JP2001106936A - Additive for pigment, pigment composition and toner for electrostatic image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an additive for pigment, capable of imparting better heat resistance than conventionals and to obtain a monoazo pigment composition having excellent heat resistance. SOLUTION: This additive for monoazo pigment (X) comprises a monoazo compound (Y) of the general formula y and obtained by reacting an aniline compound diazonium salt (A) with an acetoacetic arylamide compound (B) having a carboxyl group and a hydroxy group. The other subject a pigment composition includes a monoazo pigment and the additive. (RX, RY and RZ are each H, CH3, C2H5, OCH3, OCH2H5, NO2 or Cl independently; R7 is OH; R8 is COOH).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azo pigment used as a coloring material, and more particularly to an azo pigment for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like using the same. Of the color toner.

[0002]

2. Description of the Related Art Monoazo yellow pigments have long been used as colorants for printing inks, paints, plastics, and the like. More recently, however, they have developed electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like. Japanese Patent Application Laid-Open No. 2-136865 discloses the use of a color toner.

However, the heat resistance of the monoazo yellow pigment is not always sufficient, and the heat-setting printing ink,
When used in plastic molded products that have undergone a melt-kneading process, transparency and tinting strength are often reduced.

In order to prevent such adverse effects, Japanese Patent Publication No. Sho 55-10630 (Japanese Patent Application Laid-Open No. Sho 46-2828) discloses an aniline compound diazonium salt, an acetoacetic acid arylamide compound (non-polar coupler) 80. ~ 9
9.5% and 0.5 of an acetoacetic arylamide compound (polar coupler) containing a carboxyl group, a sulfonic acid group, a carboxylic acid amide group, or a sulfonic acid amide group
A monoazo pigment mixture obtained by coupling 〜20% is disclosed.

[0005]

However, even when the azo pigment composition described in the examples of the publication is used as a pigment, the heat resistance is not sufficient and the composition is subjected to a high heat history, such as a heat setting process. When used in a color toner that has passed through, it lacked sharpness and color reproducibility.
The problem to be solved by the present invention is an additive for a pigment which can impart excellent heat resistance to a monoazo pigment, which can be sufficiently used even in a color toner which undergoes a high heat history, for example, a color toner undergoing a heat setting process. And a color toner using the same.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that as a pigment additive, a monoazo compound (Y) having a chemical structure based on an acetoacetic arylamide compound (B) having a carboxyl group and a hydroxyl group is used. The present invention has found that the heat resistance of monoazo pigments can be remarkably improved to an extent that cannot be expected from conventional monoazo compounds having a chemical structure based on an acetoacetic acid arylamide compound having only one of a carboxyl group and a hydroxyl group. Was completed.

Further, in addition to the monoazo compound (Y), a monoazo compound having a chemical structure based on an acetoacetic acid arylamide compound (C) having a carbamoyl group or an acetylamino group other than the group (B) ( It has also been found that a pigment additive further comprising Z) further remarkably improves heat resistance.

[0008] Further, it is better not to prepare the monoazo pigment (X) and the monoazo compound (Y) separately and then to mix them, but to produce them at the same time. It has also been found that the monoazo compound (Y) can be arranged, and the heat resistance of the obtained pigment composition is further improved.

That is, the present invention provides the following inventions. 1. An additive for a monoazo pigment (X) comprising a monoazo compound (Y) having a structure obtained by reacting an aniline compound diazonium salt (A) with an acetoacetic acid arylamide compound (B) having a carboxyl group and a hydroxyl group.

[0010] 2. 2. The additive for monoazo pigments according to 1 above, wherein the monoazo compound (Y) is a monoazo compound represented by the following general formula (y). General formula (y)

Embedded image [However, in the general formula (y), R _X , R _Y and R _Z are independently
H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ , Cl
Is shown. R ₇ represents OH and R ₈ represents COOH. ]

3. Aniline compound diazonium salt (A)
2. The additive for monoazo pigments according to 1 above, further comprising a monoazo compound (Z) having a structure obtained by reacting an acetoacetic acid arylamide compound (C) having a carbamoyl group or an acetylamino group.

4. An additive for a monoazo pigment comprising a monoazo compound (Y) having a structure obtained by reacting an aniline compound diazonium salt (A) with an acetoacetic acid arylamide compound (B) having a carboxyl group and a hydroxyl group is added to the monoazo pigment (X). A pigment composition comprising:

5. 5. The pigment composition according to the above 4, wherein the monoazo compound (Y) is a monoazo compound represented by the following general formula (y). General formula (y)

Embedded image [However, in the general formula (y), R _X , R _Y and R _Z are independently
H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ , Cl
Is shown. R ₇ represents OH and R ₈ represents COOH. ]

6. 4. The method according to item 4, wherein at least a part of the monoazo compound (Y) is uniformly adsorbed on the primary particle surface of the monoazo pigment (X) or is contained in a crystal structure.
The pigment composition as described in the above.

[0015] 7. 5. The pigment composition according to the above 4, wherein the monoazo pigment (X) and the monoazo compound (Y) are simultaneously produced.

8. 8. An electrostatic charge developing toner comprising the pigment composition according to 4, 5, 6, or 7.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The pigment additive of the present invention is for a monoazo pigment (X) and comprises an aniline compound diazonium salt (A) and an acetoacetic acid arylamide compound (B) having a carboxyl group and a hydroxyl group. It is made of a monoazo compound (Y) having a reacted structure.

The production method of this monoazo compound (Y) is not particularly limited as long as it has the above-mentioned structure. For example, an aniline compound diazonium salt (A)
And an acetoacetic acid arylamide compound (B) having a carboxyl group and a hydroxyl group.

The diazonium salt (A) of the aniline compound of the present invention is a diazonium salt of aniline which may have a substituent on the benzene ring. The diazonium salt (A) can be obtained, for example, by reacting an aniline compound with hydrochloric acid and sodium nitrite.

As the aniline compound that can be used in the present invention, generally known compounds can be used.
For example, 2-nitro-4-methylaniline, 2-nitro-4-chloroaniline, 2-nitroaniline, 2-methyl-4-chloroaniline, 2-nitro-4-methoxyaniline, 2-methoxy-4-nitro Examples include aniline and 2-methoxy-4-sulfonamidophenyl-5-methoxyaniline.

On the other hand, the acetoacetic acid arylamide compound having a carboxyl group and a hydroxyl group (B) refers to an acetoacetic acid arylamide having a carboxyl group and a hydroxyl group on an aromatic ring.

The compound (B) which can be used in the present invention includes a compound represented by the general formula (III). General formula (III)

Embedded image [However, in the general formula (III), R ₇ is OH, R ₈ is COO
H is shown. ]

Examples of the acetoacetic arylamide compound (B) represented by the general formula (III) include polar couplers such as 3-hydroxy-4-carboxyacetoacetanilide and 4-hydroxy-3-carboxyacetoacetanilide. can give.

The monoazo compound (Y) can be obtained by subjecting the diazonium salt (A) and the compound (B) to a known and commonly used diazo coupling reaction at a molar ratio of 1/1. This reaction is carried out, for example, under acetic acid pH 3 to
6. After performing at a temperature of 5 to 30 ° C. for a time of 30 to 180 minutes, the temperature can be maintained at 80 to 95 ° C. and maintained for 1 to 3 hours. The reaction conditions are substantially the same for monoazo pigments (X), monoazo compounds (Y), (Z), and monoazo compounds other than (Y) and (Z) described below.

The reaction slurry containing the monoazo compound (Y) thus obtained can be used as it is as an additive for a monoazo pigment, but usually, the monoazo compound (Y) can be obtained by filtering, washing with water, drying, and pulverizing the monoazo compound (Y). Use apart.

A typical example of the monoazo compound (Y) is a monoazo compound represented by the following general formula (y). General formula (y)

Embedded image [However, in the general formula (y), R _X , R _Y and R _Z are independently
H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ , Cl
Is shown. R ₇ represents OH and R ₈ represents COOH. ]

The monoazo compound (Y), by itself, significantly improves the heat resistance of the monoazo pigment (X). In addition, the monoazo compound (Y) is based on an acetoacetic acid arylamide compound (C) having a carbamoyl group or an acetylamino group. The pigment additive further containing the monoazo compound (Z) having a chemical structure further remarkably improves the heat resistance of the monoazo pigment (X).

The acetoacetic acid arylamide compound having a carbamoyl group or an acetylamino group (C) is an acetoacetic acid arylamide having a carbamoyl group or an acetylamino group on an aromatic ring.

The monoazo compound (Z) is obtained by reacting an acetoacetic arylamide compound (C) represented by the general formula (IV) in place of the compound (B) for obtaining the monoazo compound (Y). Is a monoazo compound having a chemical structure obtained by General formula (IV)

Embedded image [However, in the general formula (IV), R ₉ is CONH ₂ or NH
COCH ₃ is shown. ]

The acetoacetic arylamide compound (C) of the general formula (IV) which can be used in the present invention is, for example, 3
-Carbamoyl acetoacetanilide, 4-carbamoylacetoacetanilide, 4-acetoacetylaminoacetoacetanilide and the like.

In the present invention, the acetoacetic arylamide compound (B) used for obtaining the monoazo compound (Y) is used.
Alternatively, instead of the acetoacetic arylamide compound (C) used to obtain the monoazo compound (Z), the compound represented by the general formula (II)
The following general formula (I) which does not belong to (I) or (IV)
A monoazo compound having a chemical structure obtained by reacting an acetoacetic acid arylamide compound as represented by I) can be further used in combination. General formula (II)

Embedded image [However, in the general formula (II), R ₄ , R ₅ and R ₆ are independently H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ ,
Cl, OH, COOH, CONH ₂ , NHCOCH ₃ , S
O ₃ H, but at least one or more OH, COOH,
CONH ₂ , NHCOCH ₃ and SO ₃ H are included. R ₄ , R ₅
And R ₆ are a combination of H, OH, COOH, H,
A combination of H, CONH ₂ , or H, H, NHCO
Except when CH ₃ is used. ]

Examples of the acetoacetic arylamide compound (C) represented by the general formula (II) which can be used in the present invention include 2-carboxyacetoacetanilide,
Carboxyacetoacetanilide, 4-carboxyacetoacetanilide, 4-carboxy-2-methylacetoacetoanilide, 4-carboxy-3-methylacetoacetoanilide, 2-chloro-4-carboxyacetoacetanilide, 3-chloro-4-carboxyacetoacetanilide, Examples include polar couplers such as 3,5-dicarboxyacetoacetanilide, 2-sulfoacetacetoanilide, 3-sulfoacetacetoanilide, and 4-sulfoacetacetoanilide.

As the monoazo pigment (X) of the present invention, any of the known and common yellow monoazo pigments can be used. I. Pigment Yellow 1, C.I.
I. Pigment Yellow 3, C.I. I. Pigment Yellow 5, C.I. I. Pigment yellow 49, C.I. I.
Pigment Yellow 65, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 97 and the like.

The pigment composition of the present invention contains the monoazo compound (Y) as an additive to the monoazo pigment (X) and, if necessary, the monoazo compound (Z). The monoazo compound (Y) is used in an amount of 1 to 100 parts by weight, and the monoazo compound (Z) is used in an amount of 1 to 100 parts by weight, per 100 parts by weight of the monoazo pigment (X).

The monoazo compound (Y), the monoazo compound (Z), and the monoazo compound that is neither (Y) nor (Z) are separately prepared, mixed, and included in the monoazo pigment (X). Yes, they can be generated at the same time.

Rather than preparing the monoazo pigment (X) and the monoazo compound (Y) separately and then mixing them, it is better to produce them at the same time. It was also found that (Y) could be arranged, and the heat resistance of the resulting pigment composition was further improved. The same applies to the case where the monoazo pigment (X) and the monoazo compound (Y) are used alone and the case where the monoazo compound (Z) is used in combination.
Of course, when both the monoazo compound (Y) and the monoazo compound (Z) are arranged near the pigment, the heat resistance of the pigment composition becomes highest.

The monoazo pigment (X) and the monoazo compound (Y) are not separately prepared and then mixed with each other, but they are formed at the same time. At least a part of the monoazo pigment (X) is uniformly adsorbed on the primary particle surface or is in a form included in the crystal structure, and the monoazo compound (Y) is arranged near the pigment. Can be done.

The monoazo pigment composition of the present invention can be synthesized so as to be produced simultaneously by using a synthesis method according to a conventionally known method. After preparing a diazonium salt (A) solution from an aniline compound and sodium nitrite, the diazonium salt (A) solution is mixed with a non-polar coupler and a polar coupler having the above-mentioned general formula (III) as an essential component. Monoazo pigment (X)
And the monoazo compound (Y) are essential and are synthesized at the same time. Then, if necessary, heat, filter, wash, dry,
By pulverizing, the yellow monoazo pigment composition according to the present invention can be obtained.

The non-polar coupler is an acetoacetic arylamide compound which reacts with the aniline compound (A) to form a monoazo pigment (X). This is an acetoacetate arylamide compound that does not belong to any of the general formulas (II) to (IV), and includes, for example, an acetoacetate arylamide compound represented by the general formula (I). General formula (I)

Embedded image [However, in the general formula (I), R ₁ , R ₂ and R ₃ independently represent
H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ , Cl
Is shown. ]

Examples of the acetoacetic arylamide compound represented by the general formula (I) which can be used in the present invention include, for example, acetoacetanilide, 2-methylacetoacetanilide, 4-methylacetoacetanilide, 2-methoxyacetoacetanilide, 4-methoxyacetoacetanilide Non-polar couplers such as acetoacetanilide, 4-ethoxyacetoacetanilide, 2-chloroacetoacetanilide, 2,4-dimethylacetoacetanilide, 2-methyl-4-chloroacetoacetanilide, 2,5-dimethoxy-4-chloroacetoacetanilide and the like. can give.

The polar coupler containing the acetoacetic acid arylamide compound of the general formula (III) as an essential component may be composed of only the compound of the general formula (III), but the compound of the general formula (IV) Or the general formula (II)
Can also be included.

In the present invention, the compounds represented by the general formulas (I) to (I) are used per mole of the diazonium salt (A) of the aniline compound.
Each mole% of the compound of V) is not particularly limited.

In a ternary system using only the compounds of the general formulas (I) to (III), first of all, the general formula (I)
Assuming that the total of (III) to (III) is 100 mol%, mol% of general formula (I) / [total mol% of general formulas (II) to (III)] is 50 to 99.5 mol% / 50 to 0 It is preferably set to 0.5 mol%.

Further, when the above preferable conditions are satisfied, when the general formula (II) is converted into 100 mol%, the general formula (III) is adjusted to be 0.5 to 50 mol%. Is more preferred.

In a four-component system using the compounds of the general formulas (I) to (IV), first of all, the general formulas (I) to (I)
Assuming that the total of V) is 100 mol%, the mol% of general formula (I) / [the total mol% of general formulas (II) to (IV)]
It is preferred to be 50-99 mol% / 50-1 mol%.

Further, the above-mentioned preferred conditions are satisfied, and at least 0.5 to 50 mol% of the acid-substituted coupler represented by the general formula (III) and at least the amide-substituted coupler represented by the general formula (IV) are added. The formulas (III) and (IV) are used independently in an amount of 0.5 mol% or more, and the total amount of the formulas (III) and (IV) is 50%. Mole% should not be exceeded.

The gist of the present invention is that a diazonium salt of an aniline compound is prepared by converting a dipolar aniline compound to a non-polar coupler represented by the general formula (I):
A monoazo yellow pigment composition obtained by coupling 99.5 mol% of an acid group-substituted coupler represented by the general formula (III) with at least 0.5 to 50 mol%; 50-99 mol% of the nonpolar coupler represented by (I), the general formula (II)
The acid-substituted coupler represented by I) is at least 0.5 to 5
The present invention relates to a monoazo yellow pigment composition obtained by coupling 0 mol% of an amide group-substituted coupler represented by the general formula (IV) with at least 0.5 to 50 mol%. The polar coupler represented by formula (II) other than (III) and formula (IV) is used in an amount of 0.5 to 50% by mole.

As described above, the yellow monoazo pigment composition of the present invention can be synthesized by a conventionally known synthesis method. If necessary, a conventionally known additive such as rosin and a surfactant may be added before and after the synthesis of the monoazo yellow pigment composition to synthesize the monoazo yellow pigment composition of the present invention.

The pigment composition of the present invention can be used in various printing inks such as lithographic inks and gravure inks, various paints such as baking paints and air-drying paints, colored molded articles such as polyolefin and polyurethane molded articles, as well as static molded articles. Charge image developing toner,
Any known and commonly used applications such as high-tech applications such as color filters can be used. However, the pigment composition of the present invention is used in applications that receive a high thermal history, for example, a colored molded article of a high melting point thermoplastic resin such as polyphenylene sulfide or polybutylene terephthalate, or an electrostatic image development through a heat-set fixing process. It can be suitably used as a toner for toner.

The color toner according to the present invention includes a one-component color toner containing a magnetic substance in the color toner (magnetic one-component development color toner) and a non-magnetic one-component color toner containing no magnetic substance (non-magnetic one-color toner). (A color toner for component development) or a color toner for a two-component developer mixed with a carrier (color toner for two-component development).

The one-component magnetic toner is, for example, a colorant, a binder resin, a magnetic powder, a charge control agent (CCA), and other additives typified by a mold release agent. Can be configured.

The amount of the colorant used in the present invention in the color toner is not particularly limited.
It is preferably used in an amount of 0.5 to 25 parts by weight with respect to 0 parts by weight.
More preferably, it is part by weight.

As the binder resin used in the color toner of the present invention, any known and commonly used resins can be used.
Any of natural resins, synthetic resins, natural rubbers, synthetic rubbers, synthetic waxes, and the like that exhibit adhesiveness under the application of heat or pressure can be used.

The natural resin useful in the present invention is, for example, balsam resin, rosin, shellac, koval, and the like. These resins are one or more selected from vinyl resins, acrylic resins, alkyd resins, phenol resins, and the like described below. It may be modified with the above resins.

The synthetic resin and synthetic wax used in the color toner of the present invention include, for example, polyvinyl chloride, polyacetal resin, polyamide, polycarbonate, polystyrene, polyacrylonitrile, polypropylene, polyethylene, fluorine resin, polyurethane, epoxy resin, and the like. Silicone resin, polyester, melamine resin, urea resin, phenolic resin, methacrylic resin,
An acrylic resin, an alkyd resin, a vinyl resin, a copolymer formed from each monomer component of these resins, an aliphatic or alicyclic hydrocarbon resin, an aromatic petroleum resin, a chlorinated paraffin, a paraffin wax and the like can be mentioned.

Examples of natural or synthetic rubber substances include natural rubber, chlorinated rubber, cyclized rubber, polyisobutylene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, polybutadiene rubber, butyl rubber, and the like.
Styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, silicone rubber, fluorine rubber, chlorohydrin rubber and the like can be mentioned.

The binder resin used in the color toner of the present invention is not limited to these, and two or more kinds of binder resin components may be appropriately mixed and used.

Of these, styrene-based resins, polyester-based resins and epoxy-based resins can be advantageously used in view of their transparency and the hue of the toner.

The magnetic powder used in the color toner of the present invention is not particularly limited, but those which hardly affect the reproduced color of the magnetic powder can be preferably used. Iron, yellow γ-iron oxide, iron oxide such as ferrite; iron, cobalt, metals such as nickel, or these metals and aluminum, cobalt,
Copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese,
Alloys with metals such as selenium, titanium, tungsten, vanadium, poly-1,4-bis (2,2,6,6,-
Organic magnetic substances such as tetramethyl-4-oxyl-4-piperidyl-1-oxyl) butadieneporphyrin metal complex, and mixtures thereof, and the like. Of these, yellow γ-iron oxide is particularly preferred from the viewpoint of hue.

The average particle diameter of these magnetic powders is 0.1 to 1
μm, from the viewpoint of charging stability and hue.
0.5 μm is preferred. The content of these in the toner is 30 to 1 with respect to 100 parts by weight of the binder resin.
It can be used in an amount of 50% by weight, and preferably 40 to 120% by weight based on 100 parts by weight of the binder resin from the viewpoint of charging stability and hue.

The color toner of the present invention further comprises various plasticizers, resistance adjusters and charge control agents for adjusting the thermal, electrical and physical properties of the toner, if necessary, in addition to the above components. May be.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, etc .; examples of the resistance adjuster include tin oxide, lead oxide, and antimony oxide; and examples of the charge control agent include quaternary ammonium salts and pyridinium salts. Examples thereof include metal dyes.

Further, in the present invention, after the production of the toner particles, fine powder such as TiO ₂ , Al ₂ O ₃ , SiO ₂ or the like is added to the toner particles to improve the fluidity of the toner, or zinc stearate, phthalic acid, etc. May be added to prevent deterioration of the photoconductor.

The color toner of the present invention can be obtained by an extremely general production method irrespective of a specific production method. For example, the above components are mixed by kneading means such as an extruder, a two-roll, a three-roll, or a heating kneader, cooled, stirred by a pulverizer such as a jet mill, and classified by an air classifier, and the present invention. Is obtained. The particle size of the color toner of the present invention is 5 to 5.
15 μm is preferred.

When used as a two-component color developer color toner, the same coloring agents, binder resins, and other additives as described above for the one-component color magnetic toner can be used.

The carrier used in the color toner of the present invention may be, for example, iron powder, nickel powder, ferrite powder, glass beads, or a styrene-acrylate copolymer, styrene- Methacrylic acid ester copolymer, acrylic acid ester polymer, methacrylic acid ester polymer, silicone resin, polyamide resin, ionomer resin, polyphenylene sulfide resin, etc. or a mixture of these resins can be used. Those having a range of 50 to 300 μm are preferred.

A color toner for a two-component color developer can be obtained by friction-mixing these carrier particles with the color toner of the present invention using a horizontal cylindrical or V-shaped container rotating mixer.

The mixing ratio of the carrier and the color toner can be generally used in the range of 2 to 10 parts by weight of the color toner with respect to 100 parts by weight of the carrier in order to obtain an appropriate image density. -6 parts by weight.

Next, preferred embodiments of the present invention will be described.

The yellow monoazo pigment composition is prepared by reacting a diazonium salt solution of an aniline compound with a suspension comprising a mixture of a non-polar and a polar coupler, heating if necessary, filtering, washing and drying. , Crush and get.

100 parts by weight of at least one binder resin selected from the group consisting of a styrene resin, a polyester resin and an epoxy resin, 2 to 15 parts by weight of the pigment composition, and 40 to 1 per part by weight
20 parts by weight of a magnetic powder, a charge controlling agent, and a wax are kneaded at a temperature at which the binder resin melts, crushed and classified, and a dry powder color for electrostatic charge image development having a volume average particle diameter of 5 to 15 microns. Obtain toner.

To 100 parts by weight of the above, 0.3 to 5 parts by weight of hydrophobic silica having a smaller particle diameter than that described above is externally added, and the silica particles are adhered to the surface of the toner particles. A dry powder color toner for developing an electrostatic charge image for magnetic one-component development.

When the toner is used in the two-component developing method, 3 to 6 parts by weight per 100 parts by weight of the carrier is mixed with the toner to prepare a developer.

[0074]

The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified.

Production Example 1 4.3 parts of 2-nitro-4-methylaniline were added to 100 parts of water.
To this part, 8.6 parts of 32% hydrochloric acid was added while stirring and dispersing.
After stirring for 1 hour, 7.0 parts of 30% sodium nitrite was added in an ice bath to carry out a diazotization reaction.

Separately, 5.1 parts of acetoacetanilide and 0.28 part of 4-hydroxy-3-carboxyacetoacetoanilide were added to 100 parts of water, and 6.0 parts of 20% sodium hydroxide was further added and dissolved by stirring. In this, 2
24.7 parts of 0% acetic acid was added over 1 hour at room temperature to precipitate a coupler. Further, 7.9 parts of 20% caustic soda was added thereto, and the pH was adjusted to 5.5. While maintaining the internal temperature at 5 to 15 ° C. in an ice bath, the diazo solution was added over 2 hours to perform a coupling reaction.

After the coupling is completed, the mixture is heated to 90 ° C.
Hold for hours. Next, it was filtered, washed with water, and dried with a dryer at 90 ° C. The obtained solid was pulverized with a juicer mixer to obtain a monoazo yellow pigment composition according to the present invention.

This monoazo yellow pigment composition is C.I. I.
and Pigment Yellow 1, monoazo compounds of the general formula (y) (Y) [R _X = CH ₃ in the 4-position of the benzene ring of the aniline compound, R _Y = NO ₂ in the 2-position, R _Z is H, the other hand, coupler R ₇ = 0 at the 4-position of the benzene ring of the compound
H and R ₈ = COOH at the same position. Wherein at least a part of the monoazo compound (y) is C.I.
I. Pigment Yellow 1 was presumed to be uniformly adsorbed on the primary particle surface or contained in the crystal structure.

Production Example 2 5.1 parts of acetoacetanilide and 4-hydroxy-
Except for using 5.4 parts of acetoacetanilide instead of 0.28 part of 3-carboxyacetoacetanilide,
Monoazo yellow pigment (CI pi) according to Production Example 1
gment Yellow 1) was produced.

Production Example 3 (A method according to the method described in Example 1 of JP-B-55-10630) 5.1 parts of acetoacetanilide and 4-hydroxy-
Instead of using 0.28 parts of 3-carboxyacetoacetanilide, 4.7 parts of acetoacetanilide and 0.26 parts of 2-carboxyacetoacetoanilide were used,
According to Production Example 1, a monoazo yellow pigment was produced.

Production Example 4 5.1 parts of acetoacetanilide and 4-hydroxy-
Instead of 0.28 parts of 3-carboxyacetoacetanilide, 5.1 parts of acetoacetoanilide, 4-hydroxy-
A monoazo yellow pigment composition according to the present invention was prepared according to Preparation Example 1, except that 0.14 part of 3-carboxyacetoacetanilide and 0.13 part of 4-carbamoylacetoacetanilide were used.

This monoazo yellow pigment composition is C.I. I.
and Pigment Yellow 1, monoazo compounds of the general formula (y) (Y) [R _X = CH ₃ in the 4-position of the benzene ring of the aniline compound, R _Y = NO ₂ in the 2-position, R _Z is H, the other hand, coupler R ₇ = 0 at the 4-position of the benzene ring of the compound
H and R ₈ = COOH at the same position. 〕When,
Monoazo compound (z) [the 4-position of the benzene ring of the aniline compound _{R X = CH 3, R Y} = NO 2, R Z in the 2-position is H, whereas, CONH the 4-position of the benzene ring of the coupler compound ₂
Respectively. Wherein at least a part of the monoazo compounds (y) and (z) is C.I. I. pigment
It was presumed that it was uniformly adsorbed on the surface of the primary particles of Yellow 1 or contained in the crystal structure.

Production Example 5 (A method according to the method described in Example 7 of JP-B-55-10630) 4.3 parts of 2-nitro-4-methylaniline was added to 100 parts of water.
To this part, 8.6 parts of 32% hydrochloric acid was added while stirring and dispersing.
After stirring for 1 hour, 7.0 parts of 30% sodium nitrite was added in an ice bath to carry out a diazotization reaction.

Separately, 5.1 parts of acetoacetanilide and 0.27 part of 4-acetoacetylaminobenzenesulfonamide were added to 100 parts of water, and 6.0 parts of 20% sodium hydroxide was further added, followed by stirring and dissolving. In this, 20
24.7 parts of acetic acid was added over 1 hour at room temperature to precipitate a coupler. Further, 7.9 parts of 20% caustic soda was added thereto, and the pH was adjusted to 5.5. While maintaining the internal temperature at 5 to 15 ° C. in an ice bath, the diazo solution was added over 2 hours to perform a coupling reaction. Simultaneously with the addition of the diazo solution, an aqueous solution in which 0.04 part of 3-acetoacetylaminobenzenesulfonic acid was dissolved in 10 parts of water was added from another dropping funnel so that the dropwise addition was completed about 10 minutes before the completion of the coupling. .

After completion of the coupling, the mixture was heated to 90 ° C.
Hold for hours. Next, it was filtered, washed with water, and dried with a dryer at 90 ° C. The obtained solid was pulverized with a juicer mixer to obtain a monoazo yellow pigment composition.

Production Example 6 4.7 parts of 2-methoxy-4-nitroaniline were added to 10 parts of water.
8.6 parts of 32% hydrochloric acid was added while stirring and dispersing to 0 parts. After stirring for 1 hour, 30% sodium nitrite 7.0 in an ice bath.
Was added to carry out a diazotization reaction.

Separately, 6.0 parts of 2-methoxyacetoacetanilide and 0.28 part of 4-hydroxy-3-carboxyacetoacetanilide were added to 100 parts of water, and 6.0 parts of 20% caustic soda was further added. did.
Into this, 24.7 parts of 20% acetic acid was added over 1 hour at room temperature to precipitate a coupler. In addition, 20
% Caustic soda was added and the pH was adjusted to 5.5. While maintaining the internal temperature at 5 to 15 ° C. in an ice bath, the diazo solution was added over 2 hours to perform a coupling reaction.

After completion of the coupling, the mixture was heated to 90 ° C.
Hold for hours. Next, it was filtered, washed with water, and dried with a dryer at 90 ° C. The obtained solid was pulverized with a juicer mixer to obtain a monoazo yellow pigment composition according to the present invention.

This monoazo yellow pigment composition is C.I. I.
pigment Yellow 74 and the general formula (y)
The monoazo compound (Y) [R _X = NO ₂ in the 4-position of the benzene ring of the aniline compound, R _Y = OCH ₃ in the 2-position, R _Z is H, whereas, R ₇ at the 4-position of the benzene ring of the coupler compound
ＯＨOH and R ₈ ＣＯCOOH at the 3-position. ]
Wherein at least a part of the monoazo compound (y) is
C. I. Pigment Yellow 1 was presumed to be uniformly adsorbed on the primary particle surface or contained in the crystal structure.

Production Example 7 6.0 parts of 2-methoxyacetoacetanilide and 4-part
Hydroxy-3-carboxyacetoacetanilide 0.
Monoazo yellow pigment (CI pigment Yellow) according to Production Example 6 except that 6.2 parts of 2-methoxyacetoacetanilide was used instead of 28 parts.
74) was manufactured.

Production Example 8 (method according to the method described in Example 3 of JP-B-55-10630, 6.0 parts of 2-methoxyacetoacetanilide and 4-part of 4-methoxyacetoacetanilide)
Hydroxy-3-carboxyacetoacetanilide 0.
A monoazo yellow pigment composition was produced according to Production Example 6, except that 6.0 parts of 2-methoxyacetoacetanilide and 0.26 parts of 3-carboxyacetoacetanilide were used instead of 28 parts.

Production Example 9 (method according to the method described in Example 6 of JP-B-55-10630) 6.0 parts of 2-methoxyacetoacetanilide and 4-part of 4-methoxyacetoacetanilide
Hydroxy-3-carboxyacetoacetanilide 0.
A monoazo yellow pigment composition was produced according to Production Example 6, except that 6.0 parts of 2-methoxyacetoacetanilide and 0.26 parts of 4-carbamoylacetoacetanilide were used instead of 28 parts.

Production Example 10 6.0 parts of 2-methoxyacetoacetanilide and 4-
Hydroxy-3-carboxyacetoacetanilide 0.
Production Example 6 was repeated except that 6.0 parts of 2-methoxyacetoacetanilide, 0.14 part of 4-hydroxy-3-carboxyacetoacetoanilide and 0.14 part of 4-acetoacetylaminoacetoacetanilide were used instead of 28 parts. Thus, a monoazo yellow pigment composition according to the present invention was produced.

This monoazo yellow pigment composition is C.I. I.
pigment Yellow 74 and the general formula (y)
The monoazo compound (Y) [R _X = NO ₂ in the 4-position of the benzene ring of the aniline compound, R _Y = OCH ₃ in the 2-position, R _Z is H, whereas, R ₇ at the 4-position of the benzene ring of the coupler compound
ＯＨOH and R ₈ ＣＯCOOH at the 3-position. ]
If, monoazo compound (z) [R _X = NO ₂ in the 4-position of the benzene ring of the aniline compound, R _Y = OCH ₃ in the 2-position, R _Z is H, whereas, CO at the 4-position of the benzene ring of the coupler compound
Each having NHCH ₃ . Wherein at least a part of the monoazo compounds (y) and (z) is C.I. I. pi
gment Yellow 74 was presumed to be uniformly adsorbed on the primary particle surface or included in the crystal structure.

Example 1 [Production of color toner] Styrene-acrylic acid copolymer (Hymer SBM100, manufactured by Sanyo Chemical Industries, Ltd.) 100.0 parts Monoazo yellow pigment composition produced in Production Example 1 5.0 parts Yellow γ-iron oxide (MAPICO Y-LOP, manufactured by Titanium Industry Co., Ltd.) 40.0 parts

After kneading the above components with an extruder, the mixture was pulverized and classified by a jet mill to obtain a toner having an average particle diameter of 10 μm, and hydrophobic silica (Aerosil R-972, manufactured by Nippon Aerosil Co., Ltd.) was added to the toner at a concentration of 1.0% This was mixed to obtain a one-component yellow magnetic toner.

[Evaluation of Color Toner] Using this one-component yellow magnetic toner, a dry plain paper copying machine (Recopy F
T3010 (manufactured by Ricoh Co., Ltd .; the same applies hereinafter). As a result, a clear yellow image without background fog was obtained even on the 5000th copy (evaluation: ○).

Next, C.I. I. Pigment Yellow
When development was performed in combination with a cyan developer using ow 15: 3, a clear green color was reproduced.

Further, C.I. I. Pigment Red 1
When developed in combination with a magenta developer using No. 22, a clear orange color was reproduced.

Comparative Example 1 The procedure of Example 1 was repeated, except that 5.0 parts of the monoazo yellow pigment produced in Comparative Example 1 was used instead of 5.0 parts of the monoazo yellow pigment composition produced in Production Example 1. The same components as in Example 1 were kneaded, pulverized and classified in the same manner as in Example 1 to obtain a toner having an average particle diameter of 10 μm, and 1.0% by weight of hydrophobic silica (Aerosil R-972) was added thereto. This was a one-component yellow magnetic toner.

Using this one-component yellow magnetic toner,
When development was carried out using the same dry-type plain paper copier as described above, a clear yellow image as obtained in Example 1 was not obtained.

Further, C.I. I. Pigment Yellow
When development was performed in combination with a cyan developer using ow 15: 3, a strong bluish color was not obtained and a clear green color was not obtained.

C. I. Pigment Red 122
When the development was carried out in combination with a magenta color developer using, a strong reddish color and a clear orange color could not be obtained.

Examples 2 to 4 and Comparative Examples 2 to 6 In place of the monoazo yellow pigment composition produced in Production Example 1,
Using the monoazo yellow pigment or the monoazo yellow pigment composition shown in Table 1, a developer was prepared in accordance with Example 1.

The developer thus obtained was subjected to a development test using a dry plain paper copying machine (Recopy FT3010, manufactured by Ricoh Co., Ltd.) in the same manner as in Example 1. The results are shown in Table 1.

[0106]

[Table 1]

[Results of Developing Test] ：: Very good clarity, very good color reproducibility ：: Good clarity, good color reproducibility △: Slightly good, poor color reproducibility ×: Poor clarity, color reproducibility Bad

As is clear from Table 1, the heat resistance of the monoazo yellow pigment composition of the present invention was improved, and a clear image was obtained from a developer using the same. Since the monoazo yellow pigment or the pigment composition obtained by the method had poor heat resistance, an image obtained from a developer using the same was unclear.

Further, a developer using the monoazo yellow pigment composition according to the present invention; I. Pigment Ye
Combination with cyan developer using C.l.low 15: 3, C.I. I. When combined development with a magenta developer using Pigment Red 122 was performed, clear green and orange colors were reproduced in each of the examples.

On the other hand, a developer using a monoazo yellow pigment or a pigment composition obtained by a conventionally known method, a C.I. I. Pigment Yellow 15:
Combination with cyan developer using C.3, C.I. I.
When combined development with a magenta color developer using Pigment Red 122 was carried out, a strong blue tint and red tint were observed, and clear green and orange colors were not obtained.

[0111]

The additive for a monoazo yellow pigment according to the present invention comprises:
Since it contains a monoazo compound having a specific chemical structure having a carboxyl group and a hydroxyl group, it has a particularly remarkable effect that superior heat resistance can be imparted as compared with conventional additives for pigments. In addition, since the monoazo pigment composition containing the pigment additive has excellent heat resistance as a result,
When this is used as a color toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., it has excellent clarity, and when used in combination with cyan toner and magenta toner, color reproduction And a color toner excellent in the above can be provided.

Claims (8)

[Claims] 1. An aniline compound diazonium salt (A),
An additive for a monoazo pigment (X) comprising a monoazo compound (Y) having a structure obtained by reacting a carboxyl group and an acetoacetic acid arylamide compound (B) having a hydroxyl group. 2. The additive for a monoazo pigment according to claim 1, wherein the monoazo compound (Y) is a monoazo compound represented by the following general formula (y). General formula (y) [However, in the general formula (y), R _X , R _Y and R _Z are independently
H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ , Cl
Is shown. R ₇ represents OH and R ₈ represents COOH. ] 3. An aniline compound diazonium salt (A),
The additive for a monoazo pigment according to claim 1, further comprising a monoazo compound (Z) having a structure obtained by reacting with an acetoacetic acid arylamide compound (C) having a carbamoyl group or an acetylamino group. 4. A monoazo pigment comprising a monoazo compound (Y) having a structure obtained by reacting a monoazo pigment (X) with a diazonium salt of an aniline compound (A) and an acetoacetic arylamide compound (B) having a carboxyl group and a hydroxyl group. A pigment composition comprising a pigment additive. 5. The pigment composition according to claim 4, wherein the monoazo compound (Y) is a monoazo compound represented by the following general formula (y). General formula (y) [However, in the general formula (y), R _X , R _Y and R _Z are independently
H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ , Cl
Is shown. R ₇ represents OH and R ₈ represents COOH. ] 6. The monoazo compound (Y), wherein at least a part of the monoazo pigment (X) is uniformly adsorbed on the surface of the primary particles of the monoazo pigment (X) or is contained in the crystal structure.
The pigment composition as described in the above. 7. The pigment composition according to claim 4, wherein the monoazo pigment (X) and the monoazo compound (Y) are simultaneously produced. 8. An electrostatic charge developing toner comprising the pigment composition according to claim 4, 5, 6 or 7.