JPH0570725A - Colored composition for image recording - Google Patents

Abstract

PURPOSE:To provide the title compsn. excellent in properties including fastness. CONSTITUTION:The title compsn. is prepd. by compounding a resin with a colorant which is a mixture of pigments, is formed during the synthesis of the pigments, and comprises 99.8-80mol% yellow monoazo pigment having a specified structure and selected from among those of formula I and 0.2-20mol% yellow monoazo pigment consisting of a yellow monoazo pigment of formula I having substitutents different from those of the foregoing monoazo pigment and/or a yellow monoazo pigment of formula II. If necessary, the colorant is treated with rosins or one of other well-known treating agents.

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 in image recording such as electrostatic recording, thermal transfer recording, inkjet recording, or a coloring composition used for its production. More specifically, the present invention relates to a recording material for image recording containing a pigment and a resin, wherein the pigment is a yellow monoazo pigment having excellent fastness, transparency, sharpness and the like and having a very fine particle size. The present invention provides a colored composition for image recording which is a composition.

[0002]

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

[0003]

However, since oil-soluble dyes and dispersible dyes can be dissolved in coloring resin media, they have high coloring power, but light resistance and solvent resistance are high. However, there is a problem that the fastness such as chemical resistance is poor. 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 colored composition for image recording, which is excellent in various properties including fastness.

[0004]

The above object can be achieved by the present invention described below. That is, the present invention provides a coloring composition for image recording containing a dye and a resin, wherein the dye is 99.8 to 80 mol% of a yellow monoazo pigment having a specific structure among those represented by the following formula (I). And 0.2 to 20 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). It is a colored composition for image recording, which is a yellow monoazo pigment composition produced at the time of synthesis and mixed and further treated with a rosin or a known treating agent as required.

[Chemical 3] (However, X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ and Y ₃ in the above formula are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or a carbon number. 1-3 alkoxyl group, halogen atom, nitro group, sulfo group or alkaline earth metal salt or higher amine salt thereof, N-phenylaminosulfonyl group, carboxyl group or alkaline earth metal salt or higher amine salt thereof, carboxamide group , N-phenylcarbamoyl group, ureylene group, iminodicarbonyl group or carboxylic acid ester group.)

[0005]

The present inventors have conducted various researches on the development of a yellow pigment which can solve the above-mentioned defects of the conventional recording materials, have excellent colorability, and can satisfy various fastness and economical efficiency. By using a specific manufacturing method, the monoazo pigment has a smaller particle size than conventional pigments used for applications such as paints and plastic coloring, and also improves heat resistance, resulting in clear hue and sharpness. It was found that excellent properties such as transparency, transparency, etc. can be exhibited and various physical properties can be satisfied, and an excellent image recording agent can be obtained by using this as a colorant for the image recording agent. The present invention has been completed. That is, when the azo pigment is conventionally used for coloring paints, plastics, synthetic fibers, etc., the average particle diameter of the azo pigment is adjusted to a large value in order to emphasize color hiding property and color developability. Although heat resistance is improved by reducing the rate of change, the resulting coloring agent for image recording agents lacks sharpness of hue, transparency and dullness.
Since the image recording agent is used in full color or in an over head projector, it is desired that the image recording agent has clear hue, sharpness, and transparency.

In the production of an electrophotographic dry developer or the like, heat kneading is often carried out at a temperature of about 100 to 150 ° C., and pigment particles grow under such heating conditions,
In many cases, the color tone changes, the color becomes dull, the color density decreases, and the color becomes opaque due to the change of crystals. In the present invention, in synthesizing the desired azo pigment, the color and physical properties are similar to that,
By simultaneously synthesizing azo pigment compounds with different structures,
The produced pigment particles are brought into a mixed crystal or fine crystal mixture or locally mixed amorphous state to bring about an effect of suppressing crystal growth, and as a result, under the heating conditions as described above. It is considered that the heat resistance of the is improved. Therefore, with the image recording agent obtained by using the above-mentioned azo pigment composition, an excellent image having a clear hue, a clear hue and not impairing the transparency was obtained.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The specific yellow monoazo pigment composition used in the present invention and which mainly characterizes the present invention, the production method thereof is a diazo component containing an aromatic amino compound having a specific structure among those represented by the following formula (III): When the acetoacetamide compound having a specific structure among the compounds represented by the following formula (IV) is coupled as a coupling component, the total molar amount of the diazo component and the coupling component is 0.1-10.
Aromatic amino compounds represented by the following formula (III), whose mol% has a substituent different from the above specific aromatic amino compounds, and aromatic amino compounds represented by the following general formula (V) And represented by the following formula (IV), it is used by substituting with a compound selected from acetoacetamide compounds having a substituent different from the above-mentioned specific acetoacetamide compound, and is also formed as necessary. It is obtained by further treating the pigment composition with a rosin or a known treating agent.

[Chemical 4] (However, X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ and Y ₃ in the above formula are as defined above.)

The above-mentioned cyazo formation reaction and coupling reaction are carried out according to conventional methods. More specifically, the specific yellow pigment described above includes, as the pigment, an amino compound represented by the structural formula (III) as a diazo component, the substituents of which are shown in Table 1 below and represented by the structural formula (IV). Examples of the coupling component include monoazo pigments obtained by coupling the respective intermediate compounds whose substituents are shown in Table 2 below.

[Table 1]

[0009]

[Table 2]

Examples of the typical monoazo pigments are as follows. Yellow azo pigment obtained by diazotizing 2-methoxy-4-nitroaniline and coupling it with acetoaceto-2-methoxyanilide. 2-Nitro-4-chloroaniline was diazotized to acetoacet-2-methyl-4-chloro. Yellow azo pigment obtained by coupling with anilide 2-nitro-4-chloroaniline is diazotized to acetoacet-2-yellow azo pigment obtained by coupling with 2-chloroanilide 4-aminophthalimide is diazotized to acetoacetate Yellow azo pigment obtained by coupling with 2,4-dimethylanilide 2-trifluoromethylaniline was diazotized to give N.
A yellow azo pigment obtained by coupling with-(2-oxo-5-benzimidazolinyl) acetoacetamide. As the aromatic amino compound represented by the general formula (V), which is used by substituting a part of the diazo component of the pigment as described above, for example, 2-aminonaphthalene-1-
Examples thereof include sulfonic acid.

For the production of the yellow azo pigment composition used in the present invention, the above-mentioned pigment C.I. I. Pigment Yellow 74 will be specifically described. As the diazo component, an aromatic amino compound other than 2-methoxy-4-nitroaniline and as the coupling component other than acetoaceto-2-methoxyanilide. The acetoacetamide compound is used as a mixture of 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 can be mentioned. Preferred acetoacetamide compounds include, for example, 2-carboxy-
Examples thereof 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 added after the coupling reaction. The mixing ratio of the diazo component and the coupling component brings about an effect by being used more as the conditions under which the pigment is used are stricter, but there is also a performance relationship as a pigment, and the diazo component and the cupping component are mixed. 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 arranging the crystals of the product after the coupling reaction and arranging the particle shape and particle diameter in a desired range are carried out as necessary in the same manner as in the usual method. When the monoazo pigment is used for applications such as coloring of paints, plastics, and 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 choose However, when it is used as a colorant for an image recording agent, particularly as a colorant for a full-color recording agent that requires clearness and transparency of hue, and a sharpness, 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 light resistance, heat resistance, chemical resistance as a colorant for an image recording agent,
It showed excellent properties such as water resistance.

The resin used in the present invention functions as a pigment dispersion medium in a solid color composition, and as a pigment dispersion aid in a liquid color composition. It also acts as a pigment fixing agent when it is actually used as a recording agent. Resins used for such purposes are usually used for dry and wet developers such as electrophotography, electrostatic printing and electrostatic recording, thermal transfer ink ribbons and films, and image recording agents such as oil-based and water-based inkjet inks. Any resin used may be used. If necessary, conventionally known additives such as a charge control agent, a fluidizing agent, or the like, or a solvent or an aqueous medium may be used as a medium, depending on each application.
The coloring composition for image recording of the present invention also includes a high-concentration coloring composition. Its purpose is to facilitate the subsequent steps by containing the pigment in a high concentration and thoroughly kneading and dispersing it in advance, or performing toning.
It can be used in any form of solid such as coarse powder, fine powder, sheet, and small lump, or paste or liquid.

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

[0015]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In addition, "parts" and "%" are based on weight. Example 1 182.7 parts and 2 of 2-methoxy-4-nitro-aniline
5.1 parts of -nitro-4-methylaniline and water 1,3
Add to a mixture of 00 parts and 290 parts of 35% hydrochloric acid and stir, then cool to 0 ° C. and diazotize by adding 80 parts of sodium nitrite. Separately, 241.8 parts of 2-methoxyacetoacetanilide was 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 coupling components is obtained. The clarified diazo solution is added with vigorous stirring to the acetic acid suspension of the above coupling components at 15 ° C. within 1 hour 30 minutes to 2 hours. After the coupling was completed, 45 parts of rosin was added for 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. When the obtained pigment composition was kneaded and dispersed by heating, the average particle diameter was about 0.15 μm or less, and the hue was vivid yellow.

30 parts of the yellow monoazo pigment composition obtained above was added to a styrene-methacrylic copolymer resin (softening point of about 11).
The pigment was dispersed by sufficiently kneading with 0 part, glass transition point of about 56 ° C., 70 parts of GPC method weight average molecular weight of about 90,000) using a three-roll mill. After cooling, the mixture was crushed to obtain coarse powder of a high-concentration colored composition containing a yellow pigment at a concentration of 30%. Next, 14.7 parts of the high-concentration coloring composition containing the yellow pigment thus obtained and 3 parts of the chromium complex salt-based negative charge control agent and 82.3 parts of the styrene-methacrylic copolymer resin used above were used. The mixture was kneaded according to the method, cooled, coarsely pulverized, then finely pulverized with a jet mill, and further 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 sufficiently to obtain a yellow electrophotographic dry developer. As a result of mixing this with magnetic iron powder as a carrier and making a monochrome copy with an electrophotographic copying machine for negative charge full color development, a clear yellow image was obtained. The image had a clear and bright yellow color and showed excellent fastness with various physical properties such as light resistance.

Further, when it was 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. Further, using copper phthalocyanine blue pigment as a cyan pigment, dimethylquinacridone pigment as a magenta pigment, and carbon black pigment as a black pigment, respectively, in the same manner as described above, as a cyan color developer, a magenta color developer, and a black color developer, respectively. Four-color full-color copying was performed together with the obtained yellow developer to obtain a clear full-color image. In addition, a full-color image was obtained by copying on an overhead projector sheet and displaying a clear full-color image on the screen.

Example 2 According to the method described in Example 1, 86.3 parts of 2-nitro-4-chloroaniline were diazotized to give 110 parts of 2-chloroacetoacetanilide and 2,4-dimethyl-acetoacetate. Coupling with 5.6 parts of anilide as a coupling component, filtration, washing with water, drying and crushing, 19
7.0 parts of pigment composition are obtained. The average particle diameter of the obtained pigment composition when kneaded and dispersed by heating is about 0.
It was 15 μm or less, and the hue was vivid and clear yellow. A high-concentration coloring composition was prepared from the obtained monoazo pigment composition according to the method described in Example 1, and the composition was used to prepare a dry developer for electrophotography. As a result of mixing this with a carrier and performing monochromatic and full-color copying with a full-color electrophotographic copying machine, a clear image was obtained. The image shows a clear, crisp yellow and four-color full-color image,
It showed robustness with excellent 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 methoxyacetoacetanilide and 6.1 parts of 2-carboxyacetoacetanilide were coupled as a coupling component, filtered, washed with water, dried and pulverized to obtain 332 parts of a pigment composition. The obtained pigment composition had an average particle diameter of about 0.15 μm or less when it was kneaded and dispersed by heating, and its hue was vivid yellow. The obtained monoazo pigment composition was used according to the method described in Example 1 to prepare a highly concentrated coloring composition, which was further used to prepare a dry developer for electrophotography. As a result of mixing this with a carrier and performing monochromatic and full-color copying with a full-color electrophotographic copying machine, a clear image was obtained. The images were clear, crisp yellow and four-color full-color images, and showed excellent fastness with various 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. 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, filtered, washed with water, dried and pulverized to obtain 424 parts of a yellow pigment composition. Obtained. The average particle size when the obtained pigment composition is kneaded and dispersed by heating,
It was about 0.15 μm or less, and the hue was vivid 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 ester wax, 41 parts of paraffin wax, 5 parts of styrene-methacrylic copolymer resin and 3 parts of silica as a binder, and yellow An ink film for thermal transfer recording was used. 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 resistance. Also, when copied on a polyester sheet for an overhead projector, a transparent image was obtained, and a clear image was shown on the screen. In addition, a copper phthalocyanine blue pigment, a dimethylquinacridone pigment, and a carbon black pigment were used in the same manner as described above to produce cyan color
Magenta and black color thermal transfer ink film, together with the yellow thermal transfer ink film obtained above,
Four-color full-color copying was performed to obtain clear full-color copied images. Further, a full-color image was obtained by copying it on a polyester sheet for an overhead projector and displaying a transparent full-color image on the 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. 74.4 parts of acetoacetanilide was coupled with the coupling component, filtered, washed with water, dried and crushed to obtain 133.0.
Part of a yellow pigment composition was obtained. The average particle size of the obtained pigment composition when heated and kneaded and dispersed is about 0.1.
It was 5 μm or less, and the hue was vivid yellow. 5 parts of the yellow pigment composition obtained above, 3 parts of a styrene-acrylate-methacrylic acid diethanolamine salt copolymer, 22 parts of ethylene glycol, 8 parts of glycerin and 62 parts of water were made into an aqueous pigment dispersion liquid, and the mixture was subjected to ultracentrifugation. The coarse pigment particles that could not be dispersed were removed to obtain a water-based inkjet yellow ink. Image information was printed using the above yellow ink with an on-demand type inkjet printer having a piezo oscillator to obtain a clear yellow image. Further, using a copper phthalocyanine blue pigment, a dimethylquinacridone pigment, and a carbon black pigment, cyan ink, magenta ink, and black ink jet 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-methoxyacetoacanilide 21.
By coupling 6.0 parts as a coupling component,
Filtration, washing with water, drying and crushing gave 385 parts of 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 became opaque yellow. A high-concentration coloring 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. As a result of mixing this with a carrier and performing monochromatic copying with a full-color electrophotographic copying machine, only an opaque yellow image with poor definition was obtained.

[0023]

[Effect] The coloring composition for image recording of the present invention uses a specific yellow monoazo pigment composition as its dye component. This yellow monoazo pigment composition has a high coloring power, sharpness, and It is clear and transparent, and has excellent lightfastness, heat resistance, chemical resistance, water resistance, and other various fastnesses, so it can be stably manufactured even in the process of manufacturing colored products. Even when used as a coloring composition for image recording, it is possible to stably record a clear, clear and highly transparent image. Further, when used as a liquid recording material, it is possible to stably record for a long period of time.

Claims (7)

[Claims] 1. A coloring composition for image recording containing a dye and a resin, wherein the dye is a yellow monoazo pigment having a specific structure among those represented by the following formula (I): 99.8.
.About.80 mol%, and 0.2 to 20 of the yellow monoazo pigment represented by the formula (I) and having a substituent different from that of the above monoazo pigment and / or the yellow monoazo pigment represented by the following formula (II). A coloring composition for image recording, characterized in that a yellow monoazo pigment composition which is produced by mixing mol% at the time of synthesizing a pigment and is mixed and further treated with a rosin or a known treating agent as required. object. [Chemical 1] (However, X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ and Y ₃ in the above formula are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or a carbon number. 1-3 alkoxyl group, halogen atom, nitro group, sulfo group or alkaline earth metal salt or higher amine salt thereof, N-phenylaminosulfonyl group, carboxyl group or alkaline earth metal salt or higher amine salt thereof, carboxamide group , N-phenylcarbamoyl group, ureylene group, iminodicarbonyl group or carboxylic acid ester group.) 2. The yellow monoazo pigment has an average particle diameter of 0.
The coloring composition for image recording according to claim 1, which has a thickness of 2 μm or less. 3. A yellow monoazo pigment composition has the formula (I
Aromatic amino compounds having a specific structure among those represented by II) are diazotized as a diazo component, and acetoacetamide compounds having a specific structure among those represented by the following formula (IV) are coupled as a coupling component. In this case, 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), and has an aromatic group different from the above specific aromatic amino compound. Group amino compounds, aromatic amino compounds represented by the following general formula (V) and the following formula (I
The pigment represented by V) is used by substituting at least one compound selected from acetoacetamide compounds having a substituent different from the above-mentioned specific acetoacetamide compound, and is also formed as necessary. The colored composition for image recording according to claim 1, which is a yellow monoazo pigment composition obtained by further treating the composition with a rosin or a known treating agent. [Chemical 2] (However, X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ and Y ₃ in the above formula are as defined above.) 4. The coloring composition for image recording according to claim 1, which is a solid, paste or liquid containing a dye in a high concentration. 5. The coloring composition for image recording according to claim 1, which is in the form of fine powder. 6. The coloring composition for image recording according to claim 1, which is a liquid image recording agent. 7. The coloring composition for image recording according to claim 1, which is a transferable thin film image recording agent applied to a substrate such as paper or film.