TWI404765B - Disazo pigment composition - Google Patents

Abstract

Disclosed is a disazo pigment composition characterized by containing a reaction product obtained by a coupling reaction of a diazo component composed of a tetrazonium salt of a compound represented by the general formula (I) below, a first coupling component composed of an acetoacetanilide compound and a second coupling component composed of a compound selected from the group consisting of an optionally substituted uracil, isocyanuric acid, barbituric acid and xanthine. [chemical formula 1] (I) (In the formula, R<SUP>1</SUP>, R<SUP>2</SUP>, R<SUP>3</SUP> and R<SUP>4</SUP> independently represent a hydrogen, a halogen, an alkyl group having 1-4 carbon atoms, an alkoxyl group having 1-4 carbon atoms or an alkoxycarbonyl group having an alkoxyl group having 1-4 carbon atoms.)

Description

Bisazo pigment composition

The present invention relates to a disazo pigment composition which is suitable for use in printing inks or coatings and the like.

The so-called disazo pigment is a general term for a pigment having two diazo groups in a molecular structure, but is mainly used for a diazo component such as 3,3'-dichlorobenzidine as a dinitrogen component. A general term for yellow pigments (also known as disazo yellow) obtained by coupling a diazo component with an even component comprising an N-acetyl oxime anilide compound. In the present invention, the bisazo pigment refers to the general meaning of the latter. Such bisazo pigments are widely used in printing inks, paints, plastics and the like.

The bisazo pigment is generally modified to improve various properties in the above-mentioned field of use. For example, in the field of printing inks, the following improvements are known for the purpose of improving fluidity or transparency.

That is, in place of the N-acetamidine anilide compound of the previous coupling component, a coupling reaction is carried out using an N-acetamidine anilide compound to which a specific substituent is introduced, and the bisazo compound thus obtained is mixed with the former a method of using a bisazo pigment (main pigment) (pigment mixing method), or a heterogeneous N-acetyl group introduced into a specific substituent by a coupling reaction with a previous N-acetamidine aniline compound A method of obtaining a pigment mixture by an anilide-based compound (mixed coupling method) or the like. Among such methods, the latter method (i.e., mixed-coupled law), which is excellent in productivity and can be obtained under various control conditions under relatively easy control conditions, has recently undergone most research and development.

For example, a method of introducing a water-soluble substituent to an N-acetamidine-aniline compound (Japanese Patent Laid-Open Publication No. SHO-49-105822 (Patent Document 1) and JP-A-55-135165 (Patent Document 2)) Or a method of introducing a sulfhydryl group or a quinone imine group as a substituent (JP-A-59-008761 (Patent Document 3)).

These methods have been proposed for the purpose of improving the fluidity or transparency as described above, or the coloring power or heat resistance, but it is required to further enhance the characteristics of the disazo pigment.

Patent Document 1: Japanese Laid-Open Patent Publication No. SHO-59-105165 (Patent Document No. JP-A-59-135165)

The present invention has been made in view of the above circumstances, and an object thereof is to provide a disazo pigment composition which further enhances properties such as transparency, gloss, coloring power, fluidity, and heat resistance.

In order to solve the above problems, the inventors of the present invention have obtained a coupling reaction as a coupling compound and an N-acetamidine anilide compound, and a specific compound having a basic structure is used to carry out a coupling reaction, thereby improving transparency and gloss. The knowledge of the characteristics such as coloring power, fluidity, heat resistance, etc., based on this knowledge and further research, finally completed the present inventors.

That is, the present invention relates to a disazo pigment composition characterized by comprising a diazo component comprising a bisazo salt of a compound represented by the following formula (I); N-acetamidine aniline a first coupling component composed of a compound; and a second coupling reaction coupling reaction selected from the group consisting of a compound having a substituent such as uracil, isocyanuric acid, barbituric acid and xanthine; Reaction product: Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Alkoxycarbonyl group.

The mixing ratio of the first coupling component to the second coupling component is preferably 85 mol% or more and 99 mol% or less of the first coupling component, and the second coupling is preferably 1 mol% or more and 15 mol% or less.

Further, in the above coupling reaction, it is preferred to further use a third coupling synthesis comprising a compound represented by the following formula (II). The blending ratio of the third coupling component is 95 mol% or more and 99.9 mol% or less of the total amount of the first coupling component and the second coupling component, and the third coupling is preferably 0.1 mol% or more and 5 mol% or less. Wherein R ⁵ and R ⁶ each independently represent hydrogen, halogen, methyl, methoxy, carboxyl, or sulfo, and R ⁷ represents methyl, methoxy, ethyl, ethoxy, methoxy. Carbonyl or ethoxycarbonyl.

Further, in the above coupling reaction, the fourth coupling synthesis of the compound represented by the following formula (III) or (IV) is further preferably used. The blending ratio of the fourth coupling component is a total amount of the first coupling component and the second coupling component, and the total amount of the first coupling component and the second coupling component and the third coupling component is 85 mol% or more and 99 mol. In the following or less, it is preferred that the fourth coupling is 1 mol% or more and 15 mol% or less.

Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and an alkyl group having 1 to 4 carbon atoms; a mercaptoamine group, an anthracene having an alkyl group having 1 to 4 carbon atoms, an phthalimide, an alkoxycarbonyl group having an alkyl group having 1 to 4 carbon atoms, and an alkane having 1 to 4 carbon atoms An alkoxysulfonyloxy group, a benzimidazolidinone, a carboxyl group, a carboxylate, a sulfonic acid group, or a sulfonate. Further, R ⁸ , R ⁹ and R ¹⁰ also include two of them bonded to each other to form an imidazolinone. Further, in the case of the general formula (IV), R ⁸ , R ⁹ and R ¹⁰ are each independently represented. Can be replaced by any benzene ring.

Further, the above bisazo pigment composition contains a selected from C.I. Pigment Yellow 12, CIPigment Yellow 13, CIPigment Yellow 14, CIPigment Yellow 17, CIPigment Yellow 55, CIPigment Yellow 81, CIPigment Yellow 83, CIPigment Yellow 87, CIPigment Yellow 152, CIPigment Yellow 170, CI At least one pigment of the group consisting of Pigment Orange 15 and CIPigment Orange 16 is preferred.

The bisazo pigment composition of the present invention has such a configuration that at least one of the properties of transparency, gloss, coloring power, fluidity, heat resistance and the like is improved as compared with the prior art. Therefore, when the bisazo pigment composition of the present invention is used in various applications, it is extremely useful in industrial applicability because it can obtain a coloring material excellent in transparency, gloss, coloring power, fluidity, and heat resistance.

In particular, when the bisazo pigment composition of the present invention is used in the field of one printing ink for its main use, it is possible to obtain full color printing of an ink film which is required to have high coloring power and excellent transparency. High transparency and high tinting strength are required.

Hereinafter, the present invention will be described in further detail.

<Double azo pigment composition>

The bisazo pigment composition of the present invention contains a reaction product obtained by coupling a diazo component described later with a complex couple component. The reaction Since the product is a complex couple component in the coupling reaction, two or more kinds are produced. Therefore, the bisazo pigment composition of the present invention contains such two or more kinds of reaction products.

<Diazo component>

The diazo component used in the present invention is a bisazo salt of a compound represented by the following formula (I): Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Alkoxycarbonyl group.

The compound represented by the above formula (I) is not particularly limited as long as it has the structure as described above, but particularly, 3,3'-dichlorobenzidine (the following formula (I-1)), 3,3'-dimethoxybenzidine or 2,2',5,5'-tetrachlorobenzidine is preferred. These compounds are easy to use as industrial raw materials.

Further, the bisazo salt is a method in which the two amine groups contained in the above formula (I) are each diazotized, and the method of diazotization is not particularly limited, and any of the conventional methods can be employed.

<couple synthesis>

The term "synthesis component" refers to a component which reacts with the above-mentioned diazo component in a general coupling reaction, and is classified into a feature in the present invention using a complex number as described above.

In other words, in the present invention, the first coupling component and the second coupling component, which will be described later, are used as an essential component, and the third coupling component and/or the fourth coupling component may be further used as desired. In addition, the details of each coupling component will be described later.

Further, the coupling reaction is a reaction in which a diazo component reacts with an even component to form an azo compound (reaction product). In the case of the present invention, in the coupling reaction coupling component, since the molecule of the diazo component is theoretically reacted by 2 molecules, the blending amount of the coupling component is preferably 2 to 2.5 mol per 1 mol of the diazo component.

<first coupling point>

The first coupling component of the present invention is composed of an N-acetamidine anilide compound. Here, the N-acetamidine anilide compound refers to a compound having various substituents of N-acetamidine anilide (hereinafter (C1-1)) or a phenyl group of N-acetamidine aniline. . The substituent may be, for example, a halogen, a methyl group, a methoxy group or an ethoxy group, and may have one or two or more of these substituents.

In the present invention, as the N-acetamidine anilide compound, an N-acetamidine anilide compound known as a coupling component of a conventionally known bisazo pigment can be used without particular limitation. For example, any N-acetamidine anilide compound represented by the following formula (C1-1) to formula (C1-6) can be preferably used.

In addition, as such a first coupling component, one type or two or more types of the above-mentioned N-acetamidine anilide compound can be used.

<2nd synthesis score>

The second coupling component of the present invention is selected from the group consisting of uracil, isocyanuric acid, barbituric acid and xanthine which may have a substituent. By using the second coupling component as an essential component together with the above-mentioned first coupling component, the characteristics such as transparency, gloss, coloring power, fluidity, and heat resistance can be greatly improved.

In other words, the conventional disazo pigment is usually obtained by coupling only the diazo component as described above with an N-acetylanilinium compound, and it is difficult to make any one or more of the above characteristics. Features that fully demonstrate the required performance. For example, it is easy to cause crystal growth by heating during processing or the like due to poor heat resistance, and there is a disadvantage that both the coloring power and the transparency are lowered. Further, when it is contained in an ink, there is a disadvantage that the fluidity of the ink is deteriorated due to the pigment structure.

According to the present invention, the first coupling component of the N-acetamidine anilide compound and the second coupling component different from the chemical structures are succeeded in that the problem is solved fundamentally. The characteristics such as transparency, gloss, tinting strength, fluidity, and heat resistance are greatly improved.

Here, the uracil which may have a substituent means uracil (the following formula (C2-1)) or a uracil having a substituent, and a uracil having a substituent, and for example, a 5-methyl group (the following formula) (C2-2)), 5-aminouracil (the following formula (C2-3)), 5-chlorouracil, 5-bromouracil, 5-fluorouracil, 5-nitrouracil, and the like.

Further, as such a second coupling component, one type or two or more types of the above compounds may be used. In addition, the mixing ratio of the first coupling component to the second coupling component is 85 mol% or more and 99 mol% or less of the first coupling component, and the second coupling synthesis is preferably 1 mol% or more and 15 mol% or less, and the first coupling component is 90 mol%. It is more preferably 95% by mole or less, and more preferably 5 mol% or more and 10 mol% or less of the above second coupling.

When the second coupling component is less than 1 mol%, the effect of improving the properties as described above may not be exhibited. When the amount is more than 15 mol%, the raw material cost is unfavorable and economically unrealistic.

<3rd synthesis score>

In the coupling reaction of the present invention, the third coupling component composed of the compound represented by the following formula (II) may be further used in combination with the first coupling component and the second coupling component in the coupling reaction.

In the above formula (II), R ⁵ and R ⁶ each independently represent hydrogen, a halogen, a methyl group, a methoxy group, a carboxyl group or a sulfo group, and R ⁷ represents a methyl group, a methoxy group or an ethyl group. Ethoxy, methoxycarbonyl or ethoxycarbonyl.

By using such a third coupling component in combination with the above-described first coupling component and second coupling component, characteristics such as transparency, gloss, coloring power, fluidity, and heat resistance can be further improved.

As the compound represented by the above formula (II), in particular, any compound represented by the following formula (C3-1) to formula (C3-5) is preferred, and the following formula (C3-4) or formula (C3-5) is preferred. The compound indicated is better.

Further, as such a third coupling component, one or two or more compounds represented by the above formula (II) can be used. In addition, the blending ratio is 95 mol% or more and 99.9 mol% or less of the total amount of the first coupling component and the second coupling component, and the third coupling is preferably 0.1 mol% or more and 5 mol% or less, and the first coupling component and the first coupling component are The total amount of the two coupling components is 97 mol% or more and 99.5 mol% or less, and the third coupling is preferably 0.5 mol% or more and 3 mol% or less.

When the third coupling component is less than 0.1 mol%, the effect of improving the properties as described above may not be exhibited. When the amount is more than 5 mol%, the raw material cost is unfavorable and economically unrealistic.

<4th composite score>

The coupling component of the present invention may be used in combination with the first coupling component and the second coupling component in the coupling reaction, and a fourth coupling component composed of a compound represented by the following formula (III) or (IV) may be further used. Such a fourth coupling component may be used together with the third coupling component, or may be used alone in combination with the first coupling component and the second coupling component without the third coupling component.

In the above formula (III) or (IV), R ⁸ , R ⁹ and R ¹⁰ each independently represent hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a decylamino group having an alkyl group having 1 to 4 carbon atoms, a quinone imine having an alkyl group having 1 to 4 carbon atoms, an phthalimide, an alkoxy group having an alkyl group having 1 to 4 carbon atoms A carbonyl group, an alkoxysulfonyl group having an alkoxy group having 1 to 4 carbon atoms, a benzimidazolidinone, a carboxyl group, a carboxylate, a sulfonic acid group, or a sulfonic acid salt. Further, R ⁸ , R ⁹ and R ¹⁰ also include those in which two of them are bonded to each other to form an imidazolidinone (for example, those represented by the following formula (C4-5)). Further, in the case of the general formula (IV), R ⁸ , R ⁹ and R ¹⁰ each independently represent a substituent which may be substituted by any benzene ring. Such a fourth coupling component is mainly used for the purpose of regulating fluidity or adjusting the hue. As the compound represented by the above formula (III) or (IV), in particular, any compound represented by the following formula (C4-1) to formula (C4-7) is preferred.

Further, as such a fourth coupling component, one or two or more compounds represented by the above formula (III) or (IV) can be used. Further, the blending ratio can be used in the same ratio as the above second couple component. In other words, the total amount of the first coupling component and the second coupling component, or the total amount of the first coupling component, the second coupling component, and the third coupling component is 85 mol% or more and 99 mol% or less, and the fourth coupling is 1 mol. % or more is 15 mol% or less, and the total amount of the first coupling component and the second coupling component, or the total amount of the first coupling component, the second coupling component, and the third coupling component is 90 mol% or more and 95 mol% or less. The fourth coupling composition is preferably 5 mol% or more and 10 mol% or less.

<Reaction product>

The reaction product of the present invention is obtained by coupling a reaction of the above diazo component with the above-mentioned coupling component. In the present invention, since the diazo component is a disazo salt, a reaction product is formed by reacting two molecules of the diazo component with one molecule.

Therefore, when the first coupling component and the second coupling component are used as the coupling component, as such a reaction product, it is expected that a reaction product of one molecule of the diazo component and two molecules of the first coupling component may be obtained. The reaction product of the diazo component of the molecule and the second coupling component of two molecules and the reaction product of one molecule of the diazo component and one molecule of the first coupling component and one molecule of the second coupling component are mixed and produced.

In the same manner, when the first coupling component, the second coupling component, and the third coupling component are used as the coupling component, as the reaction product, it is expected that one molecule of the diazo component and the first molecule of the molecule will be present. The reaction product of the coupling component, the reaction product of one molecule of the diazo component and the two molecules of the second coupling component, the reaction product of one molecule of the diazo component and the two molecules of the third coupling component, and one molecule of diazonium a reaction product of a first-synthesis component of one molecule and a second-synthesis component of one molecule, a reaction product of one molecule of a diazo component, a first coupling component of one molecule, and a third coupling component of one molecule, 1 The diazonium component of the molecule is mixed with a reaction product of a second coupling component of one molecule and a third coupling component of one molecule.

When the first coupling component, the second coupling component, and the fourth coupling component are used as the coupling component, or when the first coupling component, the second coupling component, the third coupling component, and the fourth coupling component are used, the same can be expected.

In other words, the reaction product of the present invention does not have one type of composition, and it is necessary to mix two or more types.

<Composition of bisazo pigment composition>

As described above, the bisazo pigment composition of the present invention is characterized in that the composition contains two or more kinds of the above reaction products.

Then, it is preferable that the reaction product is less than one type of pigment specified by the following C.I. Pigment No. (color index pigment number). That is, the disazo pigment composition of the present invention contains a selected from CIPigment Yellow 12, CIPigment Yellow 13, CIPigment Yellow 14, CIPigment Yellow 17, CIPigment Yellow 55, CIPigment Yellow 81, CIPigment Yellow 83, At least one pigment of the group consisting of CIPigment Yellow 87, CIPigment Yellow 152, CIPigment Yellow 170, CIPigment orange 15, and CIPigment orange 16 is preferred.

<Manufacturing method>

The bisazo pigment composition of the present invention contains a reaction product obtained by coupling the above diazonium component with a coupling component, but the specific conditions of the coupling reaction are not limited, and any of the previously known reaction conditions can be used. No problem. For example, a method of injecting a diazo component into a weakly acidic slurry in which the euro is synthesized and acidified (acid precipitation coupling method), or a method of simultaneously injecting a diazo component and an even component into a weakly acidic buffer solution (at the same time) Injection even law).

Here, specific conditions for exemplifying the acid evolution coupling method are as follows. That is, first, by coupling the aqueous solution of the coupling component, an aqueous solution such as acetic acid is added dropwise to adjust the pH of the system to a weakly acidic condition of 3 to 6.5 to analyze the coupling. Next, the coupling reaction was carried out by slowly dropping an aqueous solution of a diazo component by stirring.

Further, specific conditions for exemplifying simultaneous injection coupling are as follows. In other words, a buffer solution having a weak acidity (pH 3 to 6.5) is prepared by using acetic acid, sodium hydroxide or the like, and an aqueous solution of the diazo component and an aqueous solution of the dissolved coupling component are gradually added dropwise to carry out a coupling reaction. In this case, it is preferred that the diazo component is dissolved in an amount of from 2 to 2.5 mol per 1 mol of the diazo component.

<Example>

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. In addition, in the following description, unless otherwise mentioned, the "part" indicates the quality portion, and "%" indicates the mass%.

<Example 1>

Mixing 169 parts of 3,3'-dichlorobenzidine hydrochloride, 229 parts of 32% hydrochloric acid, and 4000 parts of water, and then under floating ice (conditions adjusted to 0 °C ± 2 °C) An aqueous solution containing 96 parts of sodium nitrite is added to the aqueous solution to obtain a bisazo salt of 3,3'-dichlorobenzidine (the above formula (I-1)) (that is, a compound represented by the above formula (I) The diazo component of the bis-azo salt). Hereinafter, this aqueous solution is referred to as a solution containing a diazo component. Further, the solution containing a diazo component contained 0.67 mol of a diazo component.

On the other hand, 238 parts of N-acetamidine (the above formula (C1-1) and the first couple) and 15 parts of uracil (the above formula (C2-1) and the second couple) were dissolved. An aqueous alkali solution composed of 87 parts of sodium hydroxide and 1000 parts of water. Hereinafter, this aqueous solution is referred to as a solution containing an even component. Further, the solution containing the coupling component contained 1.32 mol of the first coupling component and 0.13 mol of the second coupling component.

Next, 70 parts of acetic acid, 30 parts of sodium hydroxide, and 5000 parts of water were mixed to prepare a buffer solution at 20 °C. The solution containing the diazo component and the solution containing the coupling component were dropped into the buffer solution for 2 hours to carry out a coupling reaction.

Next, after the completion of the coupling reaction, the pH was adjusted to 5.0, and the alkali compound of the rosin 21 was added, and then 15 parts of aluminum sulfate was further added. Subsequently, the mixture was heated at 80 ° C for 30 minutes with stirring, and then filtered and washed with water to obtain a cake having a water content of 73%.

The filter cake comprising the bisazo pigment composition of the present invention contains a reaction product obtained by coupling a diazo component to a first coupling component and a second coupling component. In addition, the analysis was carried out by FD/MS (electric field deionization mass spectrometry) measurement, and it was confirmed that one of the reaction products contained C.I. Pigment Yellow 12.

<Example 2>

In Example 1, except that the solution containing the coupling component was used as the coupling component, N-acetanilide (the above formula (C1-1), the first coupling component) 238 (1.32 mol), isocyanuric acid (the above formula) (C2-4), the second coupling component) 13.2 (0.1 mol), 1-(2-chloro-5-sulfophenyl)-3-methyl-5-pyrazolone (the above formula (C3- 5), the third coupling component) 6.6 (0.02 mol), all other similarly obtained a filter cake having a water content of 72%.

The filter cake comprising the bisazo pigment composition of the present invention contains a reaction product obtained by coupling a diazo component with a first coupling component, a second coupling component, and a third coupling component. In addition, the same analysis as in Example 1 was carried out, and it was confirmed that one of the reaction products contained C.I. Pigment Yellow 12.

<Example 3>

In Example 1, except that the solution containing the coupling component was used as the coupling component, N-acetanilide (the above formula (C1-1), the first coupling component) 238 (1.32 mol), isocyanuric acid (the above formula) (C2-4), the second coupling component) 9.0 (0.07 mol), 5-acetylideneaminobenzimidazolone (the above formula (C4-5), the fourth coupling component) 15.5 (0.07 mol) In the same manner, all other filter cakes having a water content of 73% were obtained in the same manner.

The cake containing the bisazo pigment composition of the present invention contains a reaction product obtained by coupling a diazo component with a first coupling component, a second coupling component, and a fourth coupling component. In addition, the same analysis as in Example 1 was carried out, and it was confirmed that one of the reaction products contained C.I. Pigment Yellow 12.

<Example 4>

In Example 1, except that the solution containing the azo component was used as the coupling component, N-acetamidine aniline (formula (C1-1), first coupling component) 238 (1.32 mol), 5-methyluracil (Formula (C2-2), 2nd Synthesis) 8.6 (0.07 mol), 3-methyl-1-(p-sulfophenyl)-5-pyrazolone (Formula C3-4) , the third coupling component, 6.0 parts (0.02 mol), and p-ethoxy-N-acetoacetanilide (the above formula (C4-6), the fourth coupling component), 15.5 parts (0.07 mol), all others are the same A filter cake having a water content of 74% was obtained.

The filter cake comprising the bisazo pigment composition of the present invention contains a reaction in which a diazo component is coupled with a first coupling component, a second coupling component, a third coupling component, and a fourth coupling component. Object. In addition, the same analysis as in Example 1 was carried out, and it was confirmed that one of the reaction products contained C.I. Pigment Yellow 12.

<Example 5>

15 parts of N-acetamidine (the above formula (C1-1), first coupling component) and 15 parts of uracil (the above formula (C2-1) and the second coupling group) were dissolved in sodium hydroxide An aqueous alkali solution composed of 70 parts and 1000 parts of water.

Next, by dropping the aqueous solution for 30 minutes, 94 parts of acetic acid was diluted with a weakly acidic aqueous solution of 1000 parts of water to adjust the pH of the system to a weak acidic condition of 5.0, and the crystals of the even synthesis were precipitated. Hereinafter, the solution containing the precipitate is referred to as a solution containing an even component. Further, the solution containing the coupling component contained 1.32 mol of the first coupling component and 0.13 mol of the second coupling component.

Next, after cooling the solution containing the coupling component to 5 ° C, a coupling reaction containing the same diazo component as in Example 1 was carried out by stirring for 3 hours to carry out a coupling reaction.

Next, after the completion of the coupling reaction, the pH was adjusted to 5.0, and the alkali compound of the rosin 21 was added, and then 15 parts of aluminum sulfate was further added. Subsequently, the mixture was heated at 80 ° C for 30 minutes with stirring, and then filtered and washed with water to obtain a cake having a water content of 70%.

The filter cake comprising the bisazo pigment composition of the present invention contains a reaction product obtained by coupling a diazo component to a first coupling component and a second coupling component. In addition, the same analysis as in Example 1 was carried out, and it was confirmed that one of the reaction products contained C.I. Pigment Yellow 12.

<Example 6>

In Example 5, except that the solution containing the coupling component was used as the coupling component, N-acetanilide (the above formula (C1-1), the first coupling component) 238 (1.32 mol), isocyanuric acid (the above formula) (C2-4), the second coupling component) 13.2 (0.1 mol), 1-(2-chloro-5-sulfophenyl)-3-methyl-5-pyrazolone (the above formula (C3- 5), the third coupling component) 6.6 (0.02 mol), all other similarly obtained a filter cake having a water content of 71%.

The filter cake comprising the bisazo pigment composition of the present invention contains a reaction product obtained by coupling a diazo component with a first coupling component, a second coupling component, and a third coupling component. In addition, the same analysis as in Example 1 was carried out, and it was confirmed that one of the reaction products contained C.I. Pigment Yellow 12.

<Pylon Comparative Example 1>

In Example 1, 30 parts of the above-mentioned uracil (second coupling component) contained in the solution containing the azo component was used, and 2-acetic acid benzoic acid (the above formula (C4-1)) 30 parts (0.13 mol) was used. In the same manner as in Example 1, a filter cake having a water content of 75% was obtained.

The filter cake comprises a product of a coupling reaction of two kinds of coupling components composed of N-acetamidine and 2-ethylindenyl benzoic acid, but the product is in that the invention is not used. The point of the second coupling component is different from the composition of the reaction product of the present invention.

<Pylon Comparative Example 2>

In Example 1, 30 parts of 5-acetamidoaminobenzimidazolidone (formula (C4-5)) was used instead of 15 parts of uracil (second coupling component) contained in the solution containing the coupling component ( A filter cake having a water content of 74% was obtained in the same manner as in Example 1 except that 0.13 mol) was used.

The filter cake comprises a product of a coupling reaction of two kinds of coupling components composed of N-acetylindoline and 5-acetylamidobenzimidazolone, but the product is not used. The second coupling component of the present invention is different from the composition of the reaction product of the present invention.

<Comparative Example 3>

In Example 5, instead of using 15 parts of uracil (second coupling component) contained in the solution containing the coupling component, 30 parts of 2-ethylindolyl benzoic acid (the above formula (C4-1)) (0.13 mol) was used. In the same manner as in Example 5, a filter cake having a water content of 72% was obtained.

The filter cake comprises a product of a coupling reaction of two kinds of coupling components composed of N-acetamidine and 2-ethylindenyl benzoic acid, but the product is in that the invention is not used. The point of the second coupling component is different from the composition of the reaction product of the present invention.

<Comparative Example 4>

In Example 5, instead of using 15 parts of uracil (second coupling component) contained in the solution containing the azo component, 30 parts of 5-acetylindolylbenzimidazolone (formula (C4-5)) was used ( A filter cake having a water content of 74% was obtained in the same manner as in Example 1 except that 0.13 mol) was used.

The filter cake comprises a product of a coupling reaction of two kinds of coupling components composed of N-acetylindoline and 5-acetylamidobenzimidazolone, but the product is not used. The second coupling component of the present invention is different from the composition of the reaction product of the present invention.

<Ink>

The filter cakes obtained in the above Examples and Comparative Examples were inked by the following method.

In other words, a varnish for lithographic ink (trade name: soybean oil-based varnish LS-151; manufactured by Tosoh Oil Co., Ltd.) 210, which is heated to 50 ° C, is filled in a flash kneader, and further filled with a diazo pigment composition. The 100 filter cake was flashed. After removing the free water, 150 parts of the varnish for lithographic ink described above were further optimally mixed.

Then, the water was removed by vacuum dehydration at 90 ° C for 1 hour, and then the varnish 173.3 part and the solvent (trade name: AF-7 solvent; manufactured by Nippon Oil Co., Ltd.) were added to the lithographic ink varnish 173.3. A matrix ink of % bisazo pigment composition.

Then, an ink containing 9% of the disazo pigment composition was prepared by further adding 35 parts of the varnish for lithographic ink and 5 parts of the solvent to the base ink 60. Hereinafter, various tests were carried out by using the ink.

<Hue evaluation test>

The ink obtained in the above-described ink was applied to art paper using an RI tester (trade name: RI-2 type; manufactured by Ishikawajima Kogyo Co., Ltd.) to evaluate transparency, gloss, and coloring power. In addition, the application conditions of the ink were carried out using a four-part rubber roll as a roll of the RI tester, and the ink was filled in 0.125 cc in each divided portion.

First, the evaluation of the transparency is carried out by applying ink to an art paper which is divided into a white portion and a black portion by a central portion as a boundary, and visually judges the transparency of the black portion of the coating ink. Specifically, the black portion of the lower layer (the higher the blackness) is clearly observed through the ink application portion, and the transparency is good, and the one having particularly good transparency is "A", and the transparency is good. "B", those with moderate transparency are "C", and those with poor transparency are evaluated as "D".

In addition, the gloss evaluation was evaluated by measuring the 60-degree gloss of the ink-coated surface on the art paper using a digital angular gloss meter (trade name: UGV-4D; manufactured by SUGA Tester Co., Ltd.). In this measurement, the larger the value measured, the better the gloss.

In addition, the evaluation of the coloring power was evaluated by measuring the ink-coated surface on the art paper by a MACBETH reflection densitometer (trade name: RD914; manufactured by MACBETH Co., Ltd.). In this measurement, the larger the value measured, the higher the coloring power.

<Liquidity Evaluation Test>

After 2 cc of each of the inks obtained above was placed on a glass plate, the glass plate was tilted at 60 degrees to measure the flow distance of the ink after 20 minutes. The longer the flow distance, the better the fluidity.

<Heat resistance evaluation test>

At the time of producing the above-mentioned base ink, it was further kneaded at 90 ° C for 2 hours in a flash kneader, and then the ink containing the 9% disazo pigment composition was placed in the same manner as described above using the base ink. Then, the ink and the ink which was not kneaded at 90 ° C for 2 hours (ink used in the above-described hue evaluation test) were separately applied to art paper, and the difference in hue between the two was visually observed. Heat resistance. The smaller the difference in the hue, the better the heat resistance is, and the one having a particularly excellent heat resistance is "A", the one having good heat resistance is "B", and the one having moderate heat resistance is "C", and the heat resistance is poor. The rating is "D".

The above test results are shown in Tables 1 and 2.

As is apparent from Tables 1 and 2, the ink of the bisazo pigment composition of the present invention (Example) was blended in the same manufacturing method, and the ink of the comparative example was used for transparency, gloss, tinting strength, flow. Among the five items of the sex and heat resistance, excellent results were obtained in four or more items. Therefore, it is understood that the bisazo pigment composition of the present invention exhibits better characteristics than the former.

As described above, the embodiments and examples of the present invention have been described, but the configurations of the above-described respective embodiments and examples are preferably combined as they are.

The embodiments and examples disclosed herein are illustrative and not restrictive. The scope of the present invention is defined by the scope of the claims

Claims (7)

A bisazo pigment composition comprising a diazo component composed of a bisazo salt of a compound represented by the following formula (I); and a N-acetamidine anilide compound a di-synthesis component; and a reaction product obtained by a second coupling reaction coupling reaction of a compound selected from the group consisting of uracil, isocyanuric acid and xanthine having a substituent: Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Alkoxycarbonyl group. The disazo pigment composition according to claim 1, wherein a ratio of the first coupling component to the second coupling component is 85 mol% or more and 99 mol% or less to the first coupling component, and the second component is obtained. The coupling is 1 mol% or more and 15 mol% or less. The disazo pigment composition according to claim 1, wherein the third coupling component comprising the compound represented by the following formula (II) is further used in the above coupling reaction: Wherein R ⁵ and R ⁶ each independently represent hydrogen, halogen, methyl, methoxy, carboxyl, or sulfo, and R ⁷ represents methyl, methoxy, ethyl, ethoxy, methoxy. Carbonyl or ethoxycarbonyl. The disazo pigment composition according to claim 3, wherein the blending ratio of the third coupling component is 95 mol% or more and 99.9 mol% or less based on the total amount of the first coupling component and the second coupling component. The third coupling is made 0.1 mol% or more and 5 mol% or less. The disazo pigment composition according to any one of claims 1 to 4, which is in the above coupling reaction, further using a fourth coupling component composed of a compound represented by the following formula (III) or (IV) : Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and an alkyl group having 1 to 4 carbon atoms; a mercaptoamine group, an anthracene having an alkyl group having 1 to 4 carbon atoms, an phthalimide, an alkoxycarbonyl group having an alkyl group having 1 to 4 carbon atoms, and an alkane having 1 to 4 carbon atoms An alkoxysulfonyloxy group, a benzimidazolidinone, a carboxyl group, a carboxylate, a sulfonic acid group, or a sulfonate, and R ⁸ , R ⁹ , and R ¹⁰ also include two of them bonded to each other. In the case of the imidazolinone, in the case of the formula (IV), R ⁸ , R ⁹ and R ¹⁰ each independently represent a substituent which may be substituted by any benzene ring. The disazo pigment composition according to claim 5, wherein the blending ratio of the fourth coupling component is a total amount of the first coupling component and the second coupling component, or the first coupling component. The total amount of the second coupling component and the third coupling component is 85 mol% or more and 99 mol% or less, and the fourth coupling is 1 mol% or more and 15 mol% or less. The disazo pigment composition according to claim 1, wherein the disazo pigment composition contains a color selected from the group consisting of CIPigment Yellow 12, CIPigment Yellow 13, CIPigment Yellow 14, CIPigment Yellow 17, CI At least one pigment of the group consisting of Pigment Yellow 55, CIPigment Yellow 81, CIPigment Yellow 83, CIPigment Yellow 87, CIPigment Yellow 152, CIPigment Yellow 170, CIPigment Orange 15, and CIPigment Orange 16.