KR100795972B1 - Acid dye compound having antimicrobial activity and dye composition comprising the same - Google Patents

Abstract

The present invention relates to an acid dye having an antimicrobial activity represented by the following formula (1) having a structure in which two aromatic rings are linked to sulfonamide groups, and exhibiting excellent fastness properties and antibacterial properties, and an antimicrobial dye composition containing the same.

[Formula 1]

Description

Acid dye compound having antimicrobial activity and dye composition containing same {ACID DYE COMPOUND HAVING ANTIMICROBIAL ACTIVITY AND DYE COMPOSITION COMPRISING THE SAME}

1 is ¹ H NMR data of the compound of Formula 13;

Figure 2 shows ¹ H NMR data of the compound of Formula 14.

3 shows the ¹ H NMR data of the compound of formula 15.

The present invention relates to an acid dye compound having an antimicrobial activity and a dye composition containing the same.

In general, dyes which are soluble in water and whose dye ions are anionic are small in molecular weight, have high affinity for polyamide fibers such as wool and nylon fibers, and low affinity for cellulose fibers. Among acidic dyes, dyes in which metal atoms are coordinated in dye molecules are called metal complex dyes or metal acid dyes, and are often used to obtain deep colors or high fastnesses.

Acid dyes are mainly composed of azo-based dyes having an azo chromophore and anthraquinone-based dyes. In addition, acid dyes derived from basic dyes (CIAcid Violet 49, CIAcid Blue 7, etc.) and nitro acid dyes (CIAcid Brown 13, CIAcid Brown 248, etc.) are commercially available, but they do not use much.

On the other hand, antibacterial substances that have bacteriostatic action for inhibiting the growth of bacteria or bactericidal action for killing bacteria are presented in various forms, and various uses thereof have been promoted. Among them, a compound having a sulfonamide group has already been confirmed to have strong antimicrobial properties long ago, and has been applied in various structures in the synthesis of antibiotics and antibacterial agents.

Sulfonamide-based antibiotics or antimicrobials, also called sulfa agents, exhibit antimicrobial activity by inhibiting folic acid synthesis, which is essential for cell proliferation or division. These are also referred to as sulfonamide antibacterial agents, and examples thereof include Irgofen, Silver sulfadiazine, Sulfadiazine, Sulfamethoxine, Sulfaethidole, and Sulfaethidole. Sulfaminazine, Sulfamethazine, Sulfamethizole, Sulfamethomidine, Sulfamethoxypyridazine, Sulfamethoxytriazine, Sulfamethoxymethazine Sulfamonomethoxine, Sulfapyrazine, Sulfapyridine, Sulfathiazole, Sulfisomezole, Sulfisomezole, Sulfisomidine, Sulfisoxazole, Urilon, etc. Known.

The antimicrobial range of sulfonamide-based substances is known to be effective in inhibiting proliferation of intestinal bacteria such as E. coli , Klebsiella , Salmonella , Shigella , Entrobacter , Norcardia and Chlamydia Trachomatics .

Examples of the preparation of dyes using sulfonamide derivatives as starting materials or reactants, or using intermediates with antibiotic or antimicrobial properties, have been filed or registered as patents. For example, Korean Patent Nos. 544947 and 0544951. No. 0,0368990, Korean Patent Application Publication Nos. 10-2006-0002364, 10-2006-0002365, 10-2006-0002366, 10-2006-0034333, 10-2006-0034334 , 10-2006-0034335, 10-2006-0043923, 10-2006-0043924, 10-2002-0033123, and the like. Except for these patent documents, most of the methods of extracting or blending a substance having antimicrobial activity from a natural substance or using a dye in combination with an antibiotic or an antimicrobial agent.

Some of the aforementioned Korean patent documents use sulfonamide-based antimicrobial agents, which do not have only sulfonamide groups (-NHSO _2- ), and, like sulfadiazine, one to three nitrogen atoms are contained in the benzene ring. Or heterocyclic form in which neighboring benzene or aromatic ring contains sulfur, nitrogen atom or the like. Also in the case of sulfanylamide, the sulfonamide group is a substituent on the benzene ring, and the sulfonamide group is not present between the two benzene rings.

On the other hand, although a few foreign patent documents refer to antimicrobial dyes, they are completely different from the uses disclosed in the present invention.

Therefore, no literature has been reported on acidic dyes having a structure in which two aromatic rings are linked to sulfonamide groups, which exhibit antibacterial activity, within the scope of the present inventors.

It is an object of the present invention to provide an acid dye compound having an antimicrobial activity and a antimicrobial dye composition containing the same, having a structure in which two aromatic rings are linked to sulfonamide groups, and exhibiting excellent fastness properties and antimicrobial properties.

An acid dye compound having an antimicrobial activity of the present invention is characterized by having a structure in which two aromatic rings are linked to sulfonamide groups.

A dye having a benzenesulfonanilide structure has been registered or commercialized a number of similar structures long ago, including US Patent Nos. 3,272,586, 4,188,187, etc., and these compounds have been widely used in China, India, etc. It is manufactured in the country and sold under various names. Dyes having a naphthalene ring on either side of the sulfonamide structure are also known. The naphthalene ring is used as a diazo material in the synthesis of azo dyes or serves as a coupler for determining the color. Since many naphthalene derivatives have already been developed, they may be selected when one wants to produce dyes of various colors.

In order to be used as an antimicrobial dye, not only antimicrobial properties, but also dye performances such as washing fastness, water fastness and daylight fastness, and dye's original characteristics such as dye concentration and dyeing property should be good.

The inventors have found that certain compounds having two aromatic rings linked by sulfonamide structures not only have antimicrobial properties but also excellent dye performance, such as washing fastness, water fastness and daylight fastness, and dye concentration and dyeability. The present invention was completed by knowing that it can be developed as an antimicrobial dye.

Accordingly, the present invention relates to an acid dye compound having an antimicrobial activity represented by the following formula (1) having a structure in which two aromatic rings are connected to sulfonamide groups, and showing excellent fastness properties and antibacterial properties, and an antimicrobial dye composition containing the same. will be.

In the formula,

Ar ¹ and Ar ² may be the same or different from each other, and each independently an amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; A phenylamino group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms; Benzenesulfonamido substituted or unsubstituted with a halogen atom or a carboxylic acid group selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; And -N (C ₂ H ₄ OH) ₂ , a phenyl group or a naphthyl group which is substituted or unsubstituted with one or more groups selected from the group consisting of:

B ¹ and B ² are each independently a hydrogen atom; Amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Alkyl of 1 to 6 carbon atoms, alkoxy group of 1 to 6 carbon atoms; A phenylamino group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; And -N (C ₂ H ₄ OH) ₂ One or more selected from the same or different groups selected from the group consisting of, or a group represented by the formula 2 to 5,

Formula 2 and 5 of R ₁ to R ₆ the formula (3) and at least one or more among R ₁ to R ₈ is of the four azo group (-N coupling the Ar ¹ and connected to the B ¹ or B ² or Ar ² and = N-) or an amino group (-NH-), and the rest are each independently a hydrogen atom; Amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Nitro group; Halogen atoms selected from fluorine, chlorine, bromine and iodine; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Phenylamino group which is substituted or unsubstituted by 1 or more groups chosen from a C1-C6 alkyl group, a nitro group, and a sulfonic acid group; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH- (C ₆ H ₅ ) CH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; -N (C ₂ H ₄ OH) ₂ ; -NH- (C ₆ H ₅ ) NO ₂ ; -NH- (C ₆ H ₅ ) SO ₃ H; And one or more of the same or different substituents selected from the group consisting of -OC ₂ H ₅ .

The acidic dye compound of Chemical Formula 1 according to the present invention exhibiting antimicrobial activity includes the following Chemical Formulas 6 to 10 compounds.

In Chemical Formulas 6 to 10, R ₁ to R ₁₀ are each independently a hydrogen atom; Amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Nitro group; Halogen atoms selected from fluorine, chlorine, bromine and iodine; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Phenylamino group which is substituted or unsubstituted by 1 or more groups chosen from a C1-C6 alkyl group, a nitro group, and a sulfonic acid group; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH- (C ₆ H ₅ ) CH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; -N (C ₂ H ₄ OH) ₂ ; -NH- (C ₆ H ₅ ) NO ₂ ; -NH- (C ₆ H ₅ ) SO ₃ H; And one or more of the same or different substituents selected from the group consisting of -OC ₂ H ₅ .

The acid dye compound of Chemical Formula 1 according to the present invention exhibiting antimicrobial activity shows excellent dyeability and antimicrobial activity when dyed to polyamide-based fibers such as wool and nylon fibers.

The compounds represented by the following formulas (11) and (12) are known dyes having a benzenesulfonanilide structure.

Since the compounds of Chemical Formulas 11 and 12 or currently commercially available dyes are all developed with dye inherent dyeability in mind, properties other than dyeability of compounds having such a structure have not been investigated, and in particular, they may exhibit antimicrobial properties. It is not known at all before the present invention as to whether or not there is. The present inventors have newly discovered that a substance showing antimicrobial properties exists among known sulfonanilide compounds. Therefore, dye compounds that are not known to exhibit antimicrobial activity in the past may also be included as an antimicrobial dye component in an acid dye composition having antimicrobial activity according to the present invention.

On the other hand, the following formulas (13) to 15 are representative of representative compounds that are excellent in both dyeability and antimicrobial activity included in the range of the formula (1).

An acid dye compound having an antimicrobial activity represented by Formula 1 may be reacted with a benzenesulfonanilide derivative with a diazo compound, a coupling reagent and a condensation reactant, or a condensation reaction with a compound having an amine group and p-toluenesulfonyl chloride. You can get it. In addition, these compounds can be prepared using various known methods well known to those skilled in the art.

The present invention also relates to an acid dye composition having an antimicrobial activity containing as a dye component a mixture composed of two or more different Formula 1 compounds or a mixture of one or more Formula 1 compounds with other dye compounds known in the art. . At this time, the compound of Formula 1 may be contained in an amount of 1 to 50% by weight. Examples of known dye compounds that can be mixed with the compound of Formula 1 include C.I. Acid Red 337 (Formula 16), C.I. Acid Blue 324 (Formula 17), C.I. Acid Yellow 199 (Formula 18), C.I. Acid Orange 67 (Formula 19), etc. are mentioned. However, known acid dye compounds that can be mixed with the compound of formula (I) are not limited thereto, and all currently registered acid dyes, namely CIAcid Yellow, CIAcid Orange, CIAcid Red, CIAcid Blue Any of the dyes of CIAcid Brown, CIAcid Green, CIAcid Violet and CIAcid Black series can be mixed.

When the dye composition is prepared by mixing with the compound of Formula 1, these known dye compounds may be mixed in an amount of 1 to 50% by weight based on the total weight of the composition.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for illustrating the present invention, but the scope of the present invention is not limited thereto.

The production process according to the following examples can achieve the same results using industrially available dye preparation raw materials as starting materials or reactants or by using reagent grade raw compounds.

The dyeing fastness and antimicrobial properties of each dye compound were tested under the following conditions.

-Wash fastness (ISO 105 / CO3 60 ℃)

Apparatus: Lauder-O-Meter, temperature: 60 ° C. 2 ° C. 30 minutes, liquid ratio: 50: 1

Water fastness (ISO 105 / E01)

Device: Perspirometer (4.5 kg pressure), Temperature: 37 ° C. 2 ° C. 4 hours

Daylight fastness (KS K 0700: 1990, fade meter, BLUE SCALE)

-Antimicrobial test (KS K 0693)

Test strains: Staphylococcus aureus ATCC 6538 and Klebsiella pneumoniae ATCC 4352

Example 1: Preparation of Compound of Formula 12

1 part of Dywell-500 (KG Chemical Co., Ltd.) was put into 620 parts of water (30-33 degreeC), and 40 parts of bromamine acid were added. Overnight After dispersing, 5 parts of Na ₂ SO ₃ , 25 parts of Na ₂ CO ₃ , and 14.7 parts of 1,3-phenylenediamine were added thereto, and the temperature was adjusted to about 27 ° C. with stirring for 30 minutes. 4 parts of CuCl ₂ · 2H ₂ O was dissolved in water, reacted for 1 hour, and then repeatedly added twice in the same manner and stirred. After further stirring for 1 hour, the reaction was confirmed by TLC, and after mixing with 600 parts of water, 60 parts of hydrochloric acid was added dropwise, and the pH was adjusted to about 2.5 and filtered.

The filtered cake was poured into 1,200 parts of water, dispersed, and then 5 parts of Na ₂ SO ₃ was added thereto, and the temperature was raised to 80 ° C. while stirring. The pH of the solution was neutralized to about 7.5 using a 50% NaOH solution, and then dissolved with hydrochloric acid. Filtration quickly after adjusting to pH 2.5. In the same way it was purified by further filtering 1 to 2 times.

The purified cake is dispersed in 500 parts of water (room temperature), the pH is adjusted to 5.5 using Na ₂ CO ₃ , and the temperature is raised to 55 ° C. 30 parts of p-toluenesulfonyl chlorides were added in small portions, and the reaction was stirred while maintaining the conditions of pH 5.5 and 55 ° C. Confirm the reaction by TLC and further add p-toluenesulfonyl chloride if necessary to complete the reaction. The reaction solution was filtered as it was, or about 50 parts of NaCl was added, stirred for 30 minutes, filtered, and dried at 80 ° C. or lower to obtain a target compound as a blue particle (yield: 75%).

When the dye was prepared on the nylon fiber, it was dyed in light blue, and exhibited 4th grade of daylight, washing and water fastness, and the dyed fiber was 93% or more with respect to Klebsiella pneumoniae as shown in Table 1. The bacteriostatic rate was shown.

Example 2: Preparation of Compound

18.8 parts of 4-hydroxymethanylamide is added to 120 parts of water at room temperature and dispersed for 30 minutes, followed by addition of 32 parts of hydrochloric acid and stirring for 1 hour. After cooling to below 0 ℃ by adding about 80 parts of ice, 7.3 parts of NaNO ₂ is dissolved in 20 parts of water and added dropwise for 1 hour.

In a separate reaction vessel, 24 parts of 2-amino-5-naphthol-7-sulfonic acid (J-acid, Jayic acid) are dispersed in 200 parts of water (40 ° C.), and then Na ₇ CO ₃ and around pH 7 Perfect in Add ice and cool to 15 ° C., slowly add to the reaction solution for 4 hours, adjust the pH to 3-4 with 10% Na ₂ CO ₃ solution, stir overnight and filter.

The filtered cake was dispersed in 400 parts of water, adjusted to pH 5.5 with a temperature of 55 ° C. and a 10% Na ₂ CO ₃ solution, and 30 parts of p-toluenesulfonyl chloride was added in small portions, but at a pH of 5.5 and 55 ° C. React with stirring. Confirm the reaction by TLC and further add p-toluenesulfonyl chloride if necessary to complete the reaction. The reaction solution was filtered as it was or about 50 parts of NaCl was added, stirred for 30 minutes, filtered, and dried at 80 ° C. or lower to obtain a target compound in the form of particles (yield: 82%). 1 shows the ¹ H NMR data of the compound of formula 13.

Molecular Formula: C ₂₆ H ₂₃ N ₅ O ₇ S ₂

Exact Mass: 581.1

Molecular Weight: 581.62

m / e: 581.10 (100.0%), 582.11 (28.7%), 583.10 (9.6%), 583.11 (5.9%), 582.10 (3.4%), 584.10 (2.8%)

C, 53.69; H, 3. 99; N, 12.04; 0, 19.26; S, 11.03

When the dye was dyed to nylon fibers, the color was almost yellow to orange, and the dyed fibers exhibited a bacteriostatic reduction rate of 57% or more for Staphylococcus aureus and 99% or more for Klebsiella pneumoniae .

Example 3: Preparation of Compound of Formula 11

14 parts of 2-chloro-5-nitrobenzene-N- (2,4-dimethylphenyl) sulfonamide were added to 140 parts of acetic acid (at room temperature), 28.3 parts of concentrated hydrochloric acid was added, followed by stirring for 30 minutes. A solution of 3.4 parts of sodium nitrite dissolved in 10 parts of water is added dropwise for 2 hours and further stirred for 1 hour. Add 110 parts of water (room temperature) and cool it to 0 ~ 1 ℃ using ice. A small amount of sulfamic acid is added to remove excess nitrite.

11.3 parts of 2-amino-8-naphthol-6-sulfonic acid (γ-acid, gamma acid) was added to 50 parts of water, dispersed for 30 minutes, and then dissolved or neutralized to pH 6.5 using Na ₂ CO ₃ . After stirring for 30 minutes. Ice is added, cooled to 10 ° C or lower, and then added to the reaction solution for 3 hours. Stir at 20 ° C. or lower for 12 hours or overnight. 200 parts of NaCl was added, and the mixture was heated to 90 ° C. and filtered. The filtered cake was added to 500 parts of water (40 ° C.), the temperature was raised to 60 to 65 ° C., and neutralized using Na ₂ CO ₃ (Powder) to pH = 7.0. Then, the resultant was dried at 80 ° C. or lower to obtain a red target compound (yield: 90%).

The dyes produced were reddish, dyed well with a high rate of absorption on nylon fiber lines, and exhibited high grade 4 or higher performance in excellent washing, water and daylight fastness. The dyed nylon fibers showed a bacteriostatic reduction of more than 99% for Klebsiella pneumoniae .

Example 4: Preparation of Compound (14)

Add 30.8 parts of 2-aminophenol-4- (2-carboxyl-sulfonanilide) to 200 parts of water (room temperature), complete with a 50% NaOH solution at pH 7 and dissolve 8 parts of NaNO ₂ . Add ice and cool to around 0 ℃. Add 45 parts of hydrochloric acid, but vigorously stir for 30 minutes to complete the diazotization reaction.

Disperse 32.3 parts of 1- (2,5-dichloro-4-sulfophenyl) -3-methyl-5-pyrazolone in 200 parts of water (at room temperature), complete at pH 8 with 50% NaOH solution, and make up to about 50 parts of ice. Is added and cooled to about 10 ° C. Coupling reaction is completed by adding to the diazo reaction solution prepared above for 20 minutes, neutralizing the pH to 8 or more and stirring for 2 hours. 50 parts of NaCl was added and stirred for 30 minutes, and then the pH was lowered to 4 or less with hydrochloric acid. The particles began to precipitate, and the precipitated particles were filtered, dried at 80 ° C. or lower, and the desired compound was obtained as an orange particle. : 95%). Figure 2 shows ¹ H NMR data of the compound of Formula 14.

Molecular Formula: C ₂₃ H ₁₉ C ₁₂ N ₅ O ₉ S ₂

Exact Mass: 643

Molecular Weight: 644.46

m / e: 643.00 (100.0%), 645.00 (75.7%), 644.00 (28.7%), 646.00 (19.8%), 646.99 (16.2%), 648.00 (4.6%), 647.00 (4.2%), 645.01 (3.1% ), 645.99 (1.3%), 648.99 (1.2%)

C, 42.86; H, 2.97; Cl, 11.00; N, 10.87; 0, 22.34; S, 9.95

When the dye was prepared on nylon fiber, it was dyed yellow near orange, and exhibited strong antimicrobial activity that inhibits the growth of Staphylococcus aureus and Klebsiella pneumoniae by 99% or more and washes and water fastness of 4 or more.

Example 5: Preparation of Compound of Formula 15

31 parts of 2-nitro-4 ^'- amino-diphenylamine-4-sulfonic acid were dissolved in 300 parts of water (room temperature) water, 50% NaOH solution was added by dissolving the pH 7, NaNO2 8 parts On the 8 degree wanyong and ice Lower the temperature to 15-20 ℃ with a hot water bath, add 50 parts of hydrochloric acid and stir vigorously for 30 minutes to complete the diazotization reaction, and add 200 parts of ice to lower the temperature below 10 ℃.

10.72 parts of metatoluidine was added together with 30 parts of water, 30 parts of methanol, and 5 parts of hydrochloric acid, and then added to the prepared diazotized solution, neutralized with Na ₂ CO ₃ to pH 6-7, reacted for 3 hours, and reacted with TLC. Check for termination. The particles are precipitated with 150 parts of NaCl and a small amount of hydrochloric acid and filtered.

The filtered cake was dispersed in 700 parts of water, adjusted to pH 5.5 with a temperature of 55 ° C. and a 10% Na ₂ CO ₃ solution, and 40 parts of p-toluenesulfonyl chloride was added in small portions, followed by stirring at a condition of pH 5.5 and 55 ° C. And react. Confirm the reaction by TLC and further add p-toluenesulfonyl chloride if necessary to complete the reaction. The reaction solution was filtered as it was, or a little water was added according to the precipitated state, about 50 parts of NaCl was added, stirred for 30 minutes, filtered, and dried at 80 ° C. or lower to obtain a target compound (yield: 86%). 3 shows the ¹ H NMR data of the compound of formula 15.

Molecular Formula: C ₂₃ H ₂₀ N ₄ O ₉ S ₃

Exact Mass: 592.04

Molecular Weight: 592.62

m / e: 592.04 (100.0%), 593.04 (29.1%), 594.04 (16.4%), 595.04 (3.6%), 594.05 (3.1%)

C, 46.61; H, 3. 40; N, 9.45; 0, 24.30; S, 16.23

When the dye was prepared on the nylon fiber, it was dyed yellow and showed more than 4% washing, water and daylight fastness, and more than 99% strong antibacterial activity against Staphylococcus aureus and Klebsiella pneumoniae .

Example 6

A black dye composition was prepared by mixing the compounds of Formulas 11 and 12 in an amount of 1 to 50% by weight based on the total weight of the dye composition, and mixing the compounds of Formula 13 in 1 to 50% by weight.

Example 7

A black dye composition was prepared by mixing the compounds of Formulas 11 and 12 in an amount of 1 to 50 wt% based on the total weight of the dye composition, and mixing 1 to 50 wt% of the compound of Formula 14.

Example 8

A black dye composition was prepared by mixing the compounds of Formulas 11 and 12 in an amount of 1 to 50% by weight based on the total weight of the dye composition, and mixing the compounds of Formula 15 in 1 to 50% by weight.

Example 9

To 1 to 50% by weight of the compound of Formula 11 based on the total weight of the dye composition, and C.I. A dye composition was prepared by mixing Acid Red 337 to 1 to 50% by weight.

Example 10

1 to 50 wt% of the compound of Formula 12, based on the total weight of the dye composition, C.I. A dye composition was prepared by mixing Acid Blue 324 in an amount of 1 to 50 wt%.

Example 11

1 to 50 wt% of the compound of Formula 15 based on the total weight of the dye composition, and C.I. Dye compositions were prepared by mixing Acid Yellow 199 to 1 to 50% by weight.

Example 12

1 to 50 wt% of the compound of Formula 15 based on the total weight of the dye composition, and C.I. A dye composition was prepared by mixing Acid Orange 67 to 1 to 50% by weight.

Example 13

1 to 50 wt% of the compound of Formula 13 based on the total weight of the dye composition, and C.I. Dye compositions were prepared by mixing Acid Yellow 199 to 1 to 50% by weight.

Example 14

1 to 50 wt% of the compound of Formula 13 based on the total weight of the dye composition, and C.I. A dye composition was prepared by mixing Acid Orange 67 to 1 to 50% by weight.

Example 15

1 to 50 wt% of the compound of Formula 14 based on the total weight of the dye composition, and C.I. Dye compositions were prepared by mixing Acid Yellow 199 to 1 to 50% by weight.

Example 16

1 to 50 wt% of the compound of Formula 14 based on the total weight of the dye composition, and C.I. A dye composition was prepared by mixing Acid Orange 67 to 1 to 50% by weight.

All simple modifications and variations of the present invention shall fall within the scope of the present invention, and the specific protection scope of the present invention will become apparent by the appended claims.

Acid dye compound having an antimicrobial activity represented by the following formula (1) having a structure in which two aromatic rings are connected to sulfonamide groups according to the present invention, showing excellent fastness properties and antimicrobial properties, a method for preparing the same, and an antimicrobial dye containing the same A composition was provided.

Acid dye compounds having antimicrobial activity according to the present invention exhibit excellent antimicrobial activity upon dyeing on fibers. These compounds are expected to exhibit excellent antimicrobial activity against other strains within the range of sulfonamide-based antimicrobial agents, in addition to the specially tested strains, and since they are dyed in fibers, antimicrobial activity can be expected to be maintained while color remains. Can be. In addition, since it can be used freely mixed with existing commercially available acid dyes, no problem will occur during dyeing.

Claims (13)

The acid dye compound having an antimicrobial activity represented by the following formula (1). [Formula 1]

In the formula, Ar ¹ and Ar ² may be the same or different from each other, and each independently an amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; A phenylamino group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms; Benzenesulfonamido substituted or unsubstituted with a halogen atom or a carboxylic acid group selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; And -N (C ₂ H ₄ OH) ₂ , a phenyl group or a naphthyl group which is substituted or unsubstituted with one or more groups selected from the group consisting of: B ¹ is a hydrogen atom or an amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Alkyl of 1 to 6 carbon atoms, alkoxy group of 1 to 6 carbon atoms; A phenylamino group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; One or more same or different groups selected from the group consisting of -NO ₂ , -NHCONH ₂ , -CONH ₂ , = O and -N (C ₂ H ₄ OH) ₂ , or represented by the following Chemical Formulas 2 to 5 Is selected from the group, [Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

B ² is a hydrogen atom or an amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Alkyl of 1 to 6 carbon atoms, alkoxy group of 1 to 6 carbon atoms; A phenylamino group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; One or more of the same or different groups selected from the group consisting of -NO ₂ , -NHCONH ₂ , -CONH ₂ , = O and -N (C ₂ H ₄ OH) ₂ , or represented by Formula 2 or 5 It's a flag. B ¹ of the Formula 2 and 5 of R ₁ to R ₆ and R ₁ to R ₈ in the formulas (3) and (4) when selected from the groups represented by Formula 2 to 5 At least one is an azo group (-N = N-) or an amino group (-NH-) which connects Ar ¹ and B ¹ , and the rest are each independently a hydrogen atom; Amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Nitro group; Halogen atoms selected from fluorine, chlorine, bromine and iodine; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Phenylamino group which is substituted or unsubstituted by 1 or more groups chosen from a C1-C6 alkyl group, a nitro group, and a sulfonic acid group; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH- (C ₆ H ₅ ) CH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; -N (C ₂ H ₄ OH) ₂ ; -NH- (C ₆ H ₅ ) NO ₂ ; -NH- (C ₆ H ₅ ) SO ₃ H; And one or more same or different substituents selected from the group consisting of -OC ₂ H ₅ , When B ² is a group represented by Formula 2 or 5, R ₁ to R ₆ of Formulas 2 and 5 At least one is an azo group (-N = N-) or an amino group (-NH-) which connects Ar ² and B ² , and the rest are each independently a hydrogen atom; Amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Nitro group; Halogen atoms selected from fluorine, chlorine, bromine and iodine; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Phenylamino group which is substituted or unsubstituted by 1 or more groups chosen from a C1-C6 alkyl group, a nitro group, and a sulfonic acid group; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH- (C ₆ H ₅ ) CH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; -N (C ₂ H ₄ OH) ₂ ; -NH- (C ₆ H ₅ ) NO ₂ ; -NH- (C ₆ H ₅ ) SO ₃ H; And one or more of the same or different substituents selected from the group consisting of -OC ₂ H ₅ . delete delete According to claim 1, wherein the compound represented by the formula (8). [Formula 8]

In formula, R <_1> -R <_10> is respectively independently a hydrogen atom; Amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Nitro group; Halogen atoms selected from fluorine, chlorine, bromine and iodine; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Phenylamino group which is substituted or unsubstituted by 1 or more groups chosen from a C1-C6 alkyl group, a nitro group, and a sulfonic acid group; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH- (C ₆ H ₅ ) CH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; -N (C ₂ H ₄ OH) ₂ ; -NH- (C ₆ H ₅ ) NO ₂ ; -NH- (C ₆ H ₅ ) SO ₃ H; And one or more of the same or different substituents selected from the group consisting of -OC ₂ H ₅ . According to claim 1, wherein the compound represented by the formula (9). [Formula 9]

In the formula, each of R ₁ to R ₈ independently represents a hydrogen atom; Amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Nitro group; Halogen atoms selected from fluorine, chlorine, bromine and iodine; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Phenylamino group which is substituted or unsubstituted by 1 or more groups chosen from a C1-C6 alkyl group, a nitro group, and a sulfonic acid group; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH- (C ₆ H ₅ ) CH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; -N (C ₂ H ₄ OH) ₂ ; -NH- (C ₆ H ₅ ) NO ₂ ; -NH- (C ₆ H ₅ ) SO ₃ H; And one or more of the same or different substituents selected from the group consisting of -OC ₂ H ₅ . According to claim 1, wherein the compound represented by the formula (10). [Formula 10]

In formula, R <_1> -R <_10> is respectively independently a hydrogen atom; Amino group; Sulfonic acid groups; Hydroxyl group; Carboxylic acid groups; Nitro group; Halogen atoms selected from fluorine, chlorine, bromine and iodine; Alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Phenylamino group which is substituted or unsubstituted by 1 or more groups chosen from a C1-C6 alkyl group, a nitro group, and a sulfonic acid group; Benzenesulfonamido groups substituted or unsubstituted with halogen atoms or carboxylic acid groups selected from fluorine, chlorine, bromine and iodine; -NHCOCH ₃ ; -NH- (C ₆ H ₅ ) CH ₃ ; -NH ₂ CH ₃ ; -SO ₂ NH ₂ ; -NHSO ₂ CH ₃ ; -N (CH ₃ ) ₂ ; -N (C ₂ H ₅ ) ₂ ; -NO ₂ ; -NHCONH ₂ ; -CONH ₂ ; = O; -N (C ₂ H ₄ OH) ₂ ; -NH- (C ₆ H ₅ ) NO ₂ ; -NH- (C ₆ H ₅ ) SO ₃ H; And one or more of the same or different substituents selected from the group consisting of -OC ₂ H ₅ . The acid dye compound having an antimicrobial activity according to claim 1, which is represented by the following Chemical Formulas 13 to 15. [Formula 13]

[Formula 14]

[Formula 15]

An acid dye composition having an antimicrobial activity comprising at least one acid dye compound having an antimicrobial activity according to any one of claims 1 and 4 to 7. The composition of claim 8, wherein the composition exhibits antimicrobial activity against Staphylococcus aureus , Klebsiella pneumoniae or both strains. The method of claim 8, wherein C.I. Acid Red 337, C.I. Acid Blue 324, C.I. Acid Yellow 199 and C.I. The composition further comprises one or more dye compounds selected from the group consisting of Acid Orange 67. The composition of claim 10, wherein the composition exhibits antimicrobial activity against Staphylococcus aureus , Klebsiella pneumoniae or both strains. A fiber exhibiting antimicrobial activity, dyed with an acid dye compound having an antimicrobial activity according to any one of claims 1 and 4 to 7. A fiber exhibiting antimicrobial activity, dyed with an acid dye composition having an antimicrobial activity according to claim 8.

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