JP3055673B2 - Coloring composition for image recording - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic printing,
The present invention relates to an image recording agent for image recording such as electrostatic recording, thermal transfer recording, and ink jet recording, or a coloring composition used for producing the same. More specifically, the present invention relates to a recording agent for image recording containing a pigment and a resin, wherein the pigment has excellent fastness, transparency, sharpness, etc., and a yellow monoazo pigment having a very fine particle diameter. It is intended to provide a colored composition for image recording, which is a composition.

[0002]

2. Description of the Related Art Conventionally, yellow or mixed green, which is used for image recording such as full-color or mono-color electrophotography, electrostatic printing, electrostatic recording, thermal transfer recording, ink jet recording, and the like.
As yellow pigments used for yellowish red, orange or black recording agents, yellow oil-soluble dyes, dispersible dyes, disazo yellow azo pigments and ordinary monoazo yellow pigments have been used.

[0003]

However, since oil-soluble dyes and dispersible dyes can be dissolved and colored when coloring a resin medium, the coloring power is high, but the light resistance and solvent resistance are high. In addition, there is a problem in that it is inferior in fastness such as chemical resistance. In addition, disazo yellow azo pigments and ordinary monoazo yellow pigments also have insufficient fastness such as heat resistance, resulting in opacity and dullness. Therefore, the object of the present invention is to
An object of the present invention is to provide a coloring composition for image recording which is excellent in various properties including fastness.

[0004]

The above object is achieved by the present invention described below. That is, the present invention relates to an image recording coloring composition containing a dye and a resin, wherein the image recording method is an inkjet method, and the dye is a yellow monoazo having a specific structure represented by the following formula (I). 99.8 to 80 mol% of a pigment, represented by the formula (I), but having a substituent different from the above monoazo pigment, and / or a yellow monoazo pigment represented by the following formula (II): the 0.2 to 20 mol% was produced during pigment synthesis, a yellow monoazo pigment compositions are mixed, the upper
An image recording coloring composition, wherein the pigment composition has an average particle diameter of 0.2 μm or less .

Embedded image (However, X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ and Y ₃ in the above formula are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, 1-3 alkoxyl groups, halogen atoms, nitro groups, sulfo groups or alkaline earth metal salts thereof, N-phenylaminosulfonyl groups,
Carboxyl group or an alkaline earth metal salt thereof, carboamide group, N-phenylcarbamoyl group, ureylene group,
It is an iminodicarbonyl group or a carboxylic ester group. )

[0005]

The present inventors have conducted various studies on the development of a yellow pigment which solves the above-mentioned deficiencies of the conventional recording agent, is excellent in coloration, and can satisfy various fastnesses and economy. Monoazo pigments adopt a specific manufacturing method, making the particle size smaller and improving heat resistance compared to conventional pigments used for paints and plastic coloring, etc., resulting in sharpness and sharpness of hue. It has been found that excellent properties such as transparency and the like can be exhibited, and various physical properties can be satisfied. By using this as a coloring agent for an image recording agent, an excellent image recording agent can be obtained. The present invention has been completed. That is, conventionally, when using azo pigments for coating, plastics, coloring synthetic fibers, etc., in order to emphasize color concealment and coloration, the average particle diameter of the azo pigments is adjusted to be large. Although the heat resistance is increased by reducing the rate of change, the colorant for the image recording agent lacks sharpness, transparency and clearness of hue.
Since the image recording agent is used in full color or in an overhead projector, it is desired that the image recording agent has sharpness, clearness, and transparency of hue.

In the production of an electrophotographic dry developer or the like, the mixture is often heated and kneaded at a temperature of about 100 to 150 ° C., and under such heating conditions, pigment particles grow,
Changes in crystals often change the color tone, dull the color, decrease the color density, or make the color opaque. In the present invention, in synthesizing the target azo pigment, the color and physical properties are similar to that,
By simultaneously synthesizing azo pigment compounds with different structures,
The resulting pigment particles are in a state such as a mixed crystal or microcrystal mixture or a mixture of local amorphous substances, resulting in an effect of suppressing crystal growth, and as a result, under the heating conditions as described above, It is considered that the heat resistance was improved. Therefore, with the image recording agent obtained using the above azo pigment composition, a clear image with a clear hue and an excellent image without impairing the transparency were obtained.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The specific yellow monoazo pigment composition used in the present invention, which mainly characterizes the present invention, is characterized in that the method for producing the same comprises an aromatic amino compound having a specific structure among those represented by the following formula (III): When coupling as a coupling component an acetoacetamide compound of a specific structure represented by the following formula (IV) as a coupling component, the diazotization is carried out in the range of 0.1 to 10 of the total molar amount of the diazo component and the coupling component.
A mole% is represented by the following formula (III), but an aromatic amino compound having a substituent different from the above specific aromatic amino compound, an aromatic amino compound represented by the following general formula (V) And a compound selected from acetoacetamide compounds having a substituent different from the specific acetoacetamide compound described above, and used as necessary. The pigment composition can be obtained by further treating the pigment composition with a rosin or a known treating agent.

Embedded image (However, X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ and Y ₃ in the above formula are as defined above.)

[0008] The thiazotization reaction and the coupling reaction are carried out according to a conventional method. More specifically, the specific yellow pigment described above may be an amino compound of the formula (III) as a diazo component, the substituent of which is shown in Table 1 below, Examples of the coupling component include monoazo pigments whose substituents are obtained by coupling each intermediate compound shown in Table 2 below.

[Table 1]

[0009]

[Table 2]

The following are examples of typical monoazo pigments. Yellow azo pigment obtained by diazotizing 2-methoxy-4-nitroaniline and coupling with acetoaceto-2-methoxyanilide 2-acetoaceto-2-methyl-4-chloro by diazotizing 2-nitro-4-chloroaniline Yellow azo pigment obtained by coupling with anilide Diazotization of 2-nitro-4-chloroaniline and coupling with acetoaceto-2-chloroanilide Yellow azo pigment obtained by diazotization of 4-aminophthalimide and acetoacetate Yellow azo pigment obtained by coupling with -2-, 4-dimethylanilide diazotization of 2-trifluoromethylaniline to form N
And yellow azo pigments obtained by coupling with-(2-oxo-5-benzimidazolinyl) acetoacetamide. Examples of the aromatic amino compound represented by the general formula (V) used by substituting a part of the diazo component of the pigment as described above include, for example, 2-aminonaphthalene-1-sulfonic acid and the like. Can be

Regarding the production of the yellow azo pigment composition used in the present invention, the above pigment C.I. I. Specifically, Pigment Yellow 74 is used as an example. As the diazo component, other aromatic amino compounds other than 2-methoxy-4-nitroaniline are used, and as the coupling component, other aromatic amino compounds other than acetoaceto-2-methoxyanilide are used. The acetoacetamide compound is used by mixing one or both of them. Preferred amino compounds include, for example, 2-nitro-4-methylaniline, 2-methyl-5-nitroaniline, 2-nitro-4-chloroaniline, 2-amino-
5-methylbenzenesulfonic acid, 2-amino-naphthalene-1-sulfonic acid, and the like. Preferred acetoacetamide compounds include, for example, 2-carboxy-
Examples include acetoacetanilide, 4- (acetoacetylamino) phthalimide, 5- (acetoacetylamino) benzimidazolone, and 4- (acetoacetylamino) benzoic acid butyl ester. In the case of sulfonic acid, an alkaline earth metal salt, an amine salt or the like can be further obtained after the coupling reaction. The ratio in which the diazo component and the coupling component are mixed is such that the more severe the conditions under which the pigment is used, the more the pigment is used and the more the effect is brought about. It is 0.1 to 10 mol%, preferably 3 to 8 mol% of the total molar amount of the ring component.

Post-treatments such as adjusting the crystal of the product after the coupling reaction and adjusting the shape and the particle diameter of the particles to a desired range are performed in the same manner as usual, if necessary. When a monoazo pigment is used for paints, plastics, or coloring synthetic fibers, the average particle size of the azo pigment is generally increased to increase heat resistance, for example, a size of about 0.4 to 1.0 μm. It is common to do it. However, when this is used as a colorant for an image recording agent, particularly as a colorant for a full-color recording agent where sharpness and transparency of hue are required, the average particle size of the monoazo pigment when dispersed is , 0.2 μm or less, preferably 0.15 μm or less. The specific yellow monoazo pigment composition shown above is a light fastness, a heat resistance, a chemical resistance as a colorant for an image recording agent,
Excellent properties such as water resistance.

The resin used in the present invention is a dispersion medium for the pigment in the solid-state coloring composition, and functions as a pigment dispersing aid in the liquid-state coloring composition. It also acts as a fixing agent for the pigment when actually used as a recording agent. Resins used for such purposes include dry and wet developers such as electrophotography, electrostatic printing, and electrostatic recording, and thermal transfer ink ribbons and films, and image recording agents such as oil-based and aqueous inkjet inks. Any resin used may be used. In addition, conventionally known additives such as a charge controlling agent, a fluidizing agent, and the like, or a solvent and an aqueous medium as a medium are used as necessary according to each application.
The coloring composition for image recording of the present invention also includes a high-concentration coloring composition. The purpose is to contain the pigment at a high concentration, or to sufficiently disperse and disperse it in advance, or to perform toning, to facilitate the subsequent steps.
It is used in the form of a solid such as coarse powder, fine powder, sheet, or small lump, or a paste or liquid.

[0014] The content of the yellow monoazo pigment composition used in the present invention in the coloring composition containing a resin, other additives or a medium varies depending on the purpose of use. In a solid, paste or liquid colored composition containing a high concentration of the yellow monoazo pigment composition, the content is about 15% to 60% by weight, preferably about 20% to 50% by weight, When used as a colorant for an electrophotographic developer or the like, the amount is about 1% to 10% by weight, preferably about 2% to 8% by weight, and is used as a colorant for thermal transfer ink ribbons and films. In this case, 2% to 20% by weight, preferably 4% by weight to
It is about 15% by weight, and is used at the most preferable content depending on the purpose of use.

[0015]

Next, the present invention will be described more specifically with reference to examples. It should be noted that “part” or “%” in the text is based on weight. Example 1 182.7 parts of 2-methoxy-4-nitro-aniline and 2
5.1 parts of nitro-4-methylaniline in water 1,3
The mixture is stirred in a mixture of 00 parts and 290 parts of 35% hydrochloric acid, then cooled to 0 ° C., and diazotized by adding 80 parts of sodium nitrite. Separately, 241.8 parts of 2-methoxyacetoacetanilide were added to 5,000 parts of water, dissolved together with 48 parts of sodium hydroxide, and then precipitated by adding a mixed solution of 196 parts of acetic acid and 196 parts of water. A suspension of the coupling component is obtained. The clear diazo solution is dropped into the acetic acid acidic suspension of the above-mentioned coupling component at 15 ° C. within 1 hour 30 minutes to 2 hours with good stirring. After completion of the coupling, 45 parts of rosin was added to perform pigment treatment, and the obtained pigment composition was filtered, washed with water, dried and pulverized to obtain 463 parts of a yellow azo pigment composition. The average particle size when the obtained pigment composition was dispersed by heating and kneading was about 0.15 μm or less, and the hue was clear yellow.

30 parts of the yellow monoazo pigment composition obtained above was mixed with a styrene-methacrylic copolymer resin (softening point of about 11
70 parts of 0 ° C., glass transition point of about 56 ° C., GPC weight average molecular weight of about 90,000) were sufficiently kneaded with a three-roll mill to disperse the pigment. After cooling, the mixture was crushed to obtain a coarse powder of a high-concentration coloring composition containing a yellow pigment at a concentration of 30%. Next, 14.7 parts of the high-concentration coloring composition containing a yellow pigment thus obtained and 3 parts of a chromium complex-based negative charge control agent were constantly mixed with 82.3 parts of the styrene-methacrylic copolymer resin used above. The mixture was kneaded according to the method, coarsely crushed after cooling, finely pulverized by a jet mill, and classified to obtain a fine powder of a yellow resin composition of 5 to 30 μm. Next, colloidal silica was added as a fluidizing agent according to a conventional method and mixed well to obtain a yellow electrophotographic dry developer. This was mixed with the magnetic iron powder of the carrier, and a monochromatic copy was performed by a negative charge full-color developing electrophotographic copying machine. As a result, a clear yellow image was obtained. The image exhibited a clear and clear yellow color, and exhibited fastness excellent in various physical properties such as light fastness.

When copied on a polyester sheet for an overhead projector, a transparent image was exhibited, and a clear yellow image was shown on the overhead projector screen. Also, a copper phthalocyanine blue pigment as a cyan pigment, a dimethylquinacridone pigment as a magenta pigment, and a carbon developer as a black pigment, respectively, using a carbon black pigment as a cyan developer, a magenta developer, and a black developer, respectively. Four-color full-color copying was performed with the obtained yellow developer to obtain a clear full-color image. Further, the image was copied on an overhead projector sheet to obtain a full-color image showing a clear full-color image on a screen.

Example 2 According to the method described in Example 1, 86.3 parts of 2-nitro-4-chloroaniline was diazotized to give 110 parts of 2-chloroacetoacetanilide and 110 parts of 2,4-dimethylacetoacetoacetate. Coupling with 5.6 parts of anilide as a coupling component, filtration, washing with water, drying and pulverization, 19
7.0 parts of a pigment composition were obtained. The average particle size when the obtained pigment composition was dispersed by heating and kneading was about 0.1.
It was 15 μm or less, and the hue was clear and clear yellow. From the obtained monoazo pigment composition, a high-concentration colored composition was prepared according to the method described in Example 1, and further used to prepare a dry developer for electrophotography. This was mixed with a carrier, and subjected to single-color and full-color copying with a full-color electrophotographic copying machine. As a result, a clear image was obtained. The image shows a clear and clear yellow and four color full color image,
It showed excellent robustness in various physical properties.

Example 3 According to the method described in Example 1, 140.5 parts of 2-methoxy-4-nitroaniline and 4.8 parts of 2-amino-5-methylbenzenesulfonic acid were diazotized to give 2- 183.3 parts of methoxyacetoacetoanilide and 6.1 parts of 2-carboxyacetoacetoanilide were coupled as a coupling component, followed by filtration, washing with water, drying and pulverization to obtain 332 parts of a pigment composition. When the obtained pigment composition was dispersed by heating and kneading, the average particle size was about 0.15 μm or less, and the hue showed a clear yellow color. The obtained monoazo pigment composition was used in accordance with the method described in Example 1 to prepare a high-concentration colored composition, and further used to prepare a dry developer for electrophotography. This was mixed with a carrier, and subjected to single-color and full-color copying with a full-color electrophotographic copying machine. As a result, a clear image was obtained. The images showed clear and clear yellow and four-color full-color images, and exhibited fastness with excellent physical properties.

Example 4 According to the method described in Example 1, 154.5 parts of 2-methoxy-4-nitro-aniline and 15.0 parts of p-toluidine-m-sulfonic acid were diazotized to give 2-methoxy-4-nitro-aniline. 217.0 parts of acetoacetanilide was coupled as a coupling component, and pigment treatment was performed using 38 parts of rosin and 13 parts of calcium chloride, followed by filtration, washing with water, drying and pulverization, to obtain 424 parts of a yellow pigment composition. Obtained. The average particle size when the obtained pigment composition was dispersed by heating and kneading,
It was about 0.15 μm or less, and the hue was clear yellow. 10 parts of the yellow pigment composition obtained above was applied to a polyethylene film according to a conventional method using 41 parts of an ester wax, 41 parts of a paraffin wax, 5 parts of a styrene-methacrylic copolymer resin, and 3 parts of silica as a binder. This was an ink film for thermal transfer recording. This was copied by a full-color thermal transfer copying machine to obtain a clear yellow copied image. This image showed fastness excellent in various physical properties such as light fastness. Further, when copied on a polyester sheet for an overhead projector, a transparent image was obtained, and a clear image was shown on the screen. Further, in the same manner as described above using a copper phthalocyanine blue pigment, dimethylquinacridone pigment, carbon black pigment, respectively, cyan,
Magenta and black thermal transfer ink films, together with the yellow thermal transfer ink film obtained above,
Four-color full-color copying was performed to obtain a clear full-color copied image. Furthermore, the image was copied on a polyester sheet for an overhead projector to obtain a full-color image showing a transparent full-color image on a screen.

Example 5 According to the method described in Example 1, 55.0 parts of 2-methoxy-4-nitro-aniline and 3.2 parts of p-toluidine-m-sulfonic acid were diazotized to give 2-methoxy-4-methoxyaniline. 74.4 parts of acetoacetanilide was coupled with the coupling component, filtered, washed with water, dried and pulverized to 133.0.
Parts of a yellow pigment composition were obtained. The average particle size when the obtained pigment composition was dispersed by heating and kneading was approximately 0.1%.
5 μm or less, and the hue was clear yellow. An aqueous pigment dispersion of 5 parts of the yellow pigment composition obtained above, 3 parts of styrene-acrylate-methacrylic acid diethanolamine salt copolymer, 22 parts of ethylene glycol, 8 parts of glycerin and 62 parts of water was prepared, and was subjected to ultracentrifugation. The pigment coarse particles that could not be dispersed were removed to obtain an aqueous yellow ink for inkjet. The image information was printed with the above-mentioned yellow ink using an on-demand type ink jet printer having a piezo oscillator, and a clear yellow image was obtained. Using a copper phthalocyanine blue pigment, a dimethylquinacridone pigment, and a carbon black pigment, cyan, magenta, and black inkjet inks were respectively obtained in the same manner as described above. Color full-color printing was performed to obtain a clear full-color image.

COMPARATIVE EXAMPLE 2-Methoxy-4-nitro-aniline (168.0 parts) was diazotized to give 2-methoxyacetoanilide 21
6.0 parts are coupled as a coupling component,
Filtration, washing, drying and pulverization gave 385 parts of a pigment. When the obtained pigment was heated and kneaded and dispersed, the average particle diameter was about 0.4 to 1.0 μm, the particles were coarse, and the hue was unclear and opaque yellow. A high-concentration colored composition was prepared from the obtained azo pigment according to the method described in Example 1, and further used to prepare a dry developer for electrophotography. This was mixed with a carrier and subjected to single-color copying using a full-color electrophotographic copying machine. As a result, only an opaque yellow image with poor definition was obtained.

[0023]

The coloring composition for image recording of the present invention uses a specific yellow monoazo pigment composition as a coloring matter component. The yellow monoazo pigment composition has high coloring power, sharpness, It is clear and transparent, and has excellent light fastness, heat resistance, chemical resistance, water resistance, etc., so it can be manufactured stably in the process of manufacturing colored products. Also, when used as a coloring composition for image recording, a clear, sharp, and highly transparent image can be stably recorded. Also, when used as a liquid recording agent, it can record stably for a long period of time.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-56-166252 (JP, A) JP-A-55-84360 (JP, A) JP-A-58-84873 (JP, A) JP-A-54-84873 7430 (JP, A) JP-A-53-21604 (JP, A) JP-A-2-662 (JP, A) JP-A-3-76767 (JP, A) UK Patent 1460967 (GB, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/00-11/20 C09B 67/00-67/54

Claims (2)

(57) [Claims] 1. An image recording coloring composition containing a dye and a resin, wherein the image recording method is an ink jet method, and the dye is a yellow monoazo pigment having a specific structure represented by the following formula (I): Of 99.8 to 80 mol% of the yellow monoazo pigment represented by the formula (I) but having a substituent different from the above monoazo pigment and / or the yellow monoazo pigment represented by the following formula (II): .2
~ 20 mol% produced during pigment synthesis, mixed yellow
Monoazo pigment composition, the average particle size of the pigment composition
Is 0.2 μm or less . Embedded image (However, X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ and Y ₃ in the above formula are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, 1-3 alkoxyl groups, halogen atoms, nitro groups, sulfo groups or alkaline earth metal salts thereof, N-phenylaminosulfonyl groups,
Carboxyl group or an alkaline earth metal salt thereof, carboamide group, N-phenylcarbamoyl group, ureylene group,
It is an iminodicarbonyl group or a carboxylic ester group. ) 2. A yellow monoazo pigment composition according to the following formula (I)
(Ii) diazotizing an aromatic amino compound having a specific structure as a diazo component, and coupling an acetoacetamide compound having a specific structure from a compound represented by the following formula (IV) as a coupling component; In the reaction, 0.1 to 10 mol% of the total molar amount of the diazo component and the coupling component is represented by the following formula (III), but the aromatic compound having a different substituent from the above specific aromatic amino compound is used. Aromatic amino compound, aromatic amino compound represented by the following general formula (V) and the following formula (I
V), which is obtained by substituting at least one compound selected from acetoacetamide compounds having a substituent different from the above-mentioned specific acetoacetamide compound and using the same. The colored composition for image recording according to claim 1, which is a product. Embedded image (However, X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ and Y ₃ in the above formula are as defined above).