JP2003089754A - Azo pigment composition, pigment dispersing agent and organic pigment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an azo pigment composition exhibiting excellent dispersion in a dispersion system having a high viscosity and a pigment dispersing agent. SOLUTION: The azo pigment composition is obtained by coupling at least one kind diazo component or tetrazo component obtained from aromatic amines with a coupler component consisting of 60-99.8 mol% of at least one kind coupler component (1) and 0.2-40 mol% of at least one kind coupler component (2) in which phthalimide, or carbamoyl benzoic acid, its alkyl ester or its metal salt is bonded to the coupler component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azo pigment composition used as a coloring agent for high-viscosity media such as plastics such as vinyl chloride resin, polyethylene resin and polyester resin, paints, various inks, toners and color filters. And a dispersant for dispersing the pigment in the high viscosity medium as described above.

[0002]

2. Description of the Related Art When manufacturing colored plastic compositions, color toners, etc., depending on the manufacturing conditions, 1 Pa.s (100
In many cases, the colorant is dispersed in a molten plastic having a high viscosity of 0 cP) or more. Under such a highly viscous dispersion condition, the wetting promotion effect due to the penetration of the vehicle into the pigment powder cannot be expected so much, and only the crushing of the pigment powder lump by shearing force and the pigment particle diffusion effect dominate the dispersibility. It becomes a factor. However, even under such dispersion conditions, the pigment is required to have more excellent dispersibility.

When a pigment is dispersed in a high-viscosity molten polymer or polymer solution system having a viscosity of more than 1 Pa · s (1000 cP), a method of lowering the viscosity by further heating temperature to knead the pigment, a metal soap, etc. at the time of kneading A method of improving the dispersibility of the pigment by adding the dispersant is generally used. Further, in recent years, it has become possible to perform dispersion with high viscosity by using a powerful disperser.

However, the dispersant such as metal soap used at the time of kneading has the problem that not only the dispersibility of the pigment in the polymer is good, but also various physical properties such as the strength of the polymer are deteriorated. Further, in dispersing the pigment in the high-viscosity polymer with a powerful disperser, it is often difficult to control frictional heat generated during the dispersion. Therefore, in order to disperse a high-viscosity kneaded meat such as a kneaded mixture of a molten polymer and a pigment, there are many examples in which a pigment surface-treated with a rosin, a surfactant, a polymer or the like has been conventionally used. There are few examples of using pigment derivatives to improve.

[0005]

In recent years, techniques such as a pigment surface treatment agent and a surface treatment method for a dispersion system in a general low-viscosity polymer medium (medium viscosity of 1 Pa · s (1000 cP) or less) have made remarkable progress in recent years. I've been The essence of these techniques is to impart affinity to the medium by making the surface of the pigment highly polar, and the polymer as the medium exerts its effect by forming an adsorption layer with the surface of the pigment. On the other hand, making the surface of the pigment highly polar leads to strengthening the cohesiveness between the pigment particles during the production of the pigment, and rather lowers the dispersibility in the dispersion of the highly viscous polymer medium system in which the permeation action of a solvent or the like cannot be expected. Often.

The most prominent example is kneading and dispersion in molten plastic. An extruder, a roll mill, a kneader, or the like is used for this dispersion, and the dispersion mechanism is the primary particle formation of pigment particles by high shearing force. Especially in such a system, improvement in dispersibility due to the effect of forming an adsorption layer of polymer molecules on the pigment surface cannot be expected so much, and a factor due to an increase in the cohesive force between pigment particles rather than an affinity between the pigment and the polymer acts as a negative effect. It often happens.

Therefore, an object of the present invention is to provide a pigment composition and a pigment dispersant which solve the above drawbacks of conventional surface treating agents and exhibit excellent dispersibility even in a highly viscous dispersion system. The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, (a) a coupler containing a coupler component in which a phthalimide or the like is bonded to a coupler skeleton, which is the same or different from the azo pigment or the like dispersed in a highly viscous medium. The inventors have found that an azo pigment composition obtained by coupling a component with a (b) diazo component or a tetrazo component is effective as an azo pigment and as a dispersant for various pigments, and completed the present invention.

[0008]

The above object can be achieved by the present invention described below. That is, the present invention relates to at least one diazo component or tetrazo component obtained from an aromatic amine and at least one coupler component (1).
~ 99.8 mol% and the following structural formula (I) and structural formula (II)
Of at least one coupler component (2) represented by
An azo pigment composition characterized by being coupled with a coupler component consisting of 2 to 40 mol%.

[0009] (However, Q in the formula is the basic skeleton of the coupler component (2),
R is a hydrogen atom, a halogen atom, a metal, a lower alkyl group,
Alternatively, each represents a nitrogen-containing organic group. )

The present invention also provides at least one diazo component or tetrazo component obtained from an aromatic amine, at least one 0 to 70 mol% of the coupler component (1), the above structural formula (I) and the structure. A pigment dispersant characterized by being coupled with a coupler component consisting of 30 to 100 mol% of at least one coupler component (2) represented by formula (II).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in more detail. The azo pigment composition of the present invention comprises at least one diazo component or tetrazo component conventionally used in the production of azo pigments, and a coupler component (1) conventionally used in the production of azo pigments as a coupling component. ) And at least one coupler component (2) represented by the above structural formulas (I) and (II) are coupled. The pigment dispersant of the present invention comprises at least one diazo component or tetrazo component described above and at least one coupler component (2) represented by the structural formulas (I) and (II), or It is characterized in that at least one kind of the coupler component (1) and the at least one kind of the coupler component (2) are coupled.

The azo pigment composition of the present invention is used in place of a conventional azo pigment which has the same pigment skeleton as that of a colorant to be dispersed in a highly viscous medium. Therefore, the azo pigment composition is used respectively in the synthesis of this azo pigment,
Obtained by coupling at least one diazo component or tetrazo component with at least one coupler component (1) and at least one coupler component (2) represented by the structural formula (〓) and structural formula (II). An azo pigment composition comprising at least two diazo compounds. Upon coupling, the coupler component (1) was used as a coupler component in an amount of 60 to 99.8 mol% and the coupler component (2) was used in an amount of 0.2 to 40 mol%, and used in the conventional production of azo pigments. At least one diazo component or tetrazo component obtained from the aromatic amine is coupled. In that case, in order to improve the hue and various physical properties of the azo pigment composition, a diazo component or a tetrazo component composed of a plurality of aromatic amines, or a plurality of coupler components (1) may be used at the same time.

By using the azo pigment composition of the present invention, the azo pigment composition substituted by the azo pigment composition and the pigment dispersant of the present invention are dispersed in a highly viscous medium more than Excellent dispersion effect is obtained. If the proportion of the coupler component (2) in the coupler component is too small, the dispersing effect will be insufficient, and if it is too large, the dispersing effect will be remarkable, but the weather resistance and heat resistance of the pigment composition will be reduced. The preferred ratio of the coupler component (2) used in combination with the coupler component (1) is 1 to 20 mol%.

On the other hand, the pigment dispersant of the present invention contains at least one coupler component (2) represented by the structural formula (〓) or structural formula (II), or at least one coupler component (1) above. At least one of the above-mentioned coupler component (2) and at least one diazo component or tetrazo component conventionally used for producing an azo pigment.
It is a polar substance consisting of at least one diazo compound obtained by coupling with a seed. Upon coupling, as the coupler component, the coupler component (1) is 0 to 70 mol%, preferably 0 to 50 mol%, and the coupler component (2) is 30 to 100 mol%, preferably 50 to 50 mol%.
Used at a rate of 100 mol%. The polar substance that is the obtained pigment dispersant is preferably used by uniformly coating the primary particle surface of the pigment to be dispersed therein.
The dispersant effect can be seen by using it as a pigment composition mixed with a pigment, and it can be added and used as a dispersant when the pigment is dispersed. The above-mentioned polar substance which is the pigment dispersant of the present invention has an excellent dispersing effect when various pigments are dispersed in a highly viscous medium, but one having a structure similar to that of the pigment to be dispersed, A higher dispersion effect can be obtained.

The above-mentioned polar azo compound is
It can also be synthesized from an aromatic amine represented by the structural formula (@) or the structural formula (II) (wherein Q in the formula is an aromatic amine skeleton), and further, the structural formula (@) or It can also be synthesized by coupling an aromatic amine represented by the structural formula (II) with a coupler component represented by the structural formula (@) or the structural formula (II), but the structural formula (@) or the structural formula It is synthetically advantageous to use the compound represented by (II) as the coupler component.

At least one diazo component or tetrazo component obtained from an aromatic amine and at least one coupler component (2) represented by the structural formula (〓) or structural formula (II) or the coupler component (1). The pigment dispersant synthesized by coupling at least one coupler component with at least one coupler component (2),
Many absorb at least part of visible light. Therefore, in using the pigment dispersant, it is effective that the pigment dispersant has the same or similar structure as the pigment to be dispersed, as a means for reducing the adverse effect on the hue. Therefore, as described above, when the pigment to be dispersed during the coupling reaction is an azo pigment, the structural formula (〓) and structural formula (II) having the basic coupler skeleton Q having the same structure as the coupler component of the azo pigment are used. Coupler component shown (2)
Is more effective in terms of dispersion effect. Even when the pigment to be dispersed is a pigment other than the azo pigment, it is preferable to use the coupler component (2) having a skeleton similar to that of the pigment. If at least 1 obtained from an aromatic amine
If the pigment dispersant synthesized by coupling one diazo component or tetrazo component with at least one coupler component (2) or a coupler component containing the same is a substance that does not absorb a wavelength in the visible light region, It can be expected to be effective in improving the dispersion of all colorants in a highly viscous medium.

The diazo component, the tetrazo component and the coupler component (1) used in the present invention are all well-known and commonly used in the production of conventional azo pigments, and they may be used alone or in the same kind or in different kinds. Two or more types are used. The diazo component is obtained by diazotizing an aromatic monoamine by a conventional method. Examples of aromatic monoamines include o (m, p) -chloroaniline, o (m, p) -toluidine, o-nitro-p-toluidine, 2-methoxy-4-nitroaniline, 2-methoxy-5-. Nitroaniline, 2-methyl-5-nitroaniline, o-chloro-
p-nitroaniline, p-aminobenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzanilide, 2-amino-4-N, N-diethylsulfur. Famoylanisole, 2-amino-4-benzylsulfonylanisole, 2,4,5-trichloroaniline, 2-
Nitro-4-chloroaniline, 2,5-dichloroaniline, 4-chloro-3-cyanoaniline, 2,6-dichloro-4-nitroaniline, 2,5-diethoxyaniline, o-aminobenzotrifluoride, 4 -Aminophthalimide, sulfanilic acid, anthranilic acid, 2-aminonaphthalene-1-sulfonic acid, 1-amino-4-methylbenzene-3-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid , 1-amino-4-chloro-5-methylbenzene-2-sulfonic acid,
1-amino-3-methylbenzene-4-sulfonic acid and the like can be mentioned.

The tetrazo component is obtained by tetrazotizing an aromatic diamine by a conventional method. Examples of the aromatic diamine are 3,3'-dichlorobenzidine and 3,3 '.
-Dimethoxybenzidine and the like.

The coupler component (1) is an acetoacetanilide compound, a pyrazolone compound, a naphthol AS compound or the like, and these compounds may be used alone or in combination of two or more of the same kind or different kinds. Examples of the acetoacetanilide compound include acetoacetanilide, acetoaceto-o-chloroanilide, acetoaceto-p-chloroanilide, acetoaceto-o-anisidide, acetoaceto-p-anisidide, acetoaceto-o-toluidide, and the like. Acetoaceto-p-toluidide, acetoaceto-2,4-xylidide, acetoaceto-2,4-dimethoxyanilide, acetoaceto-2,5-dimethoxyanilide, acetoaceto-2,
5-dimethoxy-4-chloroanilide, acetoaceto-2-methyl-4-chloroanilide, acetoaceto-
2-methyl-4-nitroanilide, acetoacetanilide, acetoaceto-2-chloro-4-methoxyanilide, acetoaceto-p-ethoxyanilide, acetoaceto-p-butoxyanilide, acetoaceto-5.
-Aminobenzimidazolone, 4-benzoylamino-
2,5-diethoxyacetoacetanilide and the like can be mentioned.

The pyrazolone compound is, for example, 1
-Phenyl-3-carbethoxy-5-pyrazolone, 1
-Phenyl-3-methyl-5-pyrazolone, 1- (p-
Tolyl) -3-methyl-5-pyrazolone and the like are naphthol AS compounds, for example, N-phenyl-3-
Hydroxy-2-naphthalenecarboxamide, N-
(2-Methylphenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (2-methoxyphenyl)
-3-hydroxy-2-naphthalenecarboxamide,
N- (4-chlorophenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (3-nitrophenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (4-methoxyphenyl) -3-hydroxy-
2-naphthalenecarboxamide, N- (2-ethoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (2,5-dimethoxyphenyl) -3-
Hydroxy-2-naphthalenecarboxamide, N-
(2-methoxy-5-nitrophenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (2-methyl-5-chlorophenyl) -3-hydroxy-2-naphthalenecarboxamide,

N- (2-methyl-4-chlorophenyl)
-3-hydroxy-2-naphthalenecarboxamide,
N- (5-chloro-2,4-dimethoxyphenyl) -3
-Hydroxy-2-naphthalenecarboxamide, 5-
(2'-Hydroxy-3'-naphthoylamino) -benzimidazolone, N- (4-chloro-2,5-dimethoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (2-methoxy- 5-chlorophenyl) -3-hydroxy-2-naphthalenecarboxamide, β-naphthol and derivatives thereof and the like can be mentioned. Further, these may be compounds whose partial substituents are substituted with a carboxyl group, a sulfonic acid group, a carboamide group, a sulfoamide group or the like, and further substituted with an alkali metal or an alkaline earth metal or the like. It does not matter.

In the coupler component (2) represented by the above structural formula (〓), phthalimide is used as a coupler used in the production of conventional azo pigments such as acetoacetanilide type, pyrazolone type and naphthol AS type compounds. Specific examples thereof include 4-acetoacetylamino-N-phenylphthalimide, 4-acetoacetylamino-2,5-dimethyl-N-phenylphthalimide, and 4-acetoacetylamino-3-methoxy. -N-
Phenylphthalimide, 4-acetoacetylamino-3
-Chloro-N-phenylphthalimide, 4-acetoacetylamino-2-methyl-3-chloro-N-phenylphthalimide, 3-acetoacetylamino-N-phenylphthalimide, 1- (4'-N-phenylphthalimide)- 3-methyl-5-pyrazolone, 1- (3'-N-
Phenylphthalimido) -3-methyl-5-pyrazolone, 1- (2 ', 5'-dichloro-4'-N-phenylphthalimido) -3-methyl-5-pyrazolone, N-
(4-N-phthalimidophenyl) -3-hydroxy-
2-naphthalenecarboxamide,

N- (2-methyl-4-N-phthalimidophenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (2-methoxy-4-N-phthalimidophenyl) -3-hydroxy-2-naphthalene Carboxamide, N- (3-nitro-4-N-phthalimidophenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (2-ethoxy-4-N-phthalimidophenyl) -3-hydroxy-2-naphthalene Carboxamide, N- (4-N-phthalimido-2,5-dimethoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (2-methoxy-4-N-phthalimido-5-nitrophenyl) -3 -Hydroxy-2-naphthalenecarboxamide, N- (2-methyl-4-N
-Phthalimido-5-chlorophenyl) -3-hydroxy-2-naphthalenecarboxamide, N- (2-methoxy-4-N-phthalimido-5-chlorophenyl)-
3-hydroxy-2-naphthalene carboxamide and the like can be mentioned.

The coupler component (2) represented by the above structural formula (II) is a carbamoyl coupler used in the production of conventional azo pigments such as acetoacetanilide type, pyrazolone type and naphthol AS type compounds. benzoic acid,
The alkyl ester, metal salt or the like is bound, and specific examples thereof include N- (4-acetoacetylaminophenyl) -2-carbamoylbenzoic acid and N-.
(4-acetoacetylamino-2,5-dimethylphenyl) -2-carbamoylbenzoic acid, N- (4-acetoacetylamino-2-methoxyphenyl) -2-carbamoylbenzoic acid, N- (4-acetoacetylamino -2-
Chlorophenyl) -2-carbamoylbenzoic acid, N-
(4-acetoacetylamino-2-chloro-5-methylphenyl) -2-carbamoylbenzoic acid, N- (3-acetoacetylaminophenyl) -2-carbamoylbenzoic acid, 1- {4- (2'-carboxy Benzoylamino) phenyl} -3-methyl-5-pyrazolone, 1-
{3- (2'-carboxybenzoylamino) phenyl} -3-methyl-5-pyrazolone, 1- {2 ', 5'
-Dichloro-4- (2'-carboxybenzoylamino) phenyl} -3-methyl-5-pyrazolone, N-
{4- (2'-Carboxybenzoylamino) phenyl} -3-hydroxy-2-naphthalenecarboxamide, N- {2-methyl-4- (2'-carboxybenzoylamino) phenyl} -3-hydroxy-2- Naphthalenecarboxamide,

N- {2-methoxy-4- (2'-carboxybenzoylamino) phenyl} -3-hydroxy-
2-naphthalenecarboxamide, N- {3-nitro-
4- (2'-carboxybenzoylamino) phenyl}
-3-hydroxy-2-naphthalenecarboxamide,
N- {2-ethoxy-4- (2'-carboxybenzoylamino) phenyl} -3-hydroxy-2-naphthalenecarboxamide, N- {2,5-dimethoxy-4-
(2'-Carboxybenzoylamino) phenyl} -3
-Hydroxy-2-naphthalenecarboxamide, N-
{2-Methoxy-4- (2'-carboxybenzoylamino) -5-nitrophenyl} -3-hydroxy-2-
Naphthalenecarboxamide, N- {2-methyl-4-
(2'-Carboxybenzoylamino) -5-chlorophenyl} -3-hydroxy-2-naphthalenecarboxamide, N- (2-methoxy-4- {2'-carboxybenzoylamino) -5-chlorophenyl} -3-hydroxy -2-naphthalenecarboxamide and the like, and the hydrogen atom of the carboxyl group of these compounds is halogen,
Examples thereof include those substituted with an alkali metal, an alkaline earth metal, a lower alkyl group having about 1 to 4 carbon atoms, or a nitrogen-containing organic group. As the coupler component (2), one type or two or more types are used. Basic skeleton Q of the coupler component in the above structural formulas (I) and (II) in the coupler component (2)
Indicates the basic skeleton of the above compound.

The azo pigment composition and the pigment dispersant of the present invention are produced by using the above-mentioned respective raw material components, and the production method can be carried out in accordance with the conventionally known production method of an azo pigment, and is particularly limited. Not done. The above-mentioned aromatic monoamine and aromatic diamine are diazotized or tetrazotized by a conventional method to obtain a diazonium salt and tetrazonium salt solution (diazo component or tetrazo component). On the other hand, the azo pigment composition of the present invention is prepared by preparing the above-mentioned coupler component (1) and coupler component (2) as a precipitating agent according to a conventional method, mixing the diazo component and the coupler component, and coupling them according to a conventional method. And a pigment dispersant are obtained.

What is important here is that the azo pigment composition as the azo pigment is used in place of the conventional azo pigment for the purpose of dispersing it in a highly viscous medium such as molten plastic, and therefore the aromatic amine used. Alternatively, the aromatic diamine and the coupler component (1) are limited to the raw material components of the conventional azo pigment for dispersion purposes. The same applies to the coupler component (2). For example, as a typical example, the azo pigment for dispersion is P
In the case of Y (CI Pigment Yellow) -83, the aromatic amine used is 3,3'-dichlorobenzidine and the coupler component (1) is acetoaceto-2,5-dimethoxy-4-chloroanilide. Becomes Similarly, PY
In the case of -74, 2-methoxy-4-nitroaniline and acetoaceto-o-anisidide are each added with PY.
In the case of -154, o-aminobenzotrifluoride and acetoaceto-5-aminobenzimidazolo, respectively, and in the case of PR (CI Pigment Red) -3, o-nitro-p-toluidine and betanaphthol, respectively. , PR-170, p-aminobenzamide and N- (2-ethoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide, PO, respectively.
(C. I. Pigment Orange) -13,
It becomes 3,3'-dichlorobenzidine and 1-phenyl-3-methyl-5-pyrazolone.

In addition to the combination of these aromatic amines or aromatic diamines and the coupler component used in the conventional production of azo pigments, a single or a plurality of other components may be used to improve the physical properties such as transparency and viscosity of the pigment. Aromatic amines and coupler components of and some of their substituents are carboxyl groups, sulfonic acid groups, carboamide groups, sulfoamide groups, etc., which are further substituted with alkali metals or alkaline earth metals, etc. It doesn't matter.

The azo pigment composition may be in the form of paste, lump or powder, and is used in the most suitable form depending on the dispersion method. Similarly, the pigment dispersant may be in the form of paste, lump, or powder, and when dispersing the pigment in a highly viscous medium such as molten plastic, the form of the pigment to be dispersed in the highly viscous medium or the dispersion process is adjusted. Used by adding in the state.

The pigment dispersant of the present invention can also be used as a pigment composition by adding it by a method that does not adversely affect the pigment during the production of various pigments. This pigment composition may be in the form of paste, lump, or powder, and is used in the most suitable form depending on the method of dispersion in a highly viscous medium such as molten plastic. The pigment dispersant is the pigment composition 10
2.0 parts by weight or more in 0 parts by weight, preferably 3.
It is used in a proportion of 0 to 20 parts by weight. The pigment composition may be prepared by uniformly mixing the pigment and the pigment dispersant of the present invention, or may be a pigment surface treated (coated) with the pigment dispersant of the present invention. It is preferable to use a pigment because the pigment has better dispersibility. The surface treatment method of the pigment with the dispersant is not particularly limited as long as the pigment surface is uniformly coated with the pigment dispersant. It can be said that the azo pigment composition of the present invention is a typical example of treating the pigment dispersant during the production.

Examples of pigments to be dispersed are soluble azo pigments represented by Lake Red C, Resole Red, Carmine 6B, Permanent Red 2B and Bordeaux, Permanent Red 4R, Naphthol Red, Permanent Carmine FB, Permanent Carmine FBB. ,
In addition to pyrazolone red, acetoacetoarylide-based monoazo yellow, benzimidazolone-based and other insoluble azo pigments, and other azo pigments such as acetoacetoarylide-based disazo yellow and other azo pigments, copper phthalocyanine, quinacridone All general pigments such as perylene, anthraquinone, isoindolinone, dioxazine violet, diketopyrrolopyrrole, carbon black and extender pigments such as titanium oxide and iron oxide can be mentioned.

A polar substance (a pigment of the present invention, which is a coupler component (2) represented by the above structural formulas (〓) and structural formula (II) or various azo compounds obtained by using the coupler component (1) The dispersant) is a surface treatment agent that has both the effect of increasing the affinity to the dispersion medium and the effect of reducing the cohesive force between the particles of the pigment, and the pigment composition using it is a surface treatment agent. Effective for shear dispersion. Furthermore, this polar substance has the effect of preventing the formation of strong aggregates of the pigment, which is found in general pigment surface treatment agents, even though it is highly polar when the pigment surface-treated with it is dried. The present inventors have found out that.

The effect of dispersing the pigment in the highly viscous medium of the pigment dispersant of the present invention is excellent because the atomization speed of the azo compound as the dispersant is overwhelmingly faster than the dispersion speed of general pigments.
It is considered that the finely divided dispersant acts on the surface of the difficult-to-disperse pigment to exert the effect of increasing the affinity between the difficult-to-disperse pigment and a medium such as molten plastic, and facilitates shear dispersion.

A part of various polar compounds synthesized by using the compounds represented by the above structural formulas (〓) and structural formula (II) as a coupler is used for a general solvent-rich paint system or ink system. It is a pigment derivative that has been studied as a pigment dispersant. However, we have discovered that the various polar compounds described above are effective as dispersants for pigments in "highly viscous media" with completely different dispersion mechanisms. On the other hand, many pigment derivatives and dispersants that are more effective as surface treatment agents and dispersants for ordinary low-viscosity media have been proposed, but these are not more effective dispersants for high-viscosity media. It is hard to say and has a low advantage.

The object of the present invention is to provide a novel technique of excellent pigment dispersibility in a highly viscous medium such as molten plastic, not as a surface treatment agent or a dispersant in general paints and inks having a high solvent content. To provide. This new technology is a pigment treated with a coupler component (2) represented by the above structural formula (〓) and structural formula (II) or a polar component obtained by coupling using a coupler component containing the same. It is based on the discovery that it has the effect of imparting a high polarity to the pigment and at the same time preventing the formation of strong aggregates of the pigment when the pigment is dried.

That is, the above-mentioned various polar compounds are surface-treating agents having both the effect of increasing the affinity of the pigment for the highly viscous dispersion medium and the effect of reducing the cohesive force between the particles of the pigment,
The inventors of the present invention have found that the pigment composition using the pigment has a remarkable effect on the dispersion of the pigment in the highly viscous medium. Furthermore, the present inventors have found that the above-mentioned various polar compounds act as a “dispersant” of the pigment in a highly viscous medium because the above-mentioned various polar compounds having a remarkably excellent dispersion rate act on the surface of the hardly-dispersed pigment. The inventors of the present invention have found that the action of improving the dispersibility of the hardly dispersible pigment is exhibited thereby. It should be particularly noted that the pigment composition and the dispersant of the present invention have unparalleled dispersibility with respect to the dispersibility of the pigment in the hot-melt plastic.

The reason why the term "various polar compounds" is used here is that the diazo component or tetrazo component obtained from a single or a plurality of aromatic amines and the above-mentioned structural formula () and structural formula ( When a single or a plurality of coupler components containing the coupler component represented by II) are coupled, a plurality of polar compounds are produced by the combination of the species, and each of them exhibits the same effect as a pigment dispersant. This is based on what the present inventors have confirmed.

The azo pigment composition, the pigment dispersant, and the pigment composition of the present invention are dispersed by a roll mill, an extruder, a kneader, or the like in which a thinner cannot be expected to permeate and only a shear force is used for dispersion. It should also be noted that it has a particularly remarkable effect of improving dispersibility.
The dispersion system in which the azo pigment composition, the pigment dispersant, and the pigment composition of the present invention are effectively used is for various plastics in a molten state, high-viscosity media such as high-concentration paints and printing inks. For example, it is particularly effective for producing a solid image recording colored composition for electrophotography, electrostatic printing or electrostatic recording.

[0039]

EXAMPLES The present invention will be described in detail with reference to pigment production examples and examples. "Parts" in the following text are parts by weight.

Pigment Production Example 1 50.6 parts of 3,3'-dichlorobenzidine are tetrazotized by a conventional method to obtain a tetrazonium salt solution. on the other hand,
115.2 parts of acetoaceto-2,5-dimethoxy-4-chloroanilide are prepared as a precipitating agent according to a conventional method. After mixing both solutions and coupling, after the reaction is completed,
The mixture is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 160.4 parts of untreated azo pigment-1.

Example 1 50.6 parts of 3,3'-dichlorobenzidine were tetrazotized by a conventional method to obtain a tetrazonium salt solution. on the other hand,
136.5 parts of 4-acetoacetylamino-N-phenylphthalimide is prepared as a precipitating agent according to a conventional method. After mixing both solutions and coupling, after the reaction is completed, 100
The mixture is stirred at ℃ for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 180.1 parts of pigment dispersant-1 of the invention.

Example 2 50.6 parts of 3,3'-dichlorobenzidine are tetrazotized by a conventional method to obtain a tetrazonium salt solution. on the other hand,
68.3 parts of 4-acetoacetylamino-N-phenylphthalimide and acetoaceto-2,5-dimethoxy-4-
57.6 parts of chloroanilide are prepared as a precipitating agent according to a conventional method. Both solutions are mixed and coupled, and after the reaction is completed, the mixture is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further dried and crushed to 170.
3 parts of inventive pigment dispersant-2 are obtained.

Example 3 50.6 parts of 3,3'-dichlorobenzidine was tetrazotized by a conventional method to obtain a tetrazonium salt solution. on the other hand,
13.7 parts of 4-acetoacetylamino-N-phenylphthalimide and acetoaceto-2,5-dimethoxy-4-
103.7 parts of chloroanilide are prepared as a base pickling agent according to a conventional method. Both solutions are mixed and coupled, and after the reaction is completed, the mixture is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further dry and crush 16
2.3 parts of the invention azo pigment composition-1 were obtained.

Example 4 10 parts of the dried product of the pigment dispersant of the present invention in Example 1 and 90 parts of the dried product of the untreated azo pigment in Production Example 1 were ground together to give an organic pigment composition of the present invention. -1 was obtained.

Example 5 To the pigment slurry after completion of the coupling reaction in Production Example 1, the pure amount of the paste of the pigment dispersant of the present invention in Example 1 was peptized with a 21.2 parts dissolver to form a slurry. inject. This product is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further, it was dried and pulverized to obtain 181.4 parts of the organic pigment composition-2 of the present invention.

Example 6 67.2 parts of 2-methoxy-4-nitroaniline was diazotized by a conventional method to obtain a diazonium salt solution. on the other hand,
136.5 parts of 4-acetoacetylamino-N-phenylphthalimide is prepared as a precipitating agent according to a conventional method. After mixing both solutions and coupling, after the reaction is completed, 100
The mixture is stirred at ℃ for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 196.4 parts of Pigment Dispersant-3 of the invention.

Example 7 The pigment slurry after completion of the coupling reaction in Pigment Production Example 1 was peptized with a pure amount of the paste of the pigment dispersant of the present invention in Example 6 by a 22.3 parts dissolver to form a slurry. Inject. This product is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further dried and pulverized to 182.2 parts of the organic pigment composition of the present invention-
Got 3.

Example 8 64.4 parts of o-aminobenzotrifluoride was diazotized by a conventional method to obtain a diazonium salt solution. on the other hand,
136.5 parts of 4-acetoacetylamino-N-phenylphthalimide is prepared as a precipitating agent according to a conventional method. After mixing both solutions and coupling, after the reaction is completed, 100
The mixture is stirred at ℃ for 2 hours, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 193.6 parts of pigment dispersant-4 of the invention.

Example 9 Example 6 was repeated except that 148.4 parts of 4-acetoacetylamino-2,5-dimethyl-N-phenylphthalimide was used instead of 4-acetoacetylamino-N-phenylphthalimide. To obtain 207.4 parts of Pigment Dispersant-5 of the invention.

Example 10 N- (4-acetoacetylaminophenyl) -instead of 4-acetoacetylamino-N-phenylphthalimide
214.5 parts of Pigment Dispersant-6 of the present invention was obtained in the same manner as in Example 6 except that 156.0 parts of 2-carbamoylbenzoic acid was used.

Example 11 N- (4-acetoacetylamino-2-chloro-5-methylphenyl) -2-carbamoylbenzoic acid 1 in place of 4-acetoacetylamino-N-phenylphthalimide
222.5 parts of Pigment Dispersant-7 of the present invention was obtained in the same manner as in Example 6 except that 64.7 parts was used.

Pigment Production Example 2 88.6 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid was diazotized by a conventional method to obtain a diazonium salt solution. On the other hand, 2-hydroxynaphthalene 7
9.8 parts are prepared as a preservative according to a conventional method. After mixing both solutions and coupling, after the reaction is completed, rosin 13
Parts of alkaline solution are added. Next, this is heated to 95 ° C., and 136.8 parts of barium chloride (dihydrate) is added to form an lake. This is further stirred at 95 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 226.8 parts of untreated azo pigment-2.

Example 12 88.6 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid was diazotized by a conventional method to obtain a diazonium salt solution. On the other hand, 173.0 parts of N- (4-N-phthalimidophenyl) -3-hydroxy-2-naphthalenecarboxamide is prepared as a pickling agent according to a conventional method. After mixing both solutions and coupling, after the reaction is completed,
The mixture is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further, it was dried and pulverized to obtain 251.0 parts of the pigment dispersant-8 of the invention.

Example 13 In Example 12, the dye slurry obtained after completion of the coupling reaction is heated to 95 ° C. and laked by adding an aqueous solution of 34.2 parts of barium chloride (dihydrate). This is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 264.5 parts of the pigment dispersant-9 of the invention.

Example 14 88.6 parts of 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid was diazotized by a conventional method to obtain a diazonium salt solution. On the other hand, 2-hydroxynaphthalene 7
5.8 parts and N- (4-N-phthalimidophenyl) -3
-Hydroxy-2-naphthalenecarboxamide 8.6
And parts are prepared according to a conventional method as a soaking agent. Both solutions are mixed and coupled, and after the reaction is completed, an alkali solution of 13 parts of rosin is added. Then heat it to 95 ° C,
An aqueous solution of 136.8 parts of barium chloride (dihydrate) is added to form a lake. This is further stirred at 95 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further, it was dried and pulverized to obtain 206.9 parts of the organic pigment composition-4 of the present invention.

Example 15 To the pigment slurry after lake formation in Pigment Production Example 2, a pure amount of the paste of the pigment dispersant of the present invention in Example 12 was peptized with a 13.5 parts dissolver to prepare a slurry and then injected. . This is stirred at 95 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further dry and crush 23
9.6 parts of inventive organic pigment composition-5 were obtained.

Example 16 Synthesis was carried out by the method of Example 12, except that N- (4-acetoacetylaminophenyl)-was used instead of N- (4-N-phthalimidophenyl) -3-hydroxy-2-naphthalenecarboxamide. 180.6 parts of 2-carbamoylbenzoic acid is prepared as a base pickling agent according to a conventional method. Both solutions are mixed and coupled, and after the reaction is completed, the mixture is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further dried and ground to 258.1 parts of pigment dispersant of the invention-1.
I got 0.

Example 17 In Example 12, the dye slurry obtained after the coupling was completed was heated to 95 ° C., and an aqueous solution of 45.1 parts of aluminum chloride (hexahydrate) was added to form a lake. This is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 263.5 parts of pigment dispersant-11 of the invention.

Example 18 54.4 parts of p-aminobenzamide was diazotized by a conventional method to obtain a diazonium salt solution. On the other hand, N- (2-
178.9 parts of methyl-4-N-phthalimidophenyl) -3-hydroxy-2-naphthalenecarboxamide are prepared as a precipitating agent according to a conventional method. Both solutions are mixed and coupled, and after the reaction is completed, the mixture is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further dried and ground to 223.1 parts of pigment dispersant of the invention-12.
Got

Example 19 60.8 parts of 4-amino-3-nitrotoluene was diazotized by a conventional method to obtain a diazonium salt solution. On the other hand, N
-(2-Methyl-4-N-phthalimidophenyl) -3
-Hydroxy-2-naphthalenecarboxamide 17
8.9 parts are prepared as a preservative according to a conventional method. Both solutions are mixed and coupled, and after the reaction is completed, the mixture is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 229.3 parts of Pigment Dispersant-13 of the invention.

Pigment Production Example 3 77.2 parts of butyl anthranilate were diazotized by a conventional method to obtain a diazonium salt solution. On the other hand, 135.3 parts of 5- (2-hydroxy-3'-naphthoylamino) -benzimidazolone is prepared as a base pickling agent according to a conventional method. After mixing both solutions and coupling, after the reaction is completed,
The mixture is stirred at 100 ° C. for 2 hours, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 201.9 parts of untreated azo pigment-3.

Example 20 77.2 parts of butyl anthranilate are diazotized by a conventional method to obtain a diazonium salt solution. On the other hand, 5- (2'-
Hydroxyl-3'-naphthoylamino) -benzimidazolone 128.5 parts and N- (4-N-phthalimidophenyl) -3-hydroxy-2-naphthalenecarboxamide 8.6 parts according to a conventional method Adjust as.
After mixing both solutions and coupling, after completion of the reaction, 10
The mixture is stirred at 0 ° C. for 2 hours, filtered and washed with water to obtain a hydrous presscake. Further drying and pulverization gave 203.8 parts of the azo pigment composition-2 of the present invention.

Example 21 50.6 parts of 3,3'-dichlorobenzidine are tetrazotized by a conventional method to obtain a tetrazonium salt solution. on the other hand,
135.3 parts of 1- (4'-N-phenylphthalimido) -3-methyl-5-pyrazolone is prepared as a precipitating agent according to a conventional method. Both solutions are mixed and coupled, and after the reaction is completed, the mixture is stirred at 100 ° C. for 1 hour, filtered and washed with water to obtain a hydrous presscake. 175.
3 parts of inventive pigment dispersant-14 are obtained.

[Evaluation of Pigment Dispersant, Azo Pigment Composition, and Organic Pigment Composition] A combination of the pigment dispersant and the pigment of each example and the following pigments, an azo pigment composition, and an organic pigment composition were used as samples, and Was dispersed in a vinyl chloride resin, a polyethylene resin, a polyester resin, or a styrene / methacrylate copolymer resin, and the dispersion effect was confirmed by controlling the case where only the azo pigment of each pigment production example or the following pigment was dispersed.

Pigment-4: Chromo Fine Yellow 591
0 (PY-166) (manufactured by Dainichiseika Kogyo KK) Pigment-5: Chromophine Yellow 2080 (PY-1)
54) (Same as above) Pigment-6: Seika Fast Yellow 2035 (PY-
97) (same as above) Pigment-7: Seika Fast Red 3820 (PR-
170) (same as above) Pigment-8: Chromofine Red 6820 (PV-1)
9) (Same as above) Pigment-9: Chromofine Red 6605 (PR-1)
77) (Same as above) Pigment-10: Chromofine Orange 3700LD
(PO-36) (same as above) (Note) PV: C.I. I. Pigment Violet

Dispersion Example 1 (Dispersion in Polyvinyl Chloride Resin) Each of the pigment dispersant, the azo pigment composition and the organic pigment composition of each Example was dispersed in a vinyl chloride resin using a two-roll mill. Dispersion into a polyvinyl chloride resin is performed by kneading a plasticizer with a Hoover Mahler (polyvinyl chloride resin / plasticizer = 1/1 (weight ratio) is blended for 100 rotations x 3 times). Sample and diluted vinyl chloride resin, sample / diluted vinyl chloride resin = 1/40 (weight ratio)
The mixture was mixed according to the above formula and diluted and dispersed for 3 minutes with a two-roll roller controlled at 167 ° C. to prepare a dark color sheet. Next, this dark-colored sheet was mixed with an appropriate amount of white compound containing titanium oxide (5%), and the mixture was controlled at 167 ° C.
This sheet was diluted and dispersed for 3 minutes to prepare a light-colored sheet.
The evaluation of dispersibility in vinyl chloride resin was performed by placing the dark-colored sheet and light-colored sheet of the sample to be compared next to each other at a thickness of 1 mm at the same time.
It was pressed at 165 to 175 ° C. for 3 minutes so that the dispersion was visually observed in the preparation of the dark-colored sheet and the coloring power of the light-colored sheet. The tinting strength was measured by measuring the pressed light-colored sheet with a Gretag portable reflection densitometer, and setting the blank sample to 100, the tinting strength was expressed. The above results are shown in Tables 2-4. The pigments -1 to -3 in the table are azo pigments -1 to -3 (the same applies to other dispersion examples).

Dispersion Example 2 (Dispersion in Polyethylene Resin) Polyethylene for dispersion (melting point: 90 ° C.) and a sample (pigment dispersant, etc.) were mixed in a ratio of 1/1 (weight ratio), and the mixture was rolled with three rolls. Make polyethylene flake that has been passed 4 times. The dark colored sheet is prepared by mixing polyethylene resin (eg Mitsubishi Polyethylene LD (manufactured by Mitsubishi Chemical Corporation)) with the above-mentioned polyethylene flakes in a ratio of 10/1 (weight ratio), and then at 120 ° C.
It was produced by passing through 10 times. On the other hand, for the light color sheet, prepare a sheet in which titanium oxide is dispersed in polyethylene resin,
Mix the above-mentioned dispersed flakes to form an appropriate amount, and
A light-colored sheet was produced by passing 10 times at 20 ° C. The evaluation method is the same as in dispersion example 1. The results are shown in Tables 5-6.

Dispersion Example 3 (Dispersion in a polyester resin in a kneader) After thoroughly mixing each raw material composition in a compounding formulation shown in Table 1 below with a super mixer, a bus co-kneader (manufactured by Buss) was used. The mixture was kneaded at about 120 ° C., cooled, pulverized using a jet mill pulverizer, and classified to prepare a powder having an average particle diameter of 35 μm. The above powder coating material was applied to a degreased steel plate by electrostatic spraying to a film thickness of about 80 μm, and baked at 180 ° C. for 20 minutes to obtain an evaluation coating film. The evaluation method was the same as in Dispersion Example 1. The results are shown in Tables 7-8.

Table 1 (formulation)

Dispersion Example 4 (Dispersion in Styrene / Methacrylate Copolymer Resin) A styrene / methacrylate copolymer resin (softened) was prepared using the azo pigment composition, the combination of the pigment and the dispersant, and the organic pigment composition of each Example as samples. Dispersion was performed at a point of about 110 ° C., a glass transition temperature of about 56 ° C., and a weight average molecular weight (measured by GPC. Converted to standard polystyrene) of about 50,000. 30 parts of each sample and 70 parts of the styrene / methacrylate copolymer resin described above. Was sufficiently kneaded with three rolls to disperse the sample, then cooled and coarsely crushed to obtain a high-concentration colored composition containing the sample at a concentration of 30%. 11.7 parts and 3 parts of a chromium complex salt type negative charge control agent were kneaded with 85.3 parts of the above-mentioned styrene / methacrylate copolymer resin by a conventional method, cooled, ground and then finely ground by a jet mill. Classification was carried out to produce a colored composition of 5 to 20 μm.
The coloring composition and colloidal silica as a fluidizing agent were thoroughly mixed according to a conventional method, and then mixed with magnetic iron powder as a carrier to obtain an electrophotographic developer. This electrophotographic developer was copied onto paper with a negatively charged full color developing electronic copying machine, and the effects of the azo pigment composition and the dispersant were confirmed. The results are shown in Table 9.

Table 2 Dispersion in vinyl chloride resin (1)

Table 3 Dispersion in vinyl chloride resin (2)

Table 4 Dispersion in vinyl chloride resin (3)

Table 5 Dispersion in polyethylene resin (1)

Table 6 Dispersion in polyethylene resin (2)

Table 7 Kneader dispersion in polyester resin (1)

Table 8 Dispersion in polyester resin with a kneader (2)

Table 9 (Dispersion in styrene / methacrylate copolymer resin)

[0079]

According to the present invention described above, an azo pigment composition having excellent dispersibility in a highly viscous medium such as molten plastic and a pigment capable of dramatically improving the dispersibility of the pigment in a highly viscous medium. A dispersant is provided. When the pigment dispersed in the highly viscous medium is an azo pigment, the dispersing effect can be further enhanced by using a pigment dispersant synthesized using the same derivative of the diazo component and the coupler component as the azo pigment.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 365 G03G 9/08 365 9/09 361 (72) Inventor Satoru Matsuzaki Nihonbashi Bakurocho, Chuo-ku, Tokyo 1-7-6 Dainichi Seika Kogyo Co., Ltd. (72) Inventor Naonori Takami 1-7-6 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo F-term inside Dainichi Seika Kogyo Co., Ltd. (reference) 2H005 AA06 CA21 DA04 DA10 4D077 AA03 AA06 AA08 AB03 AC05 DC42Z DC47Z DE15Y

Claims (8)

[Claims] 1. At least one diazo component or tetrazo component obtained from an aromatic amine, 60 to 99.8 mol% of at least one coupler component (1), and the following structural formula (I) and structural formula ( An azo pigment composition characterized by being coupled with a coupler component consisting of 0.2 to 40 mol% of at least one coupler component (2) represented by II). (However, Q in the formula is the basic skeleton of the coupler component (2),
R is a hydrogen atom, a halogen atom, a metal, a lower alkyl group,
Alternatively, each represents a nitrogen-containing organic group. ) 2. At least one diazo component or tetrazo component obtained from an aromatic amine, at least one 0-70 mol% of the coupler component (1), and the following structural formulas (I) and (II). A pigment dispersant characterized by being coupled with a coupler component consisting of 30 to 100 mol% of at least one coupler component (2) represented by (However, Q in the formula is the basic skeleton of the coupler component (2),
R is a hydrogen atom, a halogen atom, a metal, a lower alkyl group,
Alternatively, each represents a nitrogen-containing organic group. ) 3. The azo pigment composition according to claim 1, which is used for dispersion in a highly viscous medium. 4. The pigment dispersant according to claim 2, which is used for dispersing a pigment in a highly viscous medium. 5. A method for dispersing a pigment in a highly viscous medium,
An organic pigment composition comprising an organic pigment and the pigment dispersant according to claim 2. 6. The organic pigment composition according to claim 5, wherein the organic pigment is surface-treated with a pigment dispersant. 7. A solid coloring composition for image recording used for electrophotography, electrostatic printing or electrostatic recording, which is prepared by kneading at least a polymer as a highly viscous medium and a pigment. A coloring composition for image recording, which is the azo pigment composition described in 1. 8. A solid color recording composition for image recording used for electrophotography, electrostatic printing or electrostatic recording, which is prepared by kneading at least a polymer as a highly viscous medium and a pigment, and as a dispersant for the pigment. A coloring composition for image recording, comprising the pigment dispersant according to claim 2.