JPH036189B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a novel 2:1 dyeing method for dyeing natural and synthetic polyamides to provide excellent light and weather resistance.
The present invention relates to a type cobalt complex salt compound and a dyeing method using the same, and the 2:1 cobalt complex salt compound is represented by the following general formula (). In the formula, R ₁ and R ₂ represent a hydrogen atom, a halogen, a lower alkyl group, a nitro group, or a sulfonic acid amide group, and may be the same or different. r ₁ and r ₂ represent a hydrogen atom or a halogen, and may be the same or different. A is Na, K or
Indicates _NH4 . Metal complex dyes can dye nylon easily and robustly, so they are frequently used for dyeing nylon. On the other hand, nylon is often used in carpets due to its excellent material properties, but in recent years it has come to be used in car mats, car seats, and even in some outdoor areas, and has become resistant to metal complex dyes, which are colorants. , more excellent light fastness and weather fastness are now required than ever before. In other words, the light fastness is at a temperature of 63± as specified by JIS-L0842.
Exposure is carried out at 3°C, but for use in car seats and car mats, fastness is required to withstand exposure at a high temperature of 83±3°C and for 100 to 200 hours.
Furthermore, recently, the durability in the sunshine weather test specified in ASTM-D-822, such as 60℃,
There was a need for a dye that could withstand harsh conditions at high temperatures and high humidity, such as 100% humidity for 160 hours. Especially when it comes to bright yellow dyes, there is no satisfaction.
Its development is eagerly awaited. Conventionally well-known yellow metal complex dyes include dyes represented by the following formulas. However, even these excellent dyes cannot pass weather fastness tests at high temperatures and high humidity (Sunshine in Weather Test, for example, 60°C, 100% humidity, 160 hours). The present inventors dyed bright yellow, but o, o'-
We focused on chromium complex salts of dihydroxyazomethine dyes and investigated them. Famous dyes of this type include the following formulas () and (). etc., which are known to have excellent light fastness in nylon dyeing, but these also gave unsatisfactory results in the sunshine in weather test mentioned above. Further, o,o'-dihydroxyazomethine dyes having one sulfonic acid group in the molecule as shown in the invention described in JP-A No. 48-4515:
Although the 1-cobalt complex salt has better light resistance than nylon, its washing fastness is poor and the results of the sunshine weather test are also unsatisfactory. In addition, dyeing is significantly delayed in acidic or neutral baths, making compound dyeing difficult. The present inventors investigated 2:1 cobalt complex salts of o,o'-dihydroxyazomethine dyes, which were previously unknown, and found that these 2:1 cobalt complex salts showed higher light fastness in nylon dyeing than chromium complex salts. Furthermore, the inventors discovered that the fastness is particularly excellent at high temperatures and high humidity, leading to the present invention. Examples of azomethine dyes used in the complex salt compound of the present invention include o-aminophenol, 4-methyl-
2-aminophenol, 4-chloro-2-aminophenol, 4-nitro-2-aminophenol, 2-aminophenol-4-sulfonic acid amide, 4-nitro-6-chloro-2-aminophenol, 4-methyl o-aminophenols such as -6-nitro-2-aminophenol, 4,6-dichloro-2-aminophenol, 6-nitro-2-aminophenol-4-sulfonic acid amide, etc.
-Hydroxy-benzaldehyde, 4-chloro-2-hydroxy-benzaldehyde,
Salicylaldehydes such as 4,6-dichloro-2-hydroxy-benzaldehyde and 4-bromo-2-hydroxy-benzaldehyde are prepared by a known method, that is, in water or an organic solvent, at room temperature or under heating, under neutral or acidic conditions. It can be easily obtained by condensation with In order to make the thus obtained o,o'-dihydroxy-azomethine dye a 2:1 cobalt complex salt, the o,o'-hydroxy-monoazo dye was mixed with 2:
1. Method for producing cobalt complex salts: Cobalt-imparting agents such as cobalt formate, cobalt acetate, cobalt sulfate, cobalt chloride, and sodium cobalt salt in water or an organic solvent at a neutral or alkaline temperature range of usually 70 to 100°C. However, a large amount of 1:1 cobalt complex salt, which is poorly soluble and has low dyeing power and has little practical value, was produced, and only a small amount of the desired 2:1 cobalt complex salt was obtained. Since the obtained cobalt 1:1 complex salt is poorly soluble in water, in order to obtain a 2:1 cobalt complex salt, it is further treated with an uncoordinated o,o'-dihydroxy-azomethine dye in an organic solvent. It has been found that it is difficult to obtain a highly pure 2:1 cobalt complex even with these methods. Conventionally, o of the present invention,
The reason why a 2:1 cobalt complex salt of o'-dihydroxy-azomethine dye is not known is probably due to the manufacturing process as described above. The present inventors have discovered a novel o,o'-dihydroxy-
As a result of continuing studies on industrial methods for producing 2:1 cobalt complex salts of azomethine dyes, we found that an aqueous solution of cobalt formate, cobalt acetate, cobalt sulfate, or cobalt chloride was mixed with water or an organic solvent of o,o'-dihydroxy-azomethine dye. By slowly adding it to an alkaline solution under stirring at a temperature of 50°C or lower, preferably in the range of 10 to 30°C, for example, below the liquid surface, an undesirable 1:1 cobalt complex salt is formed, thereby producing the desired 2:1 cobalt complex salt. We have found that cobalt complex salts can be selectively obtained. The novel 2:1 cobalt complex salt of the present invention thus obtained has good water solubility and dyes nylon equally or more vividly yellow than the corresponding 2:1 chromium complex salt, and surprisingly, It has exceptional light and weather fastness. The effects of the present invention will be clarified by Examples below, but the present invention is not limited only to the Examples. Example 1 25g of azomethine dye obtained from 4-chloro-2-aminophenol and salicylaldehyde was added to water.
Pour into 1000ml, add 8g of caustic soda and dissolve at 30℃. 100g of 8.9% cobalt acetate aqueous solution (cobalt
(containing 2.9 g) under the liquid surface and then stirred at about 30° C. for 3 hours until cobalt complexation is complete. After clear filtration, salting out filtration removes the desired dye at approximately 95%
% yield. This dye exhibits a bright yellow color (λmax 440 mμ) when dissolved in hot water. Dissolve 0.05 g of the obtained 2:1 cobalt complex dye in hot water to make a total volume of 300 ml, and add ammonium sulfate.
A dye bath was prepared by adding 0.1 g of amylazine D (trade name, product of Daiichi Kogyo Seiyaku Co., Ltd., nonionic cationic slow dyeing agent). 10g of BCF nylon was immersed in this as the material to be dyed, and the bath temperature was increased for 50 minutes while stirring.
The temperature was raised to 100°C. After holding the bath at 100° C. for 10 minutes, 0.05 g of glacial acetic acid was added to the bath, and the bath was kept warm for an additional 20 minutes to complete the dyeing, and the dyed object was washed with water and dried to finish. The BCF nylon to be dyed is dyed a bright yellow color, and as shown in the table, it exhibits extremely good light resistance and weather resistance, and the nylon is extremely unlikely to become brittle due to light irradiation at high temperatures (83°C). It showed good performance. Comparative Example 1 Light resistance and weather resistance of BCF nylon dyed according to the dyeing method of Example 1 using a 2:1 chromium complex dye obtained by chromium complexing the azomethine dye used in Example 1 using a conventional method. The gender is shown in the table for comparison.

[Table] Comparative Example 2 In Example 1, instead of cobalt acetate, 100 g of sodium cobaltite aqueous solution (cobalt 2.9
g) was allowed to act at 70-80°C. Large amount of 1:1
Cobalt complex salts formed and precipitated, and the resulting dye was poorly soluble in water and dyed nylon greenish yellow, but its concentration and light fastness were significantly inferior to the dye obtained in Example 1. Ta. Example 2 24.5 g of azomethine dye obtained from 4-nitro-2-aminophenol and salicylaldehyde was added to an aqueous solution of 8 g of caustic soda in 1000 ml of water.
Dissolve at °C. Slowly add 100g of cobalt sulfate aqueous solution (containing 2.9g of cobalt) below the liquid surface,
Stir at 40-50°C for 2.5 hours until cobalt complexation is complete, then salt out and filter. The dye thus obtained was dissolved in hot water and exhibited a bright yellow color (λmax 430 mμ). 0.8 g of the obtained 2:1 cobalt complex dye was dissolved in hot water, water was added to make 1000 ml, and 2.5 g of the sizing agent Indarka 7883 (product of Chugai Boeki Co., Ltd.) and 2 g of alimentary acid were added to create a dye padding bath. adjusted. This was padded with a nylon BCF tufted carpet, squeezed to a pick-up rate of 500%, and then steamed in a steamer at 100°C for 5 minutes.
After steaming, the finished nylon BCF tufted carpet is dyed with water and dried.It is dyed a bright yellow color and exhibits good light resistance and weather resistance as shown in the table. It showed good performance with extremely little embrittlement of the nylon due to light irradiation. Comparative Example 3 In a nylon BCF tufted carpet dyed according to the dyeing method of Example 1 using a 2:1 chromium complex dye obtained by chromium complexing the azomethine dye used in Example 2 by a conventional method. Light resistance and weather resistance are shown in the table for comparison.

[Table] Comparative Example 4 In Example 2, the cobalt sulfate aqueous solution was added to 70 to 75
When the mixture was added dropwise at ℃, a large amount of cobalt 1:1 complex salt was generated. Example 3 29 g of azomethine dye obtained from 2-aminophenol-4-sulfonic acid amide and salicylaldehyde are dissolved in 1000 ml of water by adding 10 g of caustic potassium. Slowly drop 100 g of cobalt chloride aqueous solution (containing 2.9 g of cobalt) under the liquid surface at 10 to 15°C.
Stir for 3 hours until cobalt complexation is complete, then salt out and filter. The dye thus obtained exhibits a bright yellow color (λmax 435 mμ) when dissolved in hot water, and is BCF
Nylon was dyed bright yellow using the dyeing method of Example 1, and exhibited good light resistance and weather resistance. The results are shown in the table. Comparative Example 5 BCF nylon was dyed according to the dyeing method of Example 1 using a 2:1 chromium complex dye (λmax 435 mμ) obtained by chromium complexing the azomethine dye used in Example 3 using a conventional method, Its light resistance and weather resistance are shown in the table.

[Table] Comparative Example 6 34 g of azomethine dye obtained from 4-nitro-2-aminophenol-6-sulfonic acid and 2-hydroxy-benzaldehyde is dissolved at 40°C in an aqueous solution of 12 g of caustic soda in 1000 ml of water. 20% cobalt sulfate aqueous solution (contains 2.9g cobalt)
After slowly adding the solution below the surface of the liquid at ~25°C, stir for 3 hours until the cobalt complexation is complete. When the dye obtained by salting out and filtration is dissolved in hot water, it immediately exhibits a bright reddish yellow color, and when BCF nylon is dyed according to the dyeing method of Example 1, it is dyed a bright reddish yellow color. The light resistance was 4th to 5th grade, and the weather resistance was 2nd to 3rd grade. Example 4 4,6-dichloro-2-aminophenol and 4
32 g of azomethine dye obtained from -chloro-2-hydroxy-benzaldehyde is dissolved in a mixture of 500 ml of ethylene glycol and 500 ml of water by adding 8 g of caustic soda. Cobalt acetate (tetrahydrate)
Dissolve 12.5g in 50ml of ethylene glycol.
The mixture is added dropwise at 30 to 35°C, and after completion of cobalt complexation, it is poured into 1000 ml of water and filtered for salting out. The thus obtained dye dissolves in hot water and exhibits a bright yellow color (λmax 435 mμ), and is applied to a BCF nylon tufted carpet using the same method as in Example 1. ) dyes a remarkable yellow color. Thereafter, 2:1 cobalt complex salt dyes of azomethine dyes as shown in the table are obtained in the same manner, and both dye nylon in bright yellow with excellent light fastness and weather fastness as shown in the table.

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Claims (1)

[Claims] 1 General formula () (In the formula, R ₁ and R ₂ represent a hydrogen atom, a halogen, a lower alkyl group, a nitro group, or a sulfonic acid amide group, and may be the same or different. _{r 1} and r ₂ represent a hydrogen atom or a halogen. , may be the same or different.A is Na, K or
Indicates _NH4 . ) A novel 2:1 cobalt complex salt compound. 2 General formula () (In the formula, R ₁ and R ₂ represent a hydrogen atom, a halogen, a lower alkyl group, a nitro group, or a sulfonic acid amide group, and may be the same or different. _{r 1} and r ₂ represent a hydrogen atom or a halogen. , may be the same or different.A is Na, K or
Indicates _NH4 . ) A method for dyeing natural and synthetic polyamides, characterized by dyeing using a novel 2:1 type cobalt complex compound represented by: