KR100891000B1 - Azo yellow pigments comprising N-substituted benzamide type and its process - Google Patents

Abstract

The present invention relates to a N -substituted benzamide-based azo yellow pigment having a novel structure containing no harmful amines or heavy metals and a method for preparing the same. Therefore, it is useful as a new yellow pigment that can replace the regulated yellow pigment in the industrial field of ink, paint and the like because solvent resistance, chemical resistance and light resistance are the same or better.

Organic pigments, azo yellow pigments, diazo bodies, couplers, amino-N-substituted benzamides, solvent resistance

Description

Azo yellow pigments comprising N-substituted benzamide type and its process

The present invention relates to a N -substituted benzamide-based azo yellow pigment having a novel structure containing no harmful amines or heavy metals and a method for preparing the same, as represented by the following general formula (1). Compared to Pigment Yellow 12, the solvent resistance, chemical resistance and light resistance are the same or better, so it is useful as a new yellow pigment that can replace the regulated yellow pigment in the industrial field such as ink and paint.

[Formula 1]

In Formula 1, X represents a bond line or an alkylene group of C ₁ -C ₆ ; R ¹ represents a hydrogen atom, an amide group, a C ₁ -C ₆ alkyl group, or a C ₁ -C ₆ haloalkyl group; R ² represents an alkoxy group of a hydrogen atom, C ₁ -C _6, or C ₁ -C _6; ^{R 3, R 4, R 5} , R 6, and R ⁷ each represent a hydrogen atom, a halogen atom, an alkoxy group of the alkyl group of C ₁ -C _6, or C ₁ -C _6, or R ⁴ and R ⁵ are each It can be combined with neighboring groups to form a fused ring of benzimidazolone.

In the case of the currently used yellow pigments, red chromate (PbCrO ₄ , Pigment Yellow 34) is mainly used as the inorganic pigment, and the organic pigment is represented by the following Chemical Formula A having 3,3-dichlorobenzidine (DCB) as an intermediate. Compounds (Pigment Yellow 12, 13, 14, 17) are mainly used for various purposes.

[Formula A]

In Formula A, R, R ₁ , and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.

However, yellow inorganic pigments contain heavy metals such as Pb and Cr, and their range of use is limited due to tightening environmental regulations on heavy metal-containing materials. It is being replaced by organic pigments. Pigment Yellow 12, 13, 14, 17, etc., which are 3,3-dichlorobenzidine (DCB) intermediates as yellow organic pigments, are generally heat stable, but can be heated continuously above 200 ° C during plastic processing. 3,3-dichlorobenzidine (DCB), known as a carcinogen, may be liberated.

In addition, since 1995, Germany has banned the import and sale of azo dyes containing 20 kinds of amines known as carcinogenic substances and household goods using them. Therefore, development of substitute dyes of dyes containing these regulatory amines is required, and research on environmentally friendly dyes in this regard is actively progressing.

Currently, red pigments and blue pigments among the three primary colors are used by selecting non-hazardous pigments from existing products. However, yellow pigments are temporarily excluded from regulation because there is no substitute pigment for harmful substances. However, if yellow pigments with excellent color and physical properties that can successfully replace harmful substances are developed, they will be applied immediately. It is expected.

As a new yellow pigment that can replace the regulated yellow pigment, 5-acetoacetylaminobenzimidazolone, 4-chloro-2,5-dimethoxyacetoacetanilide or amino- N -substituted benzamide derivatives are used as intermediates. Although pigments [US Patent No. 3,109,842, European Patent No.1422281 and Japanese Patent Publication No. 2002-179959, Japanese Patent No. 11-005917, Japanese Patent No. 9-157569 and Korean Patent No. 524703] are known, There is a continuing need for the development of yellow pigments with excellent color and physical properties.

Accordingly, the present inventors have tried to develop a new yellow pigment that can replace the regulated yellow pigment, and as a result, the amino- N -substituted benzamide derivative is used as a diazo, and the acetoacetanilide derivative is synthesized using a coupler. The present invention was completed by synthesizing the azo yellow pigment represented by the formula (1) of the novel structure.

It is an object of the present invention to provide azo yellow pigment having a novel structure excellent in solvent resistance, chemical resistance and light resistance.

It is an object of the present invention to provide a method for preparing azo yellow pigment having a novel structure prepared by coupling reaction using an amino- N -substituted benzamide derivative as a diazo and an acetoacetanilide derivative as a coupler. .

The present invention is characterized by the N -substituted benzamide-based azo yellow pigment represented by the following formula (1).

[Formula 1]

In Formula 1, X represents a bond line or an alkylene group of C ₁ -C ₆ ; R ¹ represents a hydrogen atom, an amide group, a C ₁ -C ₆ alkyl group, or a C ₁ -C ₆ haloalkyl group; R ² represents an alkoxy group of a hydrogen atom, C ₁ -C _6, or C ₁ -C _6; ^{R 3, R 4, R 5} , R 6, and R ⁷ each represent a hydrogen atom, a halogen atom, an alkoxy group of the alkyl group of C ₁ -C _6, or C ₁ -C _6, or R ⁴ And R ⁵ may be bonded to a group adjacent to each other to form a fused ring of benzimidazolone.

In addition, the present invention is characterized by a method for producing an N -substituted benzamide-based azo yellow pigment represented by the formula (1) comprising the following process:

a) diazotizing the amino- N -substituted benzamide derivative represented by the following Chemical Formula 2,

b) dissolving acetoacetanilide derivative represented by Formula 3 in an aqueous alkali solution,

c) mixing and coupling the diazo derivative solution prepared in step a) with the acetoacetanilide derivative solution prepared in step b).

[Formula 2]

[Formula 3]

In Formula 2 or 3, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and X are the same as defined in Formula 1, respectively.

Hereinafter, the substituents used to define the N -substituted benzamide-based azo yellow pigment represented by Chemical Formula 1 according to the present invention will be described in detail.

By "halogen atom" is meant a fluoro, chloro, bromo, iodo atom.

"Alkyl group" means a straight or pulverized aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, specifically methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -Butyl, n -pentyl, i -pentyl, n -hexyl, i -hexyl and the like.

"Alkoxy group" means O-alkyl in which the alkyl group defined above is bonded to oxygen, and specifically, methoxy, ethoxy, n -propoxy, i -propoxy, n -butoxy, i -butoxy , t -butoxy.

'Haloalkyl group' is one or more halogen is substituted in the alkyl group defined above, may include a chloromethyl, dichloromethyl, trifluoromethyl group, 1,2-dichloroethyl group.

In the N -substituted benzamide-based azo yellow pigment represented by Formula 1 according to the present invention, preferably:

X represents a bond line, methylene group, ethylene group, isopropylene group, isobutylene group, pentylene group, isopentylene group, hexylene group or isohexylene group; R ¹ represents a hydrogen atom, an amide group, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, a pentyl group, a hexyl group, or a trifluoromethyl group; R ² represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group; R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each represent a hydrogen atom, fluoro, chloro, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, methoxy or ethoxy , A propoxy group, or a butoxy group, or R ⁴ and R ⁵ is a case of a compound which is bonded to a group adjacent to each other to form a fused ring of benzimidazolone.

In the N -substituted benzamide-based azo yellow pigment represented by Formula 1 according to the present invention, more preferably:

X represents a bond line, methylene group, ethylene group, isopropylene group, or isobutylene group; R ¹ represents a hydrogen atom, an amide group, a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group; R ² represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group; R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each represent a hydrogen atom, chloro, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group or butoxy group, or R ⁴ and R ⁵ is a case of a compound that combines with neighboring groups to form a fused ring of benzimidazolone.

Hereinafter, the method for preparing the N -substituted benzamide-based azo yellow pigment represented by Chemical Formula 1 according to the present invention will be described in detail for each process.

First, the amino- N -substituted benzamide derivative represented by Chemical Formula 2 is diazotized. In this case, the diazotization method disperses the amino- N -substituted benzamide derivative represented by Chemical Formula 2 in water, acetic acid or acetic acid aqueous solution, and then, with hydrochloric acid at -20 ° C to 20 ° C, preferably 5 ° C to 10 ° C. It is made by diazotization by adding nitrite.

In a separate vessel, the acetoacetanilide derivative represented by Formula 3 is dissolved in an alkaline solution. At this time, the alkali solution is a solution in which an alkali metal salt is dissolved in a solvent of water, alcohol or an aqueous alcohol solution. The alcohol may be a lower alcohol such as methanol, ethanol, propanol, butanol, and preferably methanol or ethanol. Alkali metal salts may include hydroxides, carbonates, hydrogen carbonates and the like of alkali metals such as sodium and potassium, and preferably sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate. The pH of the acetoacetanilide derivative solution thus prepared is maintained in the range of 6 to 8, preferably in the range of 6 to 7.

The azo yellow pigment represented by Chemical Formula 1 is prepared by mixing and coupling a diazo derivative solution and acetoacetanilide derivative solution prepared above. That is, the two reaction solutions are mixed while maintaining a reaction temperature of -20 ° C to 20 ° C, preferably 5 ° C to 10 ° C, and adjusted so that the pH of the mixed solution is in the range of 6 to 8, preferably in the range of 6 to 7. And stirring to make a coupling reaction. When the coupling reaction is completed, the reaction solution is heated to a temperature of 40 ° C to 70 ° C, preferably 50 ° C to 60 ° C and further stirred. The reaction solution is then filtered, washed with solvent and dried to afford the desired azo yellow pigment.

The N -substituted benzamide-based azo yellow pigment represented by Formula 1 prepared by the method as described above does not contain harmful amines and heavy metals, has excellent color, and is also a harmful amine dichlorobenzidine (DCB The solvent resistance, chemical resistance, and light resistance to various solvents were equal or superior to those of Pigment Yellow 12, which is an intermediate. Therefore, the azo yellow pigment of the present invention can replace the existing yellow pigment in ink, paint, and the like.

Such a present invention will be described in more detail based on the following examples, but the present invention is not limited to these examples.

EXAMPLE

Example 1

To diazo, 100 mL of H ₂ O was added to 6.8 g (0.03 mol) of 4-amino- N- (1-benzyl) -benzimide, and stirred at room temperature for about 20 minutes, and then 10 mL (0.115 mol) of 35% hydrochloric acid was added. And the reaction solution was maintained at 5 to 10 ° C. Then, 10.5 mL (0.032 mol) of 3 N NaNO ₂ was slowly added and stirred at 5-10 ° C. for 1 hour to complete diazotization. A small amount of sulfamic acid was added to the reaction solution to remove excess nitrite.

Meanwhile, 7.0 g (0.03 mol) of 5-acetoacetylaminobenzimidazolone was dispersed in 200 mL of H ₂ O using a coupler, and 10 mL of 8 N NaOH was added to completely dissolve the coupler, and then maintained at 5 to 10 ° C. Then, the pH of the reaction was adjusted to about 6-7 using 80 mL of 10% AcOH aqueous solution.

The diazotized solution obtained above is mixed with the coupler solution, but slowly added while adjusting the pH with an aqueous 10% Na ₂ CO ₃ solution to maintain the pH of the reactant at about ₆ to 7 and stirred at 5 to 10 ° C. for 1 hour. It was. When the reaction was completed, the reaction was heated to 50 ~ 60 ℃ stirred for 1 hour, then filtered and washed several times with water and dried to give a yellow pigment.

Examples 2-12

In the same manner as in Example 1, except that amino- N -substituted benzamide derivatives shown in Table 1 below were used as diazos, and 7.0 g (0.03 mol) of 5-acetoacetylaminobenzimidazolone was used. It was used as a coupler to obtain a yellow pigment.

Table 1 below describes the coupling reaction conditions of Examples 1 to 12.

Example 13

60 mL of acetic acid (AcOH) was added to 6.8 g (0.03 mol) of 4-amino- N- (1-benzyl) -benzimide as a diazo, and stirred at room temperature for about 20 minutes, followed by 10 mL (0.115 mol) of 35% hydrochloric acid. Was added and the reaction solution was maintained at 5-10 占 폚. Then, 10.5 mL (0.032 mol) of 3 N NaNO ₂ was slowly added and stirred at 5-10 ° C. for 1 hour to complete diazotization. A small amount of sulfamic acid was added to the reaction solution to remove excess nitrite.

Meanwhile, 8.1 g (0.03 mol) of 4-chloro-2,5-dimethoxyacetoacetanilide was dispersed in 200 mL of H ₂ O using a coupler, and 10 mL of 8 N NaOH was added to completely dissolve the coupler, and then 5 to 10 ° C. Was maintained. Then, the pH of the reaction was adjusted to about 6-7 using 80 mL of 10% AcOH aqueous solution.

The diazotized solution obtained above is mixed with the coupler solution, but slowly added while adjusting the pH with an aqueous 10% Na ₂ CO ₃ solution to maintain the pH of the reactant at about ₆ to 7 and stirred at 5 to 10 ° C. for 1 hour. It was. When the reaction was completed, the reaction was heated to 50 ~ 60 ℃ stirred for 1 hour, then filtered and washed several times with water and dried to give a yellow pigment.

Examples 14-24

In the same manner as in Example 13, using amino- N -substituted benzamide derivatives as shown in Table 2 as a diazo, 8.1 g of 4-chloro-2,5-dimethoxy acetoacetanilide ( 0.03 mol) was used as a coupler to obtain a yellow pigment.

Table 2 below describes the coupling reaction conditions of Examples 13 to 24.

In addition, Table 3 below shows the infrared spectral data for confirming the structure of each of the azo yellow pigments prepared in Examples 1 to 24.

Experimental Example  : AZO  Experiment of confirming physicochemical properties of yellow pigment

For each of the azo yellow pigments prepared in Examples 1 to 24, solvent properties, chemical resistance (acid, alkali) properties and light resistance were confirmed by the following method, and the results are shown in Table 4 below.

1) solvent characteristics

To 0.05 g of the ground pigment sample, 1 mL of a solvent of water (H ₂ O), ethanol (EtOH), methyl ethyl ketone (MEK), xylene (Xy), dioctylphthalate (DOP), and perchloroethylene (PCE) was added. Each was added and dispersed by vigorous stirring, left for 10 minutes, then vigorously stirred for 1 minute, and then left for 2 hours. Evaluation of the solvent property was visually confirmed whether the pigment was eluted and classified into five grades according to the amount of the pigment eluted.

[Contents property evaluation] 5: Not eluted at all 4: Almost eluted 3: Small amount eluted 2: Comparatively much eluted 1: Very much eluted.

2) Chemical resistance

To 0.05 g of the pulverized pigment sample, 1 mL of 2% aqueous hydrochloric acid (acid resistance) and 2% aqueous sodium hydroxide solution (alkali resistance) were added, dispersed by vigorous stirring, left for 10 minutes, and then vigorously stirred for 1 minute. Left for 2 hours. Evaluation of the solvent property was visually confirmed whether the pigment was eluted and classified into five grades according to the amount of the pigment eluted.

[Drug resistance evaluation] 5: Not eluted at all 4: Almost eluted 3: Small amount eluted 2: Comparatively much eluted 1: Very much eluted.

3) light resistance

After the pigment-coated paper was irradiated with ultraviolet light for 10 hours with a carbon arc meter, the degree of fading was visually evaluated using JIS L-0841 blow scale grade 8. The evaluation of light resistance was divided into 5 grades according to the degree of discoloration.

[Light resistance evaluation] 5: No change at all 4: Almost no change 3: Slightly discolored 2: Comparatively much discolored 1: Very much discolored.

N -substituted benzamide azo yellow pigment represented by the formula (1) characterized by the present invention is a novel structure material containing no harmful amines or heavy metals, Pigment Yellow currently commonly used as a yellow pigment Yellow) It was confirmed that solvent resistance, chemical resistance and light resistance were equivalent to or superior to those of 12.

Therefore, the N -substituted benzamide-based azo yellow pigment represented by the formula (1) characterized by the present invention can replace the regulated yellow pigment in ink, paint, and the like.

Claims (7)

N -substituted benzamide-based azo yellow pigment represented by Formula 1 below: [Formula 1]

In Chemical Formula 1, X represents an alkylene group of C ₁ -C ₆ ; R ¹ represents a hydrogen atom, an amide group, a C ₁ -C ₆ alkyl group, or a C ₁ -C ₆ haloalkyl group; R ² represents an alkoxy group of a hydrogen atom, C ₁ -C _6, or C ₁ -C _6; ^{R 3, R 4, R 5} , R 6, and R ⁷ each represent a hydrogen atom, a halogen atom, an alkoxy group of the alkyl group of C ₁ -C _6, or C ₁ -C _6, or R ⁴ and R ⁵ are each Can combine with neighboring groups to form a fused ring of benzimidazolone, However, when R ⁴ and R ⁵ are bonded to each other to form a fused ring of benzimidazolone, R ² represents a C ₁ -C ₆ alkoxy group, and R ³ , R ⁶ , and R ⁷ each represent a hydrogen atom. Indicates. The method of claim 1, X represents a methylene group, an ethylene group, an isopropylene group, or an isobutylene group; R ¹ represents a hydrogen atom; R ² represents a methoxy group; R ³ , R ⁶ , and R ⁷ each represent a hydrogen atom, or R ⁴ and R ⁵ combine with a neighboring group to form a fused ring of benzimidazolone, N -substituted benzamide Azo yellow pigment. The method of claim 1, X represents a methylene group, an ethylene group, an isopropylene group, or an isobutylene group; R ¹ represents a hydrogen atom; R ² represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group; R ^3, R ^4, R ^5, R ^6, and R ⁷ is N, it characterized in that each represent a hydrogen atom, chloro, methyl, ethyl, propyl, methoxy, ethoxy, propoxy, or butoxy - Substituted benzamide-based azo yellow pigments. a) dispersing the amino- N -substituted benzamide derivative represented by Formula 2 in water, acetic acid or acetic acid aqueous solution, and then adding hydrochloric acid and nitrite at a temperature of -20 ° C to 20 ° C, b) adjusting the pH of the acetoacetanilide derivative represented by the following Chemical Formula 3 in an alkaline solution so that the pH is in the range of 6 to 8, c) mixing the diazo derivative solution prepared in step a) and the acetoacetanilide derivative solution prepared in step b) and coupling reaction at a pH of 6 to 8 and a temperature of -20 ° C to 20 ° C, and d) obtaining a azo yellow pigment after heating at a temperature of 40 ℃ to 70 ℃ when the coupling reaction is terminated, Method for producing azo yellow pigment represented by the formula (1) characterized in that it comprises: [Formula 2]

[Formula 3]

[Formula 1]

In Formula 1, 2 or 3, X, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are as defined in claim 1 above. delete delete delete