KR100524703B1 - Azo red pigments for textile printing and its process - Google Patents

Abstract

The present invention relates to an azo red pigment for fiber printing and a method for preparing the same, and more particularly, amino- N -substituted benzamide derivatives as diazos and 2-hydroxy-3-naphthoyl aniline derivatives as couplers. It relates to a novel azo red pigment for fibrous printing represented by the following formula 1 prepared by the coupling reaction of the two compounds using a method for producing the same.

In Chemical Formula 1, A represents a C ₁ to C ₄ straight or branched alkylene group; R ₁ represents a hydrogen atom or an alkoxy group of C _{1 to} C ₄ ; R ₂ represents an alkoxy group, a nitro group, or an aryl amide group of a hydrogen atom, a chlorine _{atom, C 1 ~C 4, C 1} ~C 4.

Description

Azo red pigments for textile printing and its process

The present invention relates to an azo red pigment for fiber printing and a method for preparing the same, and more particularly, amino- N -substituted benzamide derivatives as diazos and 2-hydroxy-3-naphthoyl aniline derivatives as couplers. It relates to a novel azo red pigment for fibrous printing represented by the following formula 1 prepared by the coupling reaction of the two compounds using a method for producing the same.

[Formula 1]

In Chemical Formula 1, A represents a C ₁ to C ₄ straight or branched alkylene group; R ₁ represents a hydrogen atom or an alkoxy group of C _{1 to} C ₄ ; R ₂ represents an alkoxy group, a nitro group, or an aryl amide group of a hydrogen atom, a chlorine _{atom, C 1 ~C 4, C 1} ~C 4.

Dyes and pigments are used as dyes for fiber printing. In the case of dye printing, the dyeing reactivity varies depending on the type of fiber (cotton, wool, polyester), and therefore, a direct dye, a disperse dye, or the like is appropriately selected and used. On the other hand, pigment printing has the advantage that can be used regardless of the type of fibers, such as synthetic fibers, blended fibers, natural fibers. In addition, the pigment printing has the advantage that the process is simple, low production cost, and waste water does not occur, which can greatly reduce the environmental pollution, the use of pigment has been steadily increasing over the last 50 years.

Azoic, carbazole (Pigment Violet 23), diarylide (Pigment Yellow 13, 14, 17, 83), pyrazolone (Pigment Orange 34), phthalocyanine (Pigment Blue 15, 15: 3) , Pigment Green 7), quinacridone (Pigment Violet 19, Pigment Red 122), bat (Pigment Red 123), black (Pigment Black 7), white (Pigment White 6) and the like are used.

However, in the field of textile printing, there is still a need for the development of new pigments with excellent color, light resistance, dry cleaning, washing and friction fastness.

In view of the above, the present inventors have conducted research efforts using amino- N -substituted benzamide derivatives as diazos, and reacting with various 2-hydroxy-3-naphthoyl aniline derivatives as couplers. The present invention was completed by synthesizing the novel azo red pigment represented by the formula (1).

Accordingly, an object of the present invention is to provide an azo red pigment suitable for fibrous printing and excellent color fastness and a method of preparing the same.

The present invention is characterized by the azo red pigment represented by the following formula (1).

[Formula 1]

In Chemical Formula 1, A represents a C ₁ to C ₄ straight or branched alkylene group; R ₁ represents a hydrogen atom or an alkoxy group of C _{1 to} C ₄ ; R ₂ represents an alkoxy group, a nitro group, or an aryl amide group of a hydrogen atom, a chlorine _{atom, C 1 ~C 4, C 1} ~C 4.

In addition, the present invention uses an amino- N -substituted benzamide derivative represented by the following formula (2) as a diazo, and couplers using various 2-hydroxy-3-naphthoyl aniline derivatives represented by the following formula (3) It characterized by a ring reaction to produce a novel azo red pigment for fiber printing represented by the following formula (1).

In the above, A, R ₁ and R ₂ are each as defined above.

Referring to the present invention in more detail as follows.

The azo red pigment represented by Chemical Formula 1 according to the present invention has excellent solvent resistance to various solvents, and when printed on cotton, silk, polyester, etc., a printing material having vivid colors and excellent fastnesses is obtained. Therefore, the azo red pigment of the present invention is useful for fiber printing.

Particularly preferred compounds for the azo red pigments according to the present invention are those wherein A in Formula 1 is a methylene group, an ethylene group or an α-methylene methylene group; R ₁ is a hydrogen atom or a methoxy group; R ₂ is a hydrogen atom, a chlorine atom, a methyl group, a methoxy group, a nitro group, or an arylamide group.

In addition, the present invention includes a method for preparing the azo red pigment represented by the formula (1), the method of the present invention is a) a process for diazotizing the amino- N -substituted benzamide derivative represented by the formula (2) b) maintaining the various 2-hydroxy-3-naphthoyl aniline derivative couplers represented by Chemical Formula 3 in an alkaline state, and c) the two reaction solutions obtained in steps a) and b) at 5 to 10 ° C. A process of preparing the azo red pigment represented by Formula 1 by mixing and stirring within the range is included.

The preparation method of the azo red pigment represented by Chemical Formula 1 according to the present invention will be described in more detail by each process as follows.

First, the amino- N -substituted benzamide derivative represented by Formula 2 is diazotized. Diazolation is performed by dispersing the amino- N -substituted benzamide derivatives in acetic acid at 5 to 10 ° C. and adding concentrated hydrochloric acid and NaNO ₂ to carry out the diazotization reaction.

In addition, 2-hydroxy-3-naphthoyl aniline derivative coupler is completely dissolved in another reaction vessel using methanol and aqueous sodium hydroxide solution to bring the pH to an alkali in the range of 10 to 11, and then the reaction is maintained at 5 to 10 ° C. This is to carry out the coupling reaction with the diazo compound.

Then, the diazo compound and the coupling solution are mixed and stirred at 5 to 10 ° C. to prepare an azo red pigment for the present invention.

The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited by the examples.

Preparation Example 1:

9.5 g (0.051 mol) of 4-nitrobenzoyl chloride was added to 20 mL of N, N- dimethylacetamide, and stirred at room temperature for about 20 minutes. Then, 5.5 mL (0.05 mol) of benzylamine was slowly added over 10 minutes. The reaction was slowly warmed up and stirred at 40-50 ° C. for 2 hours, cooled to room temperature, and then poured into 100 mL of water and stirred for 30 minutes. The reaction product was neutralized to have a pH of 6-7 using 2.6 g of Na ₂ CO ₃ , filtered, washed several times with water and dried to obtain 4-nitro- N- (1-benzyl) benzimide.

Manufacture example 2-6

The same procedure as in Preparation Example 1 was conducted, but various 4 (3) -nitro-benzimid derivatives were prepared by reacting 0.051 mol of 4 (3) -nitrobenzoyl chloride and 0.05 mol of various amine derivatives shown in Table 1 below. .

Table 1 shows the structural confirmation data of the benzimide derivatives prepared in Preparation Examples 1 to 6.

Preparation Example 7

Dissolve 6.0 g (0.03 mol) of 4-methoxy-3-nitrobenzoic acid in 30 mL of dichloromethane, add 2.7 mL (0.037 mol) of thionyl chloride and 7 drops of dimethylformamide (DMF). Stir for hours. The reaction mixture was cooled to 5-10 ° C., and a mixed solution of 4.5 mL (0.033 mol) of triethylamine and 4.0 mL (0.037 mol) of benzylamine was added slowly, taking care not to exceed 10 ° C. of the reactant. The reaction was slowly warmed up and stirred at room temperature for 2 hours, after which the excess thionyl chloride and dichloromethane were distilled off under reduced pressure. The residue was poured into 50 mL of water, stirred for about 30 minutes, filtered, and then the product was dispersed in 20 mL of 1 N aqueous sodium chloride solution, stirred for 30 minutes, filtered, washed several times with water, and dried to form 4-methoxy-3-nitro. - N - (1- benzyl) to give the mid-benjeuyi.

Manufacture example 8-9

The same method as in Preparation Example 7, except that 0.03 mol of 4-methoxy-3-nitro benzoic acid and 0.037 mol of various amine derivatives shown in the following Table 2 were reacted to produce various 4-methoxy-3-nitro-benzimid derivatives. Was prepared.

Table 2 shows the structural confirmation data of the benzimide derivatives prepared in Preparation Examples 7 to 9.

Preparation Example 10

11.5 g (0.045 mol) of 4-nitro- N- (1-benzyl) benzimide, 100 mL of methanol, and 1.2 g of Raney nickel were placed in a hydrogen reactor, and hydrogenated at 35 to 40 ° C. After completion of the reaction, Raney nickel was removed by filtration, and methanol was distilled off under reduced pressure to obtain 4-amino- N- (1-benzyl) benzimide as a solid.

Production Examples 11-18

The nitro compound shown in the following Table 3 was hydrogenated in the same manner as in Preparation Example 10.

Table 3 shows the structural confirmation data of each of the amino compounds prepared in Preparation Examples 10 to 18.

Example 1

60 mL of acetic acid was added to 6.8 g (0.03 mol) of 4-amino- N- (1-benzyl) -benzimide as a diazo compound, stirred at room temperature for about 20 minutes, and then 10 mL (0.115 mol) of 35% hydrochloric acid was added thereto. The solution was kept at 5 to 10 ° C., and then 10.5 mL (0.032 mol) of 3 N NaNO ₂ was slowly added and stirred at 5 to 10 ° C. for 1 hour to complete diazotization, and urea was added to remove excess nitrous acid.

Meanwhile, 11.5 g (0.03 mol) of 1- (2-hydroxy-3-naphthoylamino) -4- (benzoylamino) benzene was dispersed in 100 mL methanol using a coupler, and 20 mL of 8 N NaOH was added to completely dissolve the coupler. It was then kept at 5-10 ° C., slowly added to the diazotized solution obtained above, and stirred at 5-10 ° C. for 1 hour. After the reaction was completed, the reaction was heated to 50 ~ 60 ℃ stirred for 1 hour and then filtered, washed several times with water and dried to obtain a red pigment.

Examples 2-18

In the same manner as in Example 1, except that amino- N -substituted benzamide derivatives as shown in Table 4 below were used as diazos, and 1- (2-hydroxy-3-naphthoylamino) -4- Coupling reaction was carried out using a (benzoylamino) benzene derivative as a coupler to obtain an azo red pigment.

Table 4 describes the coupling reaction conditions of Examples 1 to 18, and Table 5 shows structural confirmation data of each of the azo compounds generated as a result of the coupling reaction.

Example 19

The same procedure as in Example 1 was carried out, except that 7.7 g (0.03 mol) of 3-amino-4-methoxy- N- (1-benzyl) -benzimide was used as the diazo, and 1- (2- as the coupler. The coupling reaction was carried out using 11.9 g (0.03 mol) of hydroxy-3-naphthoylamino) -4-methyl-3- (benzoylamino) benzene to obtain an azo red pigment.

Yield = 89.9%, LC / MS m / e (M + 1) ⁺ = 664, IR (KBr) 699, 1017, 1268, 1479, 1530, 1644, 1671, 3262 cm ^-1

Example 20

The same procedure as in Example 1 was carried out, except that 7.7 g (0.03 mol) of 3-amino-4-methoxy- N- (1-benzyl) -benzimide was used as the diazo, and 2-hydroxy- was used as the coupler. Coupling reaction was performed using 8.9 g (0.03 mol) of 3-naphthoyl- (4-chloro) aniline to obtain an azo red pigment.

Yield = 86.7%, m / e (M ⁺ ) = 564, IR (KBr) 756, 823, 1013, 1268, 1550, 1608, 1673, 3287 cm ^-1

Example 21

As diazos, 6.8 g (0.03 mol) of 4-amino- N- (1-benzyl) -benzimide was used by diazotization in the same manner as in Example 1.

Meanwhile, 7.9 g (0.03 mol) of 2-hydroxy-3-naphthoyl aniline was dispersed in 200 mL water with a coupler, and 20 mL of 8 N NaOH was added to completely dissolve the coupler, which was kept at 5 to 10 ° C. and obtained above. The diazotized solution was slowly added and stirred at 5-10 ° C. for 1 hour. After the reaction was completed, the reaction was heated to 50 ~ 60 ℃ stirred for 1 hour and then filtered, washed several times with water and dried to obtain a red pigment.

Yield = 94%, m / e (M ⁺ ) = 500, IR (KBr) 751, 1013, 1156, 1496, 1637, 1681, 3295 cm ^-1

Examples 22-35

In the same manner as in Example 21, except that the amino- N -substituted benzamide derivative (0.03 mol) was used as the diazo, and 2-hydroxy-3-naphthoyl aniline derivative (0.03 mol) was used as the coupler. And a coupling reaction to obtain an azo red pigment.

Table 6 shows the coupling reaction conditions of Examples 22 to 35, and Table 7 shows structural confirmation data of each of the azo compounds generated as a result of the coupling reaction.

Experimental Example 1: Solvent Characterization Experiment

For each of the azo red pigments synthesized in the Examples according to the present invention, an experiment was conducted to confirm the solvent properties and the chemical resistance (acid, alkali) properties. The results are shown in Table 8 below.

According to the result of Table 8, it was confirmed that the red pigment of the Example included in the present invention is excellent in solvent resistance and chemical resistance.

Experimental Example 2: Printing and color fastness confirmation experiment

Each of the azo red pigments synthesized in the embodiment according to the present invention was mixed at a ratio of synthetic pigments: nonionic surfactant: ethylene glycol = 1: 1: 2 (weight ratio), milled, and then mixed with a binder, water, etc. to prepare a printing foil. It was. 3% o. w. After f printing the fiber (cotton) with f, CCM and all-fastness were measured. The results of the overall fastness are shown in Table 9 below.

According to the above Table 9, the azo red pigment included in the present invention was found to have a clear color and excellent fastness.

As described above, the azo red pigment of the present invention was excellent in resistance to various organic solvents and chemical resistance. Colors are vivid when printed on textiles, wash fastness (JIS L-0844 A-4), fastness to friction (KS K0650, Crocker meter), dry cleaning (JIS L-0860), thermal stability (180 ℃, 30 sec. Mathis Dryer Type LTE.) And light fastness (Xenon Arc KS K0128, direct method) were excellent.

Claims (6)

Azo red pigment represented by the following formula (1): [Formula 1] In Chemical Formula 1, A represents a C ₁ to C ₄ straight or branched alkylene group; R ₁ represents a hydrogen atom or an alkoxy group of C _{1 to} C ₄ ; R ₂ represents an alkoxy group, a nitro group, or an aryl amide group of a hydrogen atom, a chlorine _{atom, C 1 ~C 4, C 1} ~C 4. The azo red pigment according to claim 1, wherein A is a methylene group, an ethylene group or an α-methyl methylene group. The azo red pigment according to claim 1, wherein R ₁ is a hydrogen atom or a methoxy group. The azo red pigment according to claim 1, wherein R ₂ is a hydrogen atom, a chlorine atom, a methyl group, a methoxy group, a nitro group, or an arylamide group. The amino-N-substituted benzamide derivative represented by the following Chemical Formula 2 and the 2-hydroxy-3-naphthoyl aniline derivative represented by the following Chemical Formula 3 are prepared by a coupling reaction, Preparation of Azo Red Pigment: In the above, A represents methylene, ethylene or α-methylene; R ₁ represents hydrogen or a methoxy group; R ₂ represents hydrogen, methyl, methoxy, nitro, chloro or arylamide group. The method of claim 5, a) diazotizing the amino-N-substituted benzamide derivative represented by Formula 2, b) separately preparing a coupler represented by Chemical Formula 3 in an alkaline solution state, c) mixing and agitating the two reaction solutions obtained in steps a) and b) within a range of 5 to 10 ° C., and separating the resulting azo red pigment represented by the formula (1).