JP2006160818A - Manufacturing method of pigment dispersion and pigment dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a pigment dispersion realizing color matching comparable to a dye and giving a printed matter having high fastness, and comprising a simple environment-conscious process. <P>SOLUTION: The manufacturing method of the pigment dispersion comprises dispersing in water a pigment which has at least a part of interlayer ions in an interlayer compound ionically replaced by a dye ion having an opposite polarity to the interlayer ions, where the ion replacement of the interlayer ions by the dye ion and dispersion in water and atomization of the pigment is carried out in the same reaction vessel. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a pigment dispersion to be contained in an aqueous coloring liquid, and also relates to a pigment dispersion produced using the same.

  In recent years, with the widespread use of personal computers and the like, it has been required to display image information and the like created by the personal computers on recording paper in the same way as silver halide photographs. As a means for printing on the recording paper, an ink jet recording method is used in which solution-like ink is ejected from the nozzle onto the recording paper using an electric field, heat, pressure, or the like as a drive source, and an image is formed with the ink to perform printing. ing.

  In the ink jet recording method, water-based ink is generally used as ink, and recording paper having a dye-receiving layer formed on a support is generally used as recording paper.

  Note that the water-based ink coloring material is used for printing and photographic applications with office automation equipment used indoors, from the viewpoint of convenience that it is difficult to be clogged and the maintenance of the apparatus is easy, or the image is high. Due to its quality, water-soluble dyes are generally used. On the other hand, pigments with excellent image durability are generally used for industrial applications such as printing on posters and signboards or cardboard paper used outdoors. Hereinafter, a water-based ink using a dye as a color material is referred to as a dye ink, and a water-based ink using a pigment as a color material is referred to as a pigment ink.

  As pigments used in pigment inks, organic pigments having a specific molecular structure typified by phthalocyanines and quinacridones tend to be used rather than inorganic pigments having safety problems.

  However, since such organic pigments are limited in kind, there are limitations in the synthesis technology to reproduce full color, and it is difficult to obtain an arbitrary toning. In addition, when the refractive index of the molecular aggregate itself constituting the pigment is relatively large, light scattering on the pulp increases when printed on plain paper, and is susceptible to multiple internal reflections. It is expected that the saturation of the image is lowered and that the particles do not penetrate into the receiving layer when printed on glossy paper, and the scattered light derived from the particle diameter is reflected to reduce the saturation. In addition, since the molecular extinction coefficient of general organic molecules tends to decrease due to association, the organic pigment has a lower coloring power than the dye at the same addition amount. When the coloring power and saturation are lowered, the sharpness of the image is deteriorated.

  In addition, in order to put pigment ink into practical use, use a pigment with a small particle size so as not to cause clogging at the nozzle tip where the opening is narrowing with higher definition, and excellent dispersion over a long period of time. It is also required to ensure stability.

For this reason, the proposal about the manufacturing apparatus for refinement | miniaturizing the particle size of a pigment to a colloid level (for example, refer patent document 1), and the proposal about the resin-type dispersing agent for improving dispersion stability (for example, patent) References 2 and 3) have been made. In addition, there is an example of preparing a pigment ink by ion substitution of interlayer ions in an interlayer compound with a dye having opposite ionicity (see, for example, Patent Document 4), but ion substitution and water dispersion of the pigment are performed in separate steps. The cost reduction seems to be insufficient for this purpose. In addition, environmental considerations are not possible because of the use of organic solvents.
US Pat. No. 4,533,254 US Pat. No. 4,597,794 US Pat. No. 5,229,786 Japanese Patent Laid-Open No. 10-46049

  Therefore, in the present invention, in consideration of the conventional situation, it is possible to obtain a color matching comparable to water-based ink using a dye, and the printed matter has high fastness and can be manufactured by a simple process considering the environment. Thus, it is an object of the present invention to provide a method for producing a pigment dispersion capable of reducing the cost and a pigment dispersion produced using the method for producing a pigment dispersion.

  The above object is achieved by the present invention described below.

  A method for producing a pigment dispersion in which at least a part of interlayer ions in an interlayer compound is dispersed in water with a pigment ion-substituted by dye ions having a polarity opposite to that of the interlayer ions. Ion substitution with dye ions, water dispersion and atomization of the pigment are performed in the same reaction vessel, and pigment dispersion produced using the pigment dispersion production method liquid.

  A pigment dispersion containing a pigment in which at least a part of interlayer ions in the interlayer compound is ion-substituted by dye ions having a polarity opposite to that of the interlayer ions in a dispersed state, the ion substitution and water dispersion of the pigment And the pigment is dispersed in water together with a dispersant and a surfactant without using an organic solvent having a flash point of 200 ° C. or lower. A pigment dispersion characterized by the above.

  According to the present invention, since it is not necessary to form a dye receiving layer on the recording material side, a color matching comparable to the dye can be obtained without selecting the type of the recording material. Moreover, since it can be manufactured by a simple process, the cost can be reduced as compared with the case of using a conventional pigment. Furthermore, since the image formed using this pigment has saturation, resolution, and durability comparable to silver salt photographic images, it can be used satisfactorily as ID photographs or printed materials for outdoor display. Become.

  The method for producing a pigment dispersion according to the present invention achieves the above-mentioned object, and the pigment used in the pigment dispersion is mainly composed of an interlayer compound, and at least a part of interlayer ions in the interlayer compound includes: It is ion-substituted with a specific dye ion having a polarity opposite to that of the interlayer ion.

  That is, the present invention uses the intercalation compound as a pigment by utilizing that the dye can be fixed and held by an intercalation reaction based on an ion exchange action.

  Here, the intercalation compound is preferably a hydrotalcite or a montmorillonite having a smectite structure, and in any case, at least a part of the remaining interlayer ions ion-substituted with the dye ions, ideally all are hydrophilic. It is preferable that ion substitution is performed with ions. If the ion substitution amount of the dye ions is small, the coloring power becomes insufficient, so that an image formed using the pigment ink using this pigment becomes unclear.

  When the intercalation compound is composed of hydrotalcite, the hydrotalcite is preferably a fired natural clay represented by the following general formula.

(General formula)
_{M x Al y (OH) 2} · mCO 3 · nH 2 O
(Wherein M is Mg and / or Zn, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ m ≦ 2, 0 ≦ n ≦ 2, x + y = 1)
When the intercalation compound is hydrotalcite, it is preferable that the dye ion ion-substituted with at least a part of the intercalation ions is a direct dye ion or an acid dye ion. When an anionic dye such as a direct dye or an acid dye is adsorbed between the layers of hydrotalcites, the light resistance and gas resistance can be remarkably increased. In addition, when adsorbing anionic dyes such as direct dyes and acid dyes between the layers of hydrotalcite, when the pigment is finely divided and dispersed at the same time, it contains water of crystallization and / or contains fat and oil components on the surface. Those that do not show particularly high ion substitution.

  In addition, if the intercalation ions of hydrotalcites are sufficiently ion-replaced with the above-mentioned anionic dyes and hydrophilic ions so that other ions are not adsorbed between the layers, the water dispersibility can be controlled appropriately. Become.

  On the other hand, when the intercalation compound is montmorillonite, the dye ion ion-replaced with at least a part of the interlayer ions is preferably a basic direct dye ion or a cationic dye ion, and at least a part of the other interlayer ions The hydrophilic ion to be ion-substituted is preferably a hydrogen ion. Light resistance can be increased by adsorbing a basic direct dye or cationic dye together with hydrogen ions between montmorillonite layers. This is because basic direct dyes and cationic dyes have the property that light resistance increases in an acidic atmosphere. Therefore, among the montmorillonite interlayer ions, those that are not ion-substituted by the above-mentioned dye due to steric hindrance are preferably ion-substituted by hydrogen ions as much as possible.

  If the interlayer ions of montmorillonites are sufficiently ion-replaced with the above-mentioned dyes and hydrogen ions so that other ions are not adsorbed between the layers, the water dispersibility can be controlled appropriately.

  The following can be said about the dispersant used in the pigment ink using the pigment dispersion according to the present invention.

  In both cases where the intercalation compound is hydrotalcite or montmorillonite, it is preferable to use 20% to 200% by weight of a nonionic resin or a surfactant as the dispersant. By using a nonionic resin and a surfactant, the ion substitution rate can be increased without affecting the ion substitution.

  Ion substitution, pigment water dispersion, and micronization are preferably performed using shearing force, and a ball mill, sand mill, paint shaker, homogenizer, microfluidizer, or the like can be used.

  Hereinafter, specific embodiments of the present invention will be described. The pigment dispersion according to the present invention is a method for producing a pigment dispersion in which a pigment in which at least part of interlayer ions in an interlayer compound is ion-substituted by dye ions having a polarity opposite to that of the interlayer ions is dispersed in water. In this pigment dispersion, the ion substitution of the interlayer ions into the dye ions and the water dispersion and atomization of the pigment are performed in the same reaction vessel.

  That is, in the present invention, an intercalation compound capable of fixing and holding a dye by an intercalation reaction based on an ion exchange action is used as a pigment.

  Here, the interlayer compound may be a layered inorganic substance having a layered structure and having exchangeable ions capable of ion exchange with water-soluble dyes between the hydrophilic layers.

  The exchangeable ion of the layered inorganic substance includes an exchangeable cation such as sodium ion when the water-soluble dye is a water-soluble cationic dye, and a carboxyl anion or the like when the water-soluble dye is a water-soluble anion dye. It becomes an exchangeable anion such as carbonate ion.

  Examples of the layered inorganic substance having an exchangeable cation (hereinafter referred to as a cation exchangeable intercalation compound) include natural or synthetic layered silicates or fired bodies thereof. Montmorillonites having a body type smectite structure can be preferably used.

  Specifically, depending on the combination of X and Y and the number of substitutions, montmorillonite, magnesia montmorillonite, iron montmorillonite, iron magnesia montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontronite, saponite, aluminian Examples thereof include natural products and synthetic products such as saponite, hectorite, and soconite. In addition, those in which the OH group in the above general formula is substituted with fluorine can also be used.

  In addition to montmorillonites, mica such as sodium silicic mica, sodium teniolite, lithium teniolite can be used as the cation exchangeable intercalation compound. Further, as in the case of the synthetic clay mineral, examples of the cation exchangeable intercalation compound having a layered structure and having exchangeable cations include acidic salts such as zirconium phosphate and layered hydrous titanium oxide. These have optical hiding properties or inherent colors, and can be used when transparency, glossiness, and whiteness are not required at the same time.

  In addition, there are amorphous synthetic silicas and the like as synthetic silicates that have a strong affinity with cationic dyes, but these have a dye fixing ability in a high dielectric constant medium such as water, that is, an ion exchange ability compared to montmorillonites. Not enough. However, it can also be used when high ion exchange capacity is not required.

  When a fine powder showing pure white, such as a synthetic silicate that does not contain impurities, is used as the above-described cation-exchangeable intercalation compound, the fine powder crystal itself is optically transparent, which is comparable to a silver salt photograph. It is possible to form a pigment that achieves such high saturation.

  In addition, the exchangeable cation which exists between the layers of the above-mentioned cation exchangeable intercalation compound is replaced with an organic cation which realizes the effect of extending the interlayer distance (pillar effect) and the effect of partially hydrophobizing the interlayer. It may be. Examples of such organic cations include quaternary ammonium ions, phosphonium ions, alkylphosphonium ions, and arylphosphonium ions. In the case of ion substitution with a quaternary ammonium ion, at least three of the four alkyl groups each have 4 or more carbon atoms, preferably 8 or more carbon atoms. When the number of long-chain alkyls is small, the pillar effect is not sufficient, and it becomes difficult to secure an interlayer as a fixing seat (exchangeable inorganic cation).

On the other hand, as a layered inorganic substance having an exchangeable anion (hereinafter referred to as anion exchangeable intercalation compound), it is a kind of 0: 1 type clay mineral and is a layered hydrotalcite composed of an AlO ₆ octahedron sheet. Can be preferably exemplified.

  Synthetic hydrotalcite is also commercially available, although it is slightly different from the composition of natural hydrotalcite. The fine powder of this synthetic hydrotalcite does not contain impurities and exhibits a pure white color, but the crystal itself is optically transparent, so when using this fine powder, the high saturation comparable to that of a silver salt photograph is obtained. It is possible to form a realized pigment.

In the present invention, it is particularly preferable to use a calcined body of hydrotalcite represented by a composition formula of Mg _0.75 Al _0.25 (OH) ₂ .0.13 CO ₂ .0.5H ₂ O.

  In addition to the hydrotalcites described above, examples of anion-exchangeable intercalation compounds include hydrous oxides such as titanium, zirconium, lanthanum, and bismuth, and phosphate phosphates, which are optically concealed or inherent. Therefore, it can be used when transparency, glossiness, and whiteness are not required at the same time.

  The exchangeable anions present between the layers of the above-mentioned anion exchangeable intercalation compounds are ion-substituted with organic anions that realize the effect of extending the interlayer distance (pillar effect) and the effect of partially hydrophobizing the interlayer. May be. Examples of such an organic anion include a carboxylate anion, a sulfonate anion, an ester anion, and a phosphate ester anion. Such anions usually have an alkyl group or an alkenyl group, but when their carbon number is small, the pillar effect is not sufficient, and it becomes difficult to secure a layer as a fixing seat (exchangeable inorganic anion). When the amount is too large, it is difficult to perform ion substitution.

  When a cation-exchange layered compound such as montmorillonite is used as an intercalation compound capable of fixing and retaining a dye by an intercalation reaction based on an ion exchange action, an anion-exchange layered compound such as hydrotalcite is used. In any case, it is preferable that at least a part of the remaining interlayer ions ion-substituted with the dye ions, ideally all of them are ion-substituted with hydrophilic ions. If the ion substitution amount of the dye ions is small, the coloring power becomes insufficient, so that an image formed using the pigment ink using this pigment becomes unclear.

  When the intercalation compound is composed of montmorillonites, the dye ion ion-replaced with at least part of the intercalation ions is a basic dye, in particular, at least one of a cationic dye and a basic direct dye, and at least the remaining intercalation ions The hydrophilic ion to be ion-substituted with a part is preferably a hydrogen ion.

  Here, as the cationic dye, an azo dye having an amine salt or a quaternary ammonium group, a triphenylmethane dye, an azine dye, an oxazine dye, a thiazine dye, or the like can be used. Specifically, the following dyes can be exemplified.

As yellow, C.I. I. Basic yellow: 1, 2, 11, 13, 14, 19, 21, 25, 28, 32, 33, 34, 35, 36, etc. I. Basic Red: 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 38, 39, 40, etc., C.I. I. Basic violet: 7, 10, 15, 21, 25, 26, 27, 28, etc. As cyan, C.I. I. Basic blue: 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 44, 45, 47, 54, 58, 59, 60, 64, 65 , 66, 67, 68, 75, etc. I. Basic Black: 2, 8, etc. These cationic dyes usually have an inorganic anion as a counter ion, and many of them exist as strong acid salts. Therefore, since the aqueous solution generally shows acidity, it is preferable to neutralize with a basic salt in order to prevent corrosion of the metal member in contact with the ink composition containing such a cationic dye. For example, it is preferable that an inorganic anion as a counter ion be treated with a soda salt of an organic anion such as a carboxylate ion to perform ion substitution with the organic anion. In this case, in order not to reduce the affinity of the interlayer compound for the cationic dye, it is preferable not to reduce the affinity of the interlayer compound by salt formation with an organic anion.

  Further, as the basic direct dye, trade name: Pergasol F (manufactured by CibaGeigy), trade name: Cartasol K (manufactured by Sandoz), trade name: Levacell C (manufactured by Bayer), trade name: Fastusol C (manufactured by BASF), etc. Can be mentioned.

  In addition, in order to ion-replace the remaining interlayer ions not ion-substituted with the dye ions as described above, for example, a cation exchange layered compound such as montmorillonite may be introduced into a liquid containing hydrochloric acid. .

  Light resistance can be improved by adsorbing basic dyes such as the above basic direct dyes or cationic dyes between montmorillonite layers together with hydrogen ions. This is because basic dyes such as basic direct dyes and cationic dyes have the property of improving light resistance in an acidic atmosphere. Accordingly, among the montmorillonite interlaminar ions, those that are not ion-substituted by the above-mentioned dye due to steric hindrance are preferably ion-substituted by hydrogen ions as much as possible.

  In addition, when the interlayer ions of montmorillonites are sufficiently ion-replaced with the dyes and hydrogen ions as described above and other ions are not adsorbed between the layers, the water dispersibility can be improved when this is used as an ink. It becomes possible to control appropriately.

  On the other hand, when the intercalation compound is hydrotalcite, it is preferable that the dye ion ion-replaced with at least part of the intercalation ions is an anionic dye, that is, at least one of a direct dye and an acid dye.

  Here, the anionic dye has a monoazo group, a diazo group, an anthraquinone skeleton, a triphenylmethane skeleton, etc. as a chromophore, and an anionic dye such as 1 to 3 sulfonic acid groups or carboxyl groups in the molecule. Those having a water-soluble group can be used. Specific examples include the following.

As a yellow direct dye, C.I. I. Direct yellow: 1, 8, 11, 12, 24, 26, 27, 28, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100, 110, etc. Magenta direct dye As C.I. I. Direct Red: 1, 2, 4, 9, 11, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83 84, 89, 95, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230, 321, etc. C. I. Direct blue: 1, 2, 6, 8, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 90, 98, 106, 108, 120, 158, 160, 163, 165, 168 192.193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, etc. I. Direct black: 17, 19, 22, 32, 38, 51, 56, 62, 71, 74, 75, 77, 94, 105, 106, 107, 108, 112, 113, 117, 118, 132, 133, 146 In addition, as a yellow acid dye, C.I. I. Acid Yellow: 1, 3, 7, 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 59, 61, 70, 72, 75, 76, 78, 79, 98 99, 110, 111, 112, 114, 116, 118, 119, 127, 128, 131, 135, 141, 142, 161, 162, 163, 164, 165, etc. I. Acid Red: 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 37, 42, 51, 52, 57, 75, 77, 80, 82, 83, 85, 87, 88 89, 92, 94, 97, 106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, 180, 183 , 184, 186, 194, 198, 199, 209, 211, 215, 216, 217, 219, 249, 252, 254, 256, 257, 262, 265, 266, 274, 276, 282, 283, 289, 303 317, 318, 320, 321, 322, etc. As a cyan acid dye, C.I. I. Acid Blue: 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78, 80, 82, 83, 90 , 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167 168, 170, 171, 175.182, 183, 184, 187, 192, 199, 203, 204, 205, 229, 234, 236, etc. Black acid dyes include C.I. I. Acid Black: 1, 2, 7, 24, 26, 29, 31, 44, 48, 50, 51, 52, 58, 60, 62, 63, 64, 67, 72, 76, 77, 94, 107, 108 109, 110, 112, 115, 118, 119, 121, 122, 131, 132, 139, 140, 155, 156, 157, 158, 159, 191, etc. In the present invention, dye ions are adsorbed between the layers. Further, light fastness and gas resistance can be further improved by adsorbing together fastening agents such as ultraviolet absorbers, antioxidants, and light stabilizers. As the above substances, general hardening agents can be used, such as benzotriazoles, benzophenones, salicylic acids, phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, phenylenediamines, ketones. / Amine condensates, diarylamines, diphenylamine derivatives, naphthylamines, hindered amines and hindered phenols can be preferably exemplified. The aforementioned compound is preferably used in an amount of 0.1 to 3.0 in terms of molar ratio to the dye, and more preferably 0.5 to 2.0 in terms of color developability.

  The pigment and the pigment dispersion having the above-described configuration are mainly composed of an intercalation compound, and at least a part of intercalation ions in the intercalation compound is ion-substituted with a specific dye ion having a polarity opposite to that of the intercalation ion. The pigment is dispersed in water together with a dispersant and a surfactant, and is preferably used as a coloring liquid.

  Here, nonionic polyoxyethylene or poly (oxyethylene-block-oxypropylene) resin is used as a dispersant used together with the above-described pigment when preparing a pigment dispersion, and is 10 wt% to 200 wt% with respect to the pigment. It is preferable to use by weight. From the viewpoint of color development, it is more preferable to use 20 to 150% by weight.

  Further, nonionic polyoxyethylene or polyoxyethylene derivative is preferably used in an amount of 5 to 50% by weight based on the pigment as the surfactant used together with the above-mentioned pigment when preparing the pigment dispersion. From the viewpoint of foamability, it is more preferable to use 10 to 30% by weight.

  When the pigment dispersion liquid according to the present invention having the above-described configuration is used, a dye receiving layer is not required on the recording material side when a printed material is produced, and therefore a recording material is not selected. For this reason, as the recording material, any of those generally used as a support for recording paper can be used, for example, paper such as plain paper and synthetic paper, or plastic films such as polyethylene terephthalate, Furthermore, what coated the plastics on paper etc. is mentioned.

  As described above, in the pigment dispersion according to the present invention, a pigment in which dye ions are firmly fixed between layers of an intercalation compound by an intercalation reaction based on an ion exchange action is used. Therefore, it is possible to form an image having excellent storage stability, fixing property, and durability with color matching comparable to that of the dye. In addition, the saturation and resolution of the image are sufficiently secured.

  Hereinafter, preferred embodiments to which the present invention is applied will be described based on experimental results. In this experiment, a pigment dispersion was prepared using hydrotalcite and smectite as interlayer compounds, dyes and pigments as dyes, and various fastening agents, and various properties were evaluated.

  Tables 1, 2 and 3 show the contents of the dye, intercalation compound and fastening agent used, respectively.

＜実施例１＞
前記の表１〜３及び下記に示す調合液をマヨネーズ瓶（容量：１４０ｃｃ）にとり、ジルコニアビーズ（比重：６．０ｇ／ｃｍ^３、直径：０．５ｍｍ）を２８０重量部加えて密栓し、ペイントシェーカー（東洋精機製）にて１５時間振とうして、層間化合物における層間イオンを染料イオンにイオン置換させた顔料サンプルａを得た。さらに、顔料サンプルａの分散液を脱イオン水で２倍に希釈して評価サンプルＡとした。

<Example 1>
Take the prepared liquids shown in Tables 1 to 3 and below in a mayonnaise bottle (capacity: 140 cc), add 280 parts by weight of zirconia beads (specific gravity: 6.0 g / cm ³ , diameter: 0.5 mm), seal tightly, and paint Shaking with a shaker (manufactured by Toyo Seiki Co., Ltd.) for 15 hours to obtain a pigment sample a in which interlayer ions in the interlayer compound were replaced with dye ions. Furthermore, the dispersion liquid of the pigment sample a was diluted twice with deionized water to obtain an evaluation sample A.

(Mixed solution)
Intercalation compound A 1.9 parts by weight Nonionic dispersion resin 1.9 parts by weight (Daiichi Kogyo Seiyaku, trade name: Epan 785)
-Nonionic surfactant 0.38 part by weight (Daiichi Kogyo Seiyaku, trade name: EA-177)
-Dye 1 1.9 parts by weight-Deionized water 21.6 parts by weight <Example 2>
In Example 1, a pigment sample was prepared in the same manner as in Example 1 by adding the fastening agent 2 in Table 3 so that the molar ratio with respect to the dye was 1.0, and a pigment sample b was obtained. Further, an evaluation sample was prepared in the same manner as in the evaluation sample A using the dispersion liquid of the pigment sample b, and used as an evaluation sample B.

<Examples 3-33>
In the same manner as in Example 1 or Example 2, a pigment sample was prepared by appropriately changing the dye, the intercalation compound, and the fastening agent to obtain a pigment sample c. Further, an evaluation sample was prepared in the same manner as the evaluation sample A using the dispersion liquid of the pigment sample c, and used as an evaluation sample C.

<Comparative Examples 1-20>
Excluding the intercalation compound of Example 1, using dyes 1 to 6 listed in Table 1 as appropriate, and adding a fastening agent as appropriate as in Example 2, and pigment samples as in Example 1 or Example 2. And a pigment sample was obtained. Further, an evaluation sample was prepared in the same manner as the evaluation sample A using a pigment sample dispersion, and used as an evaluation sample.

<Comparative Examples 21-23>
A pigment sample was prepared in the same manner as in Example 1 except that the intercalation compound of Example 1 was used and the dyes 9 to 11 shown in Table 1 were used as appropriate. Further, an evaluation sample was prepared in the same manner as the evaluation sample A using a pigment sample dispersion, and used as an evaluation sample.

(Characteristic evaluation)
Here, each evaluation sample obtained as described above was used to evaluate dispersibility and produce an image sample, and the density, light resistance, and gas resistance of the image sample were evaluated.

  Image samples were prepared by using a bar coater (# 0003) for each evaluation sample obtained as described above, photo glossy paper for inkjet printers (product name: PR101) and plain paper (product name: Canon product, product) Name: PB paper).

  In the evaluation of the image sample, first, the color density (reflection) was measured in order to examine the density of each image sample. The color type to be measured is the color type of the pigment. That is, the cyan density is measured for a cyan dye, the magenta density for a magenta dye, and the yellow density for a yellow dye. Hereinafter, the initial color density is used.

  Evaluation was performed according to the following criteria.

Evaluation criteria 1. Dispersibility Each sample was diluted to a predetermined concentration, and the dispersed particle size was evaluated using a particle size distribution meter (trade name: UPA-150, manufactured by Microtrac). Moreover, the sample to which no pigment was added was visually evaluated.

○: Average particle diameter of less than 100 nm or visually transparent Δ: Average particle diameter of 100 nm or more, less than 300 nm, or slightly aggregated ×: Average particle diameter of 300 nm or more, or aggregation precipitation Color developability The initial color density of each image sample (the glossy paper described above) was evaluated.

○: Initial color density of 2.2 or more Δ: Initial color density of 1.8 or more and less than 2.2 ×: Initial color density of less than 1.8 Water resistance Each image sample (the above-mentioned plain paper) was immersed in water for a predetermined time, the color density after drying was measured, the density retention with respect to the initial color density was determined, and the water resistance was evaluated.

Color density after water resistance test / initial color density (%)
○: 85% or more Δ: 70% or more, less than 85% ×: less than 70% Light Resistance Each image sample (the above glossy paper) was irradiated with light for 70 hours using a light resistance tester (manufactured by Shimadzu Corporation, Suntester XF-180CPS). The color density after the test was measured, the density retention with respect to the initial color density was determined, and the light resistance was evaluated.

Color density after light resistance test / initial color density (%)
◎: 90% or more ○: 75% or more, less than 90% Δ: 50% or more, less than 75% ×: less than 50% Gas Resistance Each image sample (the above glossy paper) was exposed for 2 hours under conditions of a temperature of 40 ° C. and a relative humidity of 55% using an ozone tester (manufactured by Suga Test Instruments, ozone weather meter). The color density after the test was measured, the density retention with respect to the initial color density was determined, and the gas resistance was evaluated.

Color density after ozone resistance test / initial color density (%)
A: 90% or more B: 75% or more, less than 90% Δ: 50% or more, less than 75% ×: less than 50% The evaluation results are shown in Tables 4 and 5.

表４及び５より、染料、層間化合物及び／又は堅牢化剤を用いて形成された画像サンプルにおいては、分散性が良好で染料単独であるサンプルと同等の発色性を確保し、加えて、高い耐水性及び、色調がほとんど変化しないレベルの高い耐光性、耐ガス性を示した。

From Tables 4 and 5, image samples formed using dyes, intercalation compounds, and / or fastening agents ensure good color developability as compared to samples with good dispersibility and dyes alone, in addition, high It showed water resistance and high light resistance and gas resistance at a level where the color tone hardly changed.

  In contrast, image samples formed using pigments as dyes showed high levels of water resistance, light resistance, and gas resistance with almost no change in color tone, but the color development was significantly inferior. .

  From the above results, a pigment dispersion composed of a pigment in which interlayer ions of an interlayer compound are sufficiently ion-substituted with dye ions has excellent dispersibility, and an image formed with this dispersion exhibits excellent fixability. It was found to have excellent color density, light resistance and gas resistance.

Claims (10)

  A method for producing a pigment dispersion in which at least a part of interlayer ions in an interlayer compound is dispersed in water with a pigment ion-substituted by dye ions having a polarity opposite to that of the interlayer ions. A method for producing a pigment dispersion, characterized in that ion substitution with dye ions, water dispersion of the pigment, and micronization are performed in the same reaction vessel.   The method for producing a pigment dispersion according to claim 1, wherein the ion substitution, water dispersion, and micronization are performed by shearing force.   The method for producing a pigment dispersion according to claim 1 or 2, wherein the intercalation compound is hydrotalcite.   The method for producing a pigment dispersion according to claim 1 or 2, wherein the intercalation compound is a montmorillonite having a smectite structure. The method for producing a pigment dispersion according to claim 3, wherein the hydrotalcite is represented by the following general formula.
(General formula)
_{M x Al y (OH) 2} · mCO 3 · nH 2 O
(Wherein M is Mg and / or Zn, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ m ≦ 2, 0 ≦ n ≦ 2, x + y = 1)   The method for producing a pigment dispersion according to any one of claims 1 to 5, wherein the dye ion is selected from the group consisting of a direct dye ion, an acidic dye ion, a basic direct dye ion, and a cationic dye ion.   The pigment dispersion liquid manufactured using the manufacturing method of the pigment dispersion liquid of any one of Claims 1-6.   A pigment dispersion containing a pigment in which at least a part of interlayer ions in the interlayer compound is ion-substituted by dye ions having a polarity opposite to that of the interlayer ions in a dispersed state, the ion substitution and water dispersion of the pigment And the pigment is dispersed in water together with a dispersant and a surfactant without using an organic solvent having a flash point of 200 ° C. or lower. A pigment dispersion characterized by the above.   The pigment dispersion according to claim 8, wherein the dispersant is a nonionic water-soluble resin, and the water-soluble resin is contained in an amount of 10 wt% to 200 wt% with respect to the pigment.   The pigment dispersion according to claim 8 or 9, wherein the surfactant is a nonionic surfactant and is contained in an amount of 5 to 50% by weight based on the pigment.