JPH03269068A - Coloring composition for image recording - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is used for recording agents in image recording such as electrophotography, electrostatic printing, electrostatic recording, thermal transfer recording, and inkjet recording, or for the production thereof. The present invention relates to a coloring composition and a coloring composition for recording images used in the recording agent for recording images.

More specifically, the present invention provides a recording agent for an image recording agent containing a pigment and a resin, in which the pigment is a high molecular weight yellow disazo pigment having excellent fastness and sharpness, and having a fine particle size. An object of the present invention is to provide a coloring composition for image recording.

(Prior Art) Traditionally, yellow, mixed green, yellowish red, and mixed color green, yellowish red, and
As yellow pigments used in orange or black recording materials, yellow oil-soluble dyes, dispersible dyes, sialylite yellow azo pigments, and monoazo yellow pigments have been used.

(The problem that the invention is trying to solve) However,
Oil-soluble dyes, dispersible dyes, etc. can also be used to color resin media by dissolving them, so although they have high coloring power, they have the problem of poor fastness such as light fastness, solvent resistance, and chemical resistance. .

Furthermore, sialylite yellow disazo pigments and monoazo yellow pigments are still insufficient in various fastness properties such as light resistance, solvent resistance, and heat resistance.

Therefore, the above dyes are insufficient as yellow dyes for recording materials that require various fastness properties, and there is a demand for the development of yellow dyes for recording materials that have excellent physical properties.

The present inventors have conducted various studies on the development of a yellow pigment that can solve the above-mentioned defects of conventional recording materials and satisfy various fastness properties.As a result, a high molecular weight yellow disazo pigment has been found to have excellent light resistance, solvent resistance, Excellent in various properties such as heat resistance and chemical resistance, and
By reducing the particle size compared to pigments used in conventional paints and plastic coloring, it is possible to exhibit excellent properties such as sharpness, brightness, and transparency of hues, and this is used as a coloring agent. The present invention was completed based on the discovery that an excellent recording agent can be obtained by using the compound as a compound.

(Means for Solving the Problems) That is, the present invention provides a coloring composition for image recording containing a dye and a resin, in which the dye is a high molecular weight yellow disazo pigment represented by the following formula [I]. This is a characteristic coloring composition for image recording.

(However, A is directly bonded, or methylene group, ether group, sulfonyl group, or thioether is a hydrogen atom,
2. It is an alkyl group, alkoxyl group or halogen atom having 1 to 3 carbon atoms. ．． 2. is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, an alkoxyl group,
It is a phenoxydyl group, a halogenated phenoxydyl group, or a halogen atom. (Preferred Embodiment) To explain the present invention in more detail, the high molecular weight yellow disazo pigment used in the present invention and which mainly characterizes the present invention is produced by, for example, Japanese Patent Publication No. 55-5
As disclosed in Publication No. 0991, the following formula [1]
A bisacetoacetamide compound represented by is used as a coupling component, and an aromatic amine compound represented by the following formula [IU] is used as a diazo component, using concentrated hydrochloric acid etc. in a hydrophobic aromatic solution. Examples include a method of diazotization and coupling in the presence of a small amount of water.

CH, C0CH, C0NH [Ar] NHCOCH, C
0CH.

[rll 2 [ITJ] [However, Ar, X, , X, , Z, , Z in the above formula.

and Y are as defined above. ] This coupling reaction is carried out in a hydrophobic aromatic solution such as dichlorobenzene, nitrobenzene, nitrotoluene, etc. at a temperature of 20°C to 60°C.

Post-treatments such as adjusting the crystals and adjusting the shape and diameter of the particles to a desired size are carried out in the same manner as in conventional methods, if necessary.

High molecular weight disazo pigments can be used in paints, plastics,
When used for purposes such as coloring synthetic fibers, the average particle size is generally large, for example, adjusted to about 0.5 to 0.7 μm.

However, when this is used as a coloring agent in an image recording material, there is a problem that the hue lacks clarity and sharpness.Especially, when it is used as a coloring agent in a full-color recording material, the hue is It is preferable that the disazo pigment has sharpness, brightness, and even transparency, and for this purpose, the average particle diameter of the disazo pigment when dispersed is 0.2 μm or less, preferably 0.2 μm or less.
It is preferable to adjust the thickness to 15 μm or less.

To be more specific about the above-mentioned high molecular weight yellow disazo pigment, the substituents of the yellow disazo pigment of the following structural formula [TV] are shown in Table 1, and the substituents of the following structural formula EV) are shown in Table 2. Each pigment shown in the table may be mentioned.

-11 to 3? -1- The high molecular weight yellow disazo pigment shown above has light resistance,
It exhibited excellent properties such as heat resistance, i+1 solvent resistance, chemical resistance, and water resistance.

The resin used in the present invention functions as a dispersion medium in a solid coloring composition, and as a pigment dispersion aid in a liquid coloring composition, and When actually used as a recording agent, it acts as a fixing agent for pigments.

Resins used for such purposes include dry and wet developers for electrophotography, electrostatic printing, electrostatic recording, etc., 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.

Further, according to the respective uses, conventionally known additives such as a charge control agent, a fluidizing agent, etc., or a solvent or an aqueous medium as a medium may be used as necessary.

The content of the high molecular weight yellow disazo pigment used in the present invention in the coloring composition containing the resin and other additives or medium varies depending on the purpose for which it is used. In solid, paste, or liquid coloring compositions containing a yellow disazo pigment at a high concentration, the content is approximately 70% to 10%, preferably 60% to 20%, and the content is approximately 70% to 10%, preferably 60% to 20%. When used as a coloring agent, it is about 15% to 2%, preferably about 10% to 3%, and when used as a coloring agent for thermal transfer ink ribbons and films, it is about 15% to 4%. Preferably 10%
It is about 6%, and is used at the most preferable content depending on the purpose of use.

Furthermore, the coloring composition for image recording of the present invention can be used in various ways depending on the purpose.

One method is to contain pigments in high concentration, and by thoroughly kneading and dispersing them in advance, or by adjusting the color.
It is used to facilitate the subsequent process, and can be used in any solid form such as coarse particles, coarse powder, fine powder, sheet form, or small lump form, or paste form or liquid form.

Also included are those having compositions used as recording agents for final image recording, such as so-called dry developers, wet developers, electrostatic recording agents, thermal transfer ink ribbons and films, and printer inks.

Additionally, if other pigments are required, appropriate selections from conventionally known pigments or dyes can be used in conjunction with the yellow disazo pigment of the present invention. For example, to obtain a green to yellow-green hue, it is used together with a blue pigment and a green pigment; to obtain a yellow-red to yellow-yellow hue, it is used together with a red pigment and a turquoise pigment, and then to black. To achieve this, two or more pigments such as red and blue are used together.

Further, the coloring composition for image recording of the present invention can be used as a yellow image recording agent or by coloring, such as green, yellow-green, yellowish red,
In addition to being used alone as an image recording agent such as black or black, it can also be used in combination with a cyan, magenta or even black image recording agent as a full color recording system. Of course.

Examples of these include organic pigments and dyes such as phthalocyanine, azo, anthraquinone, perinone/perylene, indigo/thioindigo, dioxazine, quinacridone, isoindolinone, and carbon black pigments. Inorganic pigments include titanium oxide, iron oxide, fired pigments, and extender pigments.

(Action/Effect) The coloring composition for image recording of the present invention uses a high molecular weight yellow disazo pigment as its pigment component, and this yellow disazo pigment has good light resistance, heat resistance, and solvent resistance. It has excellent fastness such as chemical resistance and water resistance, as well as high coloring power, sharpness, brightness, and transparency, so it can be manufactured stably in the process of manufacturing colored products.
Furthermore, when the composition is finally used as a coloring composition for image recording, it is possible to stably record clear, clear, and highly transparent images.

Furthermore, when used as a liquid recording agent, stable recording can be achieved for a long period of time.

Therefore, the obtained image is clear and exhibits the above-mentioned excellent properties of fastness.

(Example) Next, the present invention will be explained in more detail with reference to Synthesis Examples and Examples. Note that "%" or "%" in the text is based on weight.

Synthesis Example 1 According to the method disclosed in Japanese Patent Publication No. 55-50991, 3
-amino-4-chloro-ancho, aromatic acid-(2°-methyl-
3-dichloro)anilide was diazotized using hydrochloric acid and sodium nitrite, and N The coupling reaction was carried out at °C. Post-treatments such as pigmentation, filtration, and washing were performed, followed by drying and pulverization to obtain a high molecular weight yellow disazo pigment.

The decomposition point of the obtained pigment was 369°C.

Further, when the yellow disazo pigment prepared in this way was dispersed, the average particle diameter was approximately 0.2 Jfm or less, and the hue was slightly greenish yellow.

Synthesis Example 2 In the same manner as in Synthesis Example 1, 3-amino-4-chloro-benzoic acid-(2'',5'-dichloro)anilide was diazotized to form N,N'-(2,5-dimethyl 1.4 A coupling reaction was carried out with -phenylene)bis(acetoacetamide).The post-treatments of pigmentation, filtration and washing were carried out, followed by drying and pulverization to obtain a high molecular weight yellow disazo pigment.The decomposition point of the obtained pigment was It showed 374°C.

Further, the average particle diameter when the yellow disazo pigment prepared in this manner is dispersed is approximately 0. 21, f m or less, and 5 hues were yellow.

Synthesis Example 3 In the same manner as in Synthesis Example 1, 3-amino-4-chloro-benzoic acid-(2'-methyl-5'-chloro)anilide was diazotized to give N,N'-(2,5-dimethyl- A coupling reaction was performed with 1,4-phenylene)bis(acetoacetamide). Pigmentation, filtration, and post-washing treatments are carried out.
It was dried and ground to obtain a high molecular weight yellow disazo pigment. The decomposition point of the obtained pigment was 370°C.

Further, when the yellow disazo pigment prepared in this manner was dispersed, the average particle diameter was approximately 0.2 μm or less, and the hue was slightly reddish yellow.

Synthesis Example 4 In the same manner as in Synthesis Example 1, 3-amino-4-chloro-benzoic acid-(2',5''-dichloro)anilide was diazotized to produce N,N-(2-methyl-5-chloro-1 ,4-phenylene)bis(acetoacetamide).After-treatment of pigmentation, filtration, and washing, a high molecular weight yellow disazo moiety was obtained by drying and pulverizing. The decomposition point was 364°C.

Further, when the yellow disazo pigment was dispersed, the average particle diameter was approximately 0.2 μm or less, and the hue was yellow.

Synthesis Example 5 In the same manner as in Synthesis Example 1, 3-amino-4-chloro-benzoic acid-(2°-methyl-5-chloro)anilide was diazotized to produce bis(3-methyl-4-acetoacetamidophenyl). ) A coupling reaction was performed with methane. pigmentation,
Post-treatments such as filtration and washing were performed, followed by drying and pulverization to obtain a high molecular weight yellow disazo face. The decomposition point of the obtained pigment is 3
It showed 48°C.

When the yellow disazo pigment prepared in this manner is dispersed, the average particle diameter is approximately 0. It exhibited a diameter of 2 μm or more, and the hue was greenish yellow.

Example 1 30 parts of the yellow bisazo pigment obtained in Synthesis Example 1 was mixed with 70 parts of a styrene-methacrylic copolymer resin (softening point: 110°C, glass transition point: 56°C, weight average molecular weight by GPC method: approximately 90,000). The mixture was sufficiently kneaded with a roll to disperse the pigment.

After cooling, the mixture was crushed to obtain a coarse powder of a highly concentrated colored composition containing a yellow pigment at a concentration of 30%. Next, 14.7 parts of the high molecular weight coloring composition containing the yellow pigment thus obtained and 3 parts of a chromium complex salt-based negative charge control agent were added to the styrene resin used above.
The mixture was kneaded with 82.3 parts of a methacrylic copolymer resin according to a conventional method, cooled, crushed, finely crushed in 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 thoroughly mixed to obtain a yellow electrophotographic dry developer.

This was mixed with magnetic iron powder as a carrier and monochromatic copying was performed using electrophotographic copying for negative charge full color development, resulting in a clear yellow image. The image was clear and bright yellow, and showed excellent fastness in various physical properties such as light resistance.

Also, when copied onto a polyester sheet for an overhead projector, a transparent image was obtained, and a clear yellow image was shown on the overhead projector screen.

Further, using a copper phthalocyanine blue pigment as a cyan pigment, a dimethylquinacridone dye as a magenta pigment, and a carbon black pigment as a black pigment, a cyan color developer, a magenta color developer, and a black color developer were respectively prepared in the same manner as above. Four-color full-color copying was performed with the obtained yellow developer to obtain a clear full-color image.

Also, by copying onto an overhead projector sheet, a full-color image was obtained that displayed a clear full-color image on the screen.

Examples 2 to 9 According to the method described in Example 1, each high-concentration coloring composition was made using the ingredients listed in Table 3 below in place of the ingredients used in Example 1. A dry developer for electrophotography was prepared using this method.

This is mixed with a carrier to produce a full-color electrophotographic copying system suitable for each, that is, Examples 2 to 8 are copying machines using negatively charged two-component full-color developers, and Example 9 is a copying machine using positively-charged two-component full-color developers. I made copies of each. As a result, the third
Clear images with the hues shown in the table were obtained. In addition, it showed excellent robustness with respect to various properties such as light resistance.

Furthermore, it is copied onto an overhead projector sheet,
A clear image was obtained on the screen.

(The following is a blank space) Example 10 The yellow disazo pigment obtained in Synthesis Example 1 was kneaded with a styrene-methacrylic copolymer resin having a tertiary amino group to prepare a high 1 degree color composition containing the pigment at a concentration of 30 parts. Obtained. Next, this was cooled and then coarsely crushed and finely crushed. Obtained yellow resin powder 1
0 part was added to Isopar 61β along with 15 parts of a methacrylic ester resin soluble in an aliphatic hydrocarbon solvent, glass beads were added, and the mixture was dispersed in a paint shaker for 20 hours to prepare a concentrated colored liquid. did.

200 g of this concentrated solution was added to Isopar 61β and dispersed to obtain an electrophotographic wet developer.

This was copied using a full-color (P-type electrophotographic copying machine) to obtain a clear yellow copy image. This image showed excellent fastness in various physical properties such as light resistance.

In addition, using a copper phthalocyanine blue pigment, a dimethylquinacridone pigment, and a carbon black pigment, a cyan wet developer, a magenta black developer,
Square full-color copying was performed using a black wet developer together with the yellow wet developer obtained above to obtain a clear full-color image.

Also, using the above-mentioned four-color full-color developer, a clear full-color picture tube was outputted using a four-color full-color wet electrostatic plotter.

Example 11 10 parts of the yellow disazo pigment obtained in Synthesis Example 1 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 binders. This was applied to obtain a yellow thermal transfer recording ink film.

This was copied using a full-color thermal transfer copying machine to obtain a clear yellow copy image. This image showed excellent fastness in various physical properties such as light resistance.

When the image was copied onto a polyester sheet for an overhead projector, a transparent image was obtained and a clear image was displayed on the screen.

In addition, using a copper phthalocyanine blue pigment, a dimethylquinacridone pigment, and a carbon black pigment, cyan, magenta, and black thermal transfer ink films were made in the same manner as above, and along with a yellow thermal transfer ink film obtained by Jugo himself, Square full-color copying was performed to obtain a clear full-color copy image.

Furthermore, the image was copied onto a polyester sheet for an overhead projector to obtain a full-color image that could be projected on a screen.

Example 12 An aqueous pigment dispersion was prepared containing 5 parts of the yellow disazo pigment obtained in Synthesis Example 1, 3 parts of styrene-acrylate-methacrylic acid jetanolamine salt copolymer, 22 parts of ethylene glycol, 8 parts of glycerin, and 62 parts of water. Pigment coarse particles that could not be dispersed using an ultracentrifuge were removed to obtain a water-based yellow inkjet ink.

Image information was printed using the yellow ink described above using an on-demand inkjet printer equipped with a piezo vibrator to obtain a clear yellow image.

In addition, in the same manner as above using copper phthalocyanine blue pigment, dimethylquinacridone pigment, and carbon black pigment, cyan, magenta, and black inkjet inks were made, respectively, and together with the yellow inkjet ink obtained above, Four-color full-color printing was performed to obtain a clear full-color copy image.

Claims (7)

[Claims] (1) A coloring composition for image recording containing a dye and a resin, characterized in that the dye is a high molecular weight yellow disazo pigment represented by the following formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [However, Ar in the above formula is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, (However,
A is directly bonded or is a methylene group, ether group, sulfonyl group, or thioether group) or ▲ has a numerical formula, chemical formula, table, etc. ▼, and X_1, X_2,
Y is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group, or a halogen atom, and Z_1 and Z_2 are hydrogen atoms, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, an alkoxyl group, a phenoxyl group, It is a xyl group or a halogen atom. ] (2) The average particle diameter of the high molecular weight yellow disazo pigment is 0.
．． The coloring composition for image recording according to claim 1, which has a particle size of 2 μm or less. (3) The yellow disazo pigment is diazotized using a bisacetoacetamide compound represented by the following formula [II] as a coupling component and an aromatic amino compound represented by the following formula [III] as a diazo component. The coloring composition for image recording according to claim 1, which is a high molecular weight yellow disazo pigment obtained by coupling. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] [However, Ar, X_1, X_2, Z_1, Z in the above formula
_2 and Y are as defined above. ] (4) The coloring composition for image recording according to claim 1, which is in a solid, paste, or liquid form and contains a dye at a high concentration. (5) The coloring composition for image recording according to claim 1, which is in the form of a 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 base material such as paper or film.