1 is a cross-sectional view of the head 13 along the ink flow path.
FIG. 2 is a sectional view taken along line AB in FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating the above head. In FIG. 4, reference numeral 65 denotes a recording head which has a discharge energy generating means and discharges ink on a recording material opposed to a discharge port surface provided with discharge ports to perform recording. This is a carriage for moving. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 moves the guide shaft 6
7, the recording area by the recording head 65 and the area adjacent thereto can be moved.

Reference numeral 51 denotes a paper feeding unit for inserting a recording material,
52 is a paper feed roller driven by a motor (not shown). With such a configuration, the recording material is fed to a position facing the discharge port surface of the recording head 65, and is discharged to a discharge section provided with a discharge roller 53 as recording proceeds.

Reference numeral 61 denotes a blade serving as a wiping member, one end of which is held by a blade holding member and serves as a fixed end, forming a cantilever. Blade 6
Numeral 1 is arranged at a position adjacent to the recording area of the recording head 65, and in this example, is held in a form protruding into the movement path of the recording head 65. Reference numeral 62 denotes a cap on the ejection port surface of the recording head 65, which is disposed at a home position adjacent to the blade 61, moves in a direction perpendicular to the moving direction of the recording head 65, and comes into contact with the ink ejection port surface to perform capping. It has a configuration to perform. Further, reference numeral 63 denotes an ink absorber provided adjacent to the blade 61, which is held in a form protruding into the movement path of the recording head 65, similarly to the blade 61. The blade 61, the cap 62, and the ink absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the ink absorber 63 remove water, dust, and the like from the ink ejection port surface.

In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the cap 62 of the ejection recovery section 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. I have. As a result, the ejection port surface of the recording head 65 is wiped.
When capping is performed with the cap 62 in contact with the ejection opening surface of the recording head 65, the cap 62 moves so as to protrude into the movement path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same positions as the positions at the time of wiping described above. As a result, the ejection port surface of the recording head 65 is also wiped during this movement. The movement of the print head 65 to the home position is performed not only at the end of printing or at the time of ejection recovery, but also at the home position adjacent to the printing area at a predetermined interval while the printing head 65 moves through the printing area for printing. And the wiping is performed with this movement.

FIG. 5 is a view showing an example of an ink cartridge containing ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink storage unit that stores the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the end thereof. By inserting a needle (not shown) into this stopper 42,
The ink in the ink bag 40 can be supplied to the head. An ink absorber 44 receives the waste ink. It is preferable for the present invention that the ink absorbing portion has a liquid contact surface with the ink formed of polyolefin, particularly polyethylene.

The ink jet recording apparatus in which the ink for ink jet recording of the present invention is used is not limited to the one in which the head and the ink cartridge are separated as described above, but they are integrated as shown in FIG. It is also suitably used for those. In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink storage unit storing ink, for example, an ink absorber is stored, and a head unit having a plurality of orifices in which the ink in the ink absorber is stored. It is configured to be ejected from 71 as ink droplets.

As the material of the ink absorber, it is preferable for the present invention to use polyurethane. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 includes the recording head 6 shown in FIG.
5 and is detachable from the carriage 66.

[0075]

The present invention will be specifically described below with reference to examples and comparative examples. In the following description, "parts" and "%" are based on weight unless otherwise specified. First,
The synthesis example of the water-soluble polyester used in the present invention is shown. [Synthesis Example 1 Water-soluble polyester PEP-1] Using 1 mol (275 g) of a compound obtained by silyl esterifying the carboxylated diol of the structural formula (1) described above and 1 mol (118 g) of succinic acid, a thermometer and The condensation reaction was performed at a temperature of 160 ° C. for 3 hours in a flask equipped with a reflux condenser. The obtained substance was hydrolyzed with sodium hydroxide to restore the carboxyl group of the structural formula (1), and the generated trimethylsilanol was removed under reduced pressure. Next, ammonia was added to the reaction solution and neutralized to obtain a water-soluble polyester PEP-1 which was an approximately 45% aqueous solution. The number average molecular weight of the obtained polymer was 8,500, and the acid value was 170.
The average number of carboxyl groups contained in one molecule of this substance is 26.4 (calculated value).

[Synthesis Example 2 Water-soluble polyester PEP-
2] 1.05 mol (300 g) of a compound obtained by silyl-esterifying the sulfonated diol of the structural formula (2) described above.
And 1 mol (118 g) of succinic acid was subjected to a condensation reaction at 170 ° C. for 4 hours in a flask equipped with a thermometer and a reflux condenser. After the obtained substance was hydrolyzed with sodium hydroxide to restore the sulfone group, the generated trimethylsilanol was removed under reduced pressure. Next, ammonia was added to the reaction solution and neutralized with ammonia to obtain a water-soluble polyester PEP-2 which was an approximately 50% aqueous solution. The number average molecular weight of the obtained polymer was 5,500, and the acid value was 170.

[Synthesis Example 3 Water-soluble polyester PEP-
3] 1.10 mol (46) of a compound obtained by silyl-esterifying the aromatic disulfonic acid diol of the structural formula (4) described above.
7 g) and 1 mol of adipic acid (146 g) were subjected to a condensation reaction at 170 ° C. for 4 hours in a flask equipped with a thermometer and a reflux condenser. The obtained substance was hydrolyzed with sodium hydroxide to restore the sulfone group of the structural formula (2), and the generated trimethylsilanol was removed under reduced pressure. Then, monoethanolamine is added to the reaction solution to neutralize it, and a water-soluble polyester PEP which is an approximately 35% aqueous solution is used.
-3 was obtained. The number average molecular weight of the obtained polymer was 12,7.
00, the acid value was 230.

[Synthesis Example 4 Water-soluble polyester PEP-
4] A compound obtained by silyl-esterifying the above-mentioned aromatic disulfonic acid diol of the structural formula (5) 1.10 mol (31
3 g) and 1 mol (146 g) of adipic acid were subjected to a condensation reaction at a temperature of 180 ° C. for 4 hours in a flask equipped with a thermometer and a reflux condenser. The obtained substance was hydrolyzed with sodium hydroxide to restore the sulfone group of the structural formula (4), and the generated trimethylsilanol was removed under reduced pressure. Next, monoethanolamine is added to the reaction solution to neutralize it, and a water-soluble polyester PE which is an aqueous solution of about 35% is used.
P-4 was obtained. The number average molecular weight of the obtained polymer was 6,7.
00, the acid value was 150.

[Synthesis Example 5 Water-soluble polyester PEP-
5] Condensation reaction was carried out in the same manner as in Synthesis Example 1 using the t-butyl ester of the aromatic disulfonic acid diol represented by the structural formula (7) and adipic acid, to give a water-soluble polyester PEP-5. I got The obtained polymer was a water-soluble polymer having a number average molecular weight of 9,800 and an acid value of 235, having a sulfone group in a side chain neutralized with monoethanolamine.

[Synthesis Example 6 Water-soluble polyester PEP-
6] Synthesis example 1 using t-butyl ester of aromatic carboxylic acid diol of structural formula (9) and adipic acid described above.
The condensation reaction was carried out in the same manner as in the above to obtain a water-soluble polyester PEP-6. The obtained polymer was a water-soluble polymer having a carboxyl group in a side chain neutralized with monoethanolamine, having a number average molecular weight of 5,800 and an acid value of 180.

[Synthesis Example 7 Water-soluble polyester PEP-
7] Condensation reaction was carried out in the same manner as in Synthesis Example 1 using the t-butyl ester of the aromatic carboxylic acid diol of the structural formula (10) and adipic acid described above, to give a water-soluble polyester PEP-7. I got The obtained polymer was a water-soluble polyester having a carboxyl group on the side chain neutralized with monoethanolamine having a number average molecular weight of 6,600 and an acid value of 124.

[Synthesis Example 8 Water-soluble polyester PEP-
8] Condensation reaction was carried out in the same manner as in Synthesis Example 1 using the t-butyl ester of the aromatic carboxylic acid diol of the structural formula (11) and adipic acid described above, to give a water-soluble polyester PEP-8. I got The obtained polymer was a water-soluble polyester having a carboxyl group in a side chain neutralized with monoethanolamine having a number average molecular weight of 10,200 and an acid value of 140.

[Synthesis Example 9 Water-soluble polyester PEP-
9] A condensation reaction was carried out using trimethylsilyl ester of the aromatic carboxylic acid diol represented by the structural formula (14) and succinic acid in the same manner as in Synthesis Example 1 to obtain a water-soluble polyester PEP-9. The obtained polymer was a water-soluble polyester having a carboxyl group in the side chain neutralized with monoethanolamine having a number average molecular weight of 7,200 and an acid value of 250.

Next, using the water-soluble polyesters PEP-1 to 9 synthesized as described above, an aqueous fine particle dispersion of the disperse dye of the example of the present invention and an ink jet recording ink using the same were prepared. did. Table 1 shows the compositions together with the compositions of the dispersion and the ink for the comparative example.

[0085] In Example 1 the following method, to prepare a dispersion DBL-1, inkjet recording ink BL-1 and BL-2 in Example 1. (Dispersion DBL-1) 10 parts of PEP-1 (45% aqueous solution of neutralized ammonia, pH 7.3) I. Disperse Blue 60 Wet cake prototype (solid content 40%) 60 parts (solid content) ・ Ethanol 10 parts ・ Water 130 parts These materials were charged in a 1,000 ml batch type vertical sand mill, and 2,000 rpm for 30 minutes. After the pre-mixing, 250 ml of zirconium beads having a diameter of 1 mm was filled as a medium, and the mixture was cooled to 3,000 r with water.
Dispersion treatment was performed at pm for 5 hours. The viscosity of the liquid after dispersion was 5 cps. This dispersion is prepared at 5,000 rpm for 2 hours.
The coarse particles were removed by centrifugation under the condition of 0 minutes, the solid content was 10.3%, the average particle diameter was 135 nm, and the surface tension was 51 dyn.
/ Cm, the dispersion DBL-1 of this example having a pH of 7.2 was obtained.

(Inkjet recording ink BL-1)
Next, using the dispersion DBL-1 obtained above, the inkjet recording inks BL-1 and B
L-2 was produced.・ Dispersion DBL-1 50 parts ・ Triethylene glycol 20 parts ・ Glycerin 5 parts ・ Water 27 parts ・ Monoethanolamine aqueous solution (pH adjustment) A little amount The above components are mixed well, and then, using a 0.25 μm membrane filter. The mixture was filtered under pressure to prepare a blue inkjet ink BL-1 having a viscosity of 2.2 cps, a surface tension of 40 dyn / cm, and a pH of 8.5.

(Ink for Ink Jet BL-2) 35 parts of dispersion DBL-1 10 parts of thiodiglycol 10 parts of glycerin 45 parts of water Monoethanolamine aqueous solution (pH adjustment) Some amount The above components are mixed well. Then, the mixture was filtered under pressure using a 0.25 μm membrane filter to prepare a blue inkjet ink BL-2 having a viscosity of 2.3 cps, a surface tension of 46 dyn / cm, and a pH of 8.5.

[0088] In Example 2 the following method, dispersion DBL-2 of Example 2, was prepared inkjet ink BL-3. (Dispersion DBL-2) 20 parts of PEP-2 (50% aqueous solution of neutralized ammonia, pH 8.2) I. Disperse Blue 128 wet cake (solid content 40%) 50 parts ・ Diethylene glycol 10 parts ・ Water 120 parts These materials were dispersed in the same manner as in Example 1,
Solid content 12.5%, average particle size 146nm, surface tension 48
A dispersion DBL-2 having a dyn / cm and a pH of 8.0 was obtained.

(Ink Jet Ink BL-3) Next, using the dispersion DBL-2 obtained above, an ink jet recording ink BL-3 was prepared in the following procedure. -40 parts of dispersion DBL-2-15 parts of triethylene glycol monoethyl ether-10 parts of glycerin-36 parts of water-0.2 part of trisodium citrate (pH adjusted) 0.25 µm The mixture was filtered under pressure using a membrane filter of No. 4, and a blue inkjet ink BL-3 having a viscosity of 2.3 cps, a surface tension of 48 dyn / cm, and a pH of 8.0 was prepared.

[0090] In Example 3 the following method, dispersion DY-1 of Example 3 was prepared inkjet ink Y-1. (Dispersion DY-1) 27 parts of PEP-3 (35% aqueous solution of neutralized monoethanolamine, pH 7.0) I. Disperse Yellow 64 Wet Cake Prototype (solid content: 30%) 90 parts. Water 80 parts. Using these materials, a dispersion treatment was performed in substantially the same manner as in Example 1 to prepare a dispersion liquid having a viscosity of 4.5 cps. The obtained dispersion was centrifuged in the same manner as in Example 1 to prepare a dispersion DY-1 having a solid content of 15.5%, an average particle diameter of 155 nm, a surface tension of 45 dyn / cm, and a pH of 7.0. .

(Ink for Ink Y-1)
Using the dispersion DY-1 obtained above, an ink jet recording ink Y-1 was prepared in the following procedure. -Dispersion Y-1 25 parts-Diethylene glycol 20 parts-N-methylpyrrolidone 10 parts-Water 45 parts-Lithium hydroxide aqueous solution A little amount These components are mixed well, and pressure filtration is performed using a 0.25 µm membrane filter. Then, a yellow inkjet ink Y-1 having a viscosity of 2.4 cps, a surface tension of 45 dyn / cm, and a pH of 8.0 was prepared.

[0092] In Example 4 the following method, dispersion DBk-1 of Example 4 was prepared inkjet ink Bk-1 and Bk-2. (Dispersion DBk-1) 15 parts of PEP-4 (35% aqueous solution of neutralized monoethanolamine, pH 7.5) I. Disperse Orange 13 powder 15 parts I. Disperse Red 152 powder 3 parts ・ C. I. Disperse Blue 186 powder 6 parts I. Disperse Blue 264 powder 2 parts ・ Ethylene glycol 10 parts ・ Water 135 parts ・ Defoaming agent Surfynol 104E (manufactured by Nissin Chemical) Some amount ・ Lithium hydroxide aqueous solution (pH adjustment) Some amount Using these materials, implementation A dispersion treatment was performed in substantially the same manner as in Example 1 to prepare a dispersion having a viscosity of 3.6 cps. The obtained dispersion was centrifuged in the same manner as in Example 1 to obtain a dispersion DBk-1 having a solid content of 12.5%, an average particle size of 165 nm, a surface tension of 41 dyn / cm and a pH of 8.0.
Was prepared.

(Ink Jet Ink Bk-1) Next, using the dispersion DBk-1 obtained above, the ink jet recording inks Bk-1 and Bk-1 were obtained in the following procedure.
-2 was produced. -40 parts of dispersion DBk-1-15 parts of urea-10 parts of glycerin-5 parts of ethylene glycol-30 parts of water-a little amount of monoethanolamine These components are mixed well and pressurized using a 0.25 µm membrane filter. After filtration, a black inkjet ink Bk-1 having a viscosity of 2.6 cps, a surface tension of 41 dyn / cm, and a pH of 8.5 was prepared.

(Inkjet ink Bk-2) 40 parts of dispersion DBk-1 15 parts of bis 2-hydroxyethyl sulfone 10 parts of thiodiglycol 0.5 part of sodium lauryl sulfate 0.5 part of water 30 parts of monoethanolamine (PH adjustment) Slight amount These components were mixed well and filtered under pressure using a 0.25 μm membrane filter. The black inkjet ink Bk- having a viscosity of 2.5 cps, a surface tension of 38 dyn / cm, and a pH of 8.5 was obtained. 2 was produced.

[0095] In Example 5 the following method, dispersion DR-1 of Example 5 was prepared inkjet ink R-1. (Dispersion DR-1) 18 parts of PEP-5 (43% aqueous solution of neutralized monoethanolamine, pH 7.8) I. Disperse Red 54 Powder 25 parts ・ Ethylene glycol 10 parts ・ Defoaming agent Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.) Slight amount ・ Water 150 parts Using these materials, dispersion treatment was performed in substantially the same manner as in Example 1. A dispersion having a viscosity of 4.5 cps was prepared. This dispersion was centrifuged in the same manner as in Example 1 to prepare a dispersion DR-1 having a solid content of 13%, an average particle diameter of 125 nm, a surface tension of 38 dyn / cm, and a pH of 7.8.

(Inkjet Ink R-1)
Using the dispersion DR-1 obtained above, an ink-jet recording ink R-1 was produced in the following procedure. -35 parts of dispersion DR-1-10 parts of 2-pyrrolidone-15 parts of triethylene glycol monomethyl ether-5 parts of glycerin-35 parts of water-a little amount of aqueous lithium hydroxide solution These components are mixed well, and a 0.25 µm membrane is mixed. The mixture was filtered under pressure using a filter to prepare a red inkjet ink R-1 having a viscosity of 3.1 cps, a surface tension of 38 dyn / cm, and a pH of 8.0.

[0097] In Example 6 the following method, dispersion DR-2 of Example 6, was prepared inkjet ink R-2. (Dispersion DR-2) 11 parts of PEP-6 (monoethanolamine neutralized 45% aqueous solution, pH 7.8) I. Disperse Red 152 Powder 25 parts ・ Ethylene glycol 5 parts ・ Water 155 parts ・ Ethanol 5 parts Using these materials, a dispersion treatment was performed in substantially the same manner as in Example 1 to prepare a dispersion having a viscosity of 5.5 cps. . The obtained dispersion was centrifuged in the same manner as in Example 1 to prepare a dispersion DR-2 having a solid content of 11.2%, an average particle diameter of 142 nm, a surface tension of 47 dyn / cm, and a pH of 7.8. .

(Inkjet Ink R-2)
Using the dispersion DR-2 obtained above, an ink jet recording ink R-2 was prepared in the following procedure. -Dispersion DR-2 45 parts-Ethylene glycol 10 parts-Glycerin 15 parts-Triethylene glycol mono n-butyl ether 6 parts-Water 24 parts-Lithium hydroxide aqueous solution A little amount The above components were mixed well, and 0.25 µm The mixture was filtered under pressure using a membrane filter to prepare a red inkjet ink R-2 having a viscosity of 2.4 cps, a surface tension of 45 dyn / cm, and a pH of 8.3.

[0099] In Example 7 the following method, dispersion DG-1 of Example 7 was prepared inkjet ink G-1. (Dispersion DG-1) 20 parts of PEP-7 (40% aqueous solution of monoethanolamine neutralized, pH 7.8) I. Disperse Green 9 Powder 25 parts ・ Ethylene glycol 10 parts ・ Defoaming agent Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.) Slight amount ・ Water 145 parts Using these materials, dispersion treatment was performed in substantially the same manner as in Example 1. A dispersion having a viscosity of 3.0 cps was prepared. The obtained dispersion was centrifuged at 8,000 rpm for 20 minutes to obtain a solid content of 10%, an average particle size of 123 nm,
Dispersion DG- having a surface tension of 42 dyn / cm and a pH of 7.8
1 was produced.

(Ink for Ink G-1)
Using the dispersion DG-1 obtained above, an ink-jet recording ink G-1 was prepared in the following procedure. -Dispersion DG-1 35 parts-Diethylene glycol 15 parts-Triethylene glycol 10 parts-Urea 5 parts-Water 35 parts-Lithium hydroxide aqueous solution A little amount These components are mixed well and using a 0.25 µm membrane filter. The mixture was filtered under pressure to prepare a green inkjet ink G-1 having a viscosity of 2.2 cps, a surface tension of 42 dyn / cm and a pH of 8.2.

[0102] In Example 8 the following method, dispersion DY-2 of Example 8, to prepare an inkjet ink Y-2. (Dispersion DY-2) 15 parts of PEP-8 (a 45% aqueous solution of neutralized monoethanolamine, pH 7.0) I. Disperse Yellow 64 Wet cake prototype (solid content: 30%) 80 parts ・ Ethylene glycol 10 parts ・ Water 100 parts Using these materials, a dispersion treatment was performed in substantially the same manner as in Example 1, and a dispersion having a viscosity of 3.5 cps was performed. A liquid was prepared. The obtained dispersion was centrifuged in the same manner as in Example 1 to prepare a dispersion DY-2 having a solid content of 14.5%, an average particle diameter of 155 nm, a surface tension of 47 dyn / cm, and a pH of 7.0. .

(Ink for Ink Y-2)
Using the dispersion DY-2 obtained above, an ink jet recording ink Y-2 was produced in the following procedure. -Dispersion DY-2 35 parts-Ethylene glycol 10 parts-1,2,6-hexanetriol 15 parts-Water 40 parts-Lithium hydroxide aqueous solution a little amount-Sodium lauryl sulfate 0.5 part Mix the above components well The solution was filtered under pressure using a 0.25 μm membrane filter to prepare a yellow inkjet ink Y-2 having a viscosity of 2.5 cps, a surface tension of 38 dyn / cm, and a pH of 8.0.

[0103] In Example 9 the following method, dispersion DCN-1 of Example 9, to prepare an inkjet ink CN-1. (Dispersion DCN-1) 15 parts of PEP-9 (monoethanolamine neutralized 50% aqueous solution, pH 7.5) 15 parts I. Disperse Blue 87 powder 24 parts / ethylene glycol 10 parts / water 130 parts Using these materials, a dispersion treatment was performed in substantially the same manner as in Example 1 to prepare a dispersion having a viscosity of 3.3 cps. The obtained dispersion was centrifuged at 8,000 rpm for 20 minutes to obtain a solid content of 13.0% and an average particle size of 136 n.
m, dispersion D having a surface tension of 47 dyn / cm and a pH of 7.5
CN-1 was produced.

(Inkjet ink CN-1) Dispersion DCN-1 30 parts Diethylene glycol 20 parts Isopropyl alcohol 5 parts Urea 5 parts Water 40 parts Monoethanolamine (pH adjustment) Some amount The mixture was mixed well and filtered under pressure using a 0.25 μm membrane filter to prepare a cyan inkjet ink CN-1 having a viscosity of 2.5 cps, a surface tension of 45 dyn / cm, and a pH of 8.3.

Comparative Example 1 In the dispersion formulation of Example 1, PEP-
1 (45% ammonia neutralized aqueous solution, pH 7.3) instead of Naphthalenesulfonic acid type dispersant Demol N
Dispersion treatment was carried out in exactly the same manner as in Example 1 except that the monoethanolamine salt (manufactured by Kao Corporation) was used, to obtain a dispersion C-1 of Comparative Example 1. The dispersion obtained after centrifugation had a solid content of 18%, a pH of 7.5, and a surface tension of 56 d.
yn / cm, viscosity 5.8 cps, average particle size 250 nm. (Ink Jet Ink C-1) Next, using the dispersion C-1 obtained above, an ink jet recording ink C-1 was prepared in the following procedure. -43 parts of dispersion C-1-15 parts of ethylene glycol-4 parts of isopropyl alcohol-1 part of monoethanolamine-37 parts of water These components were mixed well and filtered under pressure using a 0.25 µm membrane filter. A blue inkjet ink C-1 having a viscosity of 2.2 cps, a surface tension of 46 dyn / cm, and a pH of 9.0 was prepared.

Comparative Example 2 In the dispersion formulation of Example 2, PEP-
In the same manner as in Example 1 except that ligninsulfonic acid type water-soluble resin (Copartin soda Kop-44, manufactured by Kojin Co., Ltd.) was used instead of 2 (aqueous ammonia solution, pH 8.2). Dispersion treatment was performed to obtain Dispersion C-2 of Comparative Example 2. The dispersion obtained after centrifugation has a solid content of 22%, pH 7.7, and a surface tension of 50 dyn / c.
m, viscosity 8.5 cps, and average particle size 300 nm. (Inkjet Ink C-2) Next, using the dispersion C-2 obtained above, an inkjet recording ink C-2 was prepared in the following procedure. -45 parts of Dispersion C-2-10 parts of ethylene glycol-10 parts of glycerin-1 part of monoethanolamine-33 parts of water These components were mixed well, and filtered under pressure using a 1 µm membrane filter to give a viscosity of 2. A blue inkjet ink C-2 having 8 cps, a surface tension of 46 dyn / cm, and a pH of 8.8 was produced.

Comparative Example 3 In the dispersion formulation of Example 2, PEP-
2 (50% aqueous ammonia, pH 8.2) instead of soda salt of styrene-acrylic acid-butyl acrylate copolymer (prototype manufactured by Seiko Chemical Co., Ltd., acid value 150,
Example 1 except that a weight average molecular weight of 9,000) was used.
The dispersion treatment was performed in exactly the same manner as described above, and the dispersion C of Comparative Example 3 was used.
-3. The dispersion obtained after the centrifugation had a solid content of 10%, a pH of 8.0, a surface tension of 50 dyn / cm, a viscosity of 8.5 cps, and an average particle size of 160 nm. (Ink Jet Ink C-3) Next, using the dispersion C-3 obtained above, an ink jet recording ink C-3 was prepared in the following procedure. -45 parts of Dispersion C-3-10 parts of ethylene glycol-10 parts of glycerin-1 part of monoethanolamine-33 parts of water These components were mixed well, and subjected to pressure filtration using a 0.25 µm membrane filter to obtain a viscosity. A blue inkjet ink C-3 having 2.8 cps, a surface tension of 46 dyn / cm, and a pH of 8.8 was produced.

[0108]

TABLE 1 Dispersions, dispersants and dyes used in ink jet recording inks

[Evaluation of Performance] Next, with respect to each of the inks for ink jet recording of the examples and comparative examples obtained above,
Evaluation of printing durability, storage stability, printing performance and dyeability on fabric, and process suitability of fabric dyeing were performed by the following evaluation methods and evaluation criteria. Table 2 shows the evaluation results for each ink with respect to each evaluation item obtained as a result.

Print Durability Test An ink jet recording apparatus equipped with a bubble jet recording head having 64 nozzles at 360 dpi was filled with each of the inks of Examples and Comparative Examples via an ink supply tube. The driving frequency of the recording apparatus is 6.2 kHz, and the amount of a single dot droplet is 80 ng. Under this condition, every other 3
A continuous ejection test of 3 × 10 ⁸ pulses using two nozzles was performed. Judgment is made at the initial stage and after discharging 3 × 10 ⁸ pulses.
A test document including a document, a solid pattern, and a ruled line was printed, and deterioration of printability was evaluated. Table 2 shows the results.

(Evaluation Rank) A: High density, clear characters, no decrease in droplet discharge speed. ：: Vivid characters, uniform and vivid solid printing, ruled line printing without distortion. Δ: Slightly blurred characters, solid printing with reduced density, and ruled line printing with curling. ×: Characters that are blurred and are difficult to read, uneven and thin solid printing, and non-discharges also occurred and disordered ruled line printing. In addition, ◎ and ○ are levels at which there is no practical problem.

Storage stability test 50 ml of each ink jet ink of Examples and Comparative Examples
Into a 100 ml shot heat-resistant bottle and sealed.
An accelerated storage test at 60 ° C. for one month was performed. The determination was made by measuring the viscosity or average particle size after storage and observing the formation of precipitates to determine the quality of storage. Table 2 shows the results. (Evaluation rank) ：: Little change in viscosity and no change in pH. Or
Increase in average particle size is within 20%. ：: The viscosity rise is within 10% of the initial stage, and the amount of precipitate is small. Or, the increase in average particle size is within 20 to 50%. Δ: Change in viscosity was 10 to 50% of the initial value, and precipitation occurred. Alternatively, precipitation occurs and cannot be redispersed. ×: Gelled or hard precipitate. In addition, ○ and ○ are levels at which there is no practical problem.

Printing on Fabric and Dyeing Test Color printing was performed on the fabric using a bubble jet printer BJC-600 (manufactured by Canon Inc.). The cloth used was polyester decine, which was padded with a 1% aqueous solution of polyvinylpyrrolidone, dried (80% squeezing rate), then adhered to a Mylar film with a double-sided adhesive tape, and recorded with a printer. After color printing, the fabric was peeled off from the mylar film, and then subjected to HT steaming treatment at 180 ° C. for 5 minutes. After this, reduction washing is carried out in the usual manner
After washing with water and drying, a polyester print was obtained. For the judgment of the obtained printed matter, the color density, the color tone and the sharpness were evaluated. Table 2 shows the results. (Evaluation rank) A: All good. ：: The boundary between different colors slightly blurred. Δ: Slightly low color density and bleeding. X: Coloring density is slightly low, there is bleeding, and washing fastness is poor.

Process Suitability Test for Fabric Dyeing The same printing and steaming as in “Printing and Dyeing Test on Fabric” was performed using polyester and cotton, and then reduced washing, water washing, and drying were performed in a conventional manner to obtain polyester and cotton. A cotton print was obtained. The obtained printed matter was evaluated for -1 hand and -2 cotton contamination. Table 2 shows the results. (Evaluation rank) -1: Texture evaluation (touch evaluation) ：: Level that has no practical problem. Δ: Somewhat hard but practical range. X: Hard and unusable. -2: Cotton contamination (gray scale evaluation) ：: Grade 4 or higher. Δ: Grade 3 or higher. X: Less than 3rd grade. Table 2 shows the results for the above evaluation items.

[0115]

[Table 2] Table 2: Performance evaluation results

[0116]

As described above, according to the present invention,
For example, fine particles are dispersed in a favorable state in a state where the average particle diameter is 0.25 μm or less, and even when a dispersion having a high solid content is obtained, the dispersion state is low, and the dispersion state is stable for a long time. Thus, an aqueous fine particle dispersion of a disperse dye exhibiting excellent storage stability capable of maintaining a stable state can be obtained. Further, according to the present invention, when an ink for inkjet recording using the above excellent dispersion, shows sufficient suitability for a dyeing process such as reducing washing properties and cotton stainability after dyeing, When color recording is performed on the fabric, the dyeing stability is excellent, and the resulting dyed product is excellent in color developability, fastness, texture, and cotton stainability.
Furthermore, according to the present invention, a writing implement, a fine particle dispersion for ink jet recording, particularly when performing recording using an ink jet recording apparatus using a bubble jet method, a stationery, a color printer using a disperse dye for recording Provides waterborne fine particle dispersions of disperse dyes with high practical value that can be used for designing recording agents for various applications such as color plotters, poster printing, signboard printing, light printing, textile printing, color filters for liquid crystal displays, etc. Is done.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a head of an ink jet recording apparatus.

FIG. 2 is a cross-sectional view of a head of the inkjet recording apparatus.

FIG. 3 is an external perspective view of a head obtained by multiplying the head shown in FIG. 1;

FIG. 4 is a perspective view illustrating an example of an ink jet recording apparatus.

FIG. 5 is a vertical sectional view of the ink cartridge.

FIG. 6 is a perspective view illustrating an example of a recording unit.

[Explanation of symbols]

 13: Head 14: Ink groove 15: Heating head 16: Protective film 17-1, 17-2: Aluminum electrode 18: Heating resistor layer 19: Heat storage layer 20: Substrate 21: Ink 22: Discharge orifice (fine hole) 23 : Meniscus 24: Ink droplet 25: Recording material 26: Multi-groove 27: Glass plate 28: Heating head 40: Ink bag 42: Plug 44: Ink absorber 45: Ink cartridge 51: Paper feed unit 52: Paper feed roller 53: paper discharge roller 61: blade 62: cap 63: ink absorber 64: ejection recovery unit 65: recording head 66: carriage 67: guide shaft 68: motor 69: belt 70: recording unit 71: head unit 72: atmosphere communication mouth

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Tomoya Yamamoto, Inventor 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Mariko Suzuki 3- 30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Shinichi Hakamada 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Cloth 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (5)

[Claims] 1. An aqueous fine particle dispersion containing at least water, a water-soluble organic solvent, a disperse dye and a water-soluble polyester, wherein the water-soluble polyester is a water-soluble polyester having an acid value of 100 to 250, and An aqueous fine particle dispersion of a disperse dye, wherein the average particle size of the fine particles is adjusted to 0.25 μm or less. 2. The aqueous fine particle dispersion of a disperse dye according to claim 1, wherein the water-soluble polyester is an anionic water-soluble polyester obtained by using a carboxylated diol as at least one of the diol components. 3. The aqueous fine particle dispersion of a disperse dye according to claim 1, wherein the water-soluble polyester is an anionic water-soluble polyester obtained by using a sulfonated diol as at least one of the diol components. 4. A disperse dye ink for inkjet recording, comprising at least an aqueous fine particle dispersion of the disperse dye according to any one of claims 1 to 3, and water and a moisturizing solvent. 5. A fabric dyeing method for forming an image on a fabric using an ink jet recording apparatus using thermal energy as a discharge source of ink droplets, wherein the ink is the ink according to claim 4. Fabric dyeing method.