JP2006037268A - Deeply dyeing method in clear blue green color - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for dyeing a synthetic polyamide-based fiber material in clear blue green color by which the synthetic polyamide-based fiber material comprising a synthetic polyamide or a composite fiber material of the synthetic polyamide and another fiber can be dyed in the clear blue green color to a deep color range, and a dyed product having excellent various fastnesses or the like is provided. <P>SOLUTION: The method for deeply dyeing the synthetic polyamide-based fiber in the clear blue green color involves carrying out exhaustion dyeing by using a dyebath of a clear blue green acid dye in a concentration of the dye regulated so as to exhibit ≤16.00 absorbance at the maximum absorption wave length of 630 nm when measured by using ion-exchanged water or soft water having ≤1 German hardness, and containing formic acid or a mixed acid containing the formic acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for vivid blue-green dyeing of synthetic polyamide fibers, in which synthetic polyamide and composite fiber materials of synthetic polyamide and other fibers are dyed in a vivid blue-green thick and highly fast.

  In recent years, there has been a strong demand for a clear blue-green and dense dyeing process of synthetic polyamides such as 6-nylon and 6,6-nylon. Similarly, for composite fiber materials of synthetic polyamide and other fibers such as cellulose, natural polyamide, polyester, polyacryl, etc., there is a great need for a clear blue-green and dense dyeing. .

  As a dyeing method for dyeing synthetic polyamide dark blue-green, exhaust dyeing at a high temperature of 104 to 140 ° C. in a dye bath containing a Turquoise reactive dye is known (Japanese Patent Laid-Open No. Sho 55- No. 26298). However, the dyed product obtained by this method has poor light fastness and is difficult to put into practical use.

  In addition, for the dyeing to a light medium color, Supranol Turquoise GGL (CI Acid Blue 279) belonging to an acid dye can be used. However, this method has a problem with leveling properties, and attention is paid to ensuring leveling properties when implementing the method. Moreover, in the case of using this dye, it is difficult to carry out dense dyeing, and only a method having many problems has been found even though various studies have been made. For example, a method of dyeing for a long time at a high temperature of 100 ° C. or higher and a high pressure is performed, but the dye remaining in the dyeing bath is unstable, often resulting in dye agglomerates, which adhere to the dyed matter. And cause big trouble.

  Further, according to the study of the present inventor, the polyamide fiber material is C.I. I. In the case of exhaust dyeing using Acid Blue 279, if the dye concentration in the dyeing bath exceeds a certain value (density limit), the density of the dyed product is decreased even if the dye concentration is increased, and in this case It has been found that an abnormal dyeing state in which there are very few parts that are normally dyed is obtained. The dye limit at the density limit corresponds to a medium color density of normal dyeing, and therefore a dense dyeing cannot be obtained even if dyeing is performed under conventional conditions.

  As a dyeing method for dyeing synthetic polyamide into a clear blue-green color, a method using a Turquoise disperse dye is also known. However, the dyed product obtained by this method has insufficient light fastness, wash fastness, sharpness, etc., and has not yet solved the problem.

Thus, depending on the conventional method, it has been difficult to dye a synthetic polyamide fiber material such as 6-nylon or 6,6-nylon to a vivid blue-green color in a robust and dark range. . In the case of dyeing composite fiber materials of synthetic polyamide and other fibers, it is more difficult to combine the dyeing conditions to improve the sharpness, density, and fastness of the dyed matter. It was more difficult to dye to a robust and dark range.
JP-A-55-26298

  The present invention can dye a synthetic polyamide fiber material, which is a composite fiber material of a synthetic polyamide or a synthetic polyamide and other fibers, into a clear blue-green color to a deep color range, and various fastnesses, etc. It is an object of the present invention to provide a method for vivid blue-green dyeing of a synthetic polyamide fiber material that can give a dyed material excellent in color.

  The present inventor is an important factor that greatly affects the density of the dyed product, such as the metal ions in the dyeing bath, the dyeing ability in the rate-determining step of dyeing, the type of acid that promotes dyeing, and the dye bath composition. I found out that there was a certain point, and sought to optimize these conditions. The inventors have found that the dye density can be improved by making the dye density appropriate and further using a specific acid. In particular, by adding a specific mixed acid as an acid, it is possible to greatly improve the dyeing density while maintaining the clearness of dyeing, and the strong demand of the market is vivid blue-green. It was found that a dark-colored dyeing product having an A of 48.00 or less can be obtained.

  In addition, by using a specific dye composition in the dye bath, or by adding a specific additive to the dye bath, the dyeing density can be improved, and each effect is accumulated (added). Thus, the inventors have found that it is possible to obtain a more excellent effect with respect to sharpness, various fastnesses, etc., in particular, a dark colored dyeing product having an L-value of 45.00 or less, and the present invention has been completed.

  The present invention is a dyeing bath of a bright blue-green acidic dye, having a dye concentration at which the absorbance by ion-exchanged water or soft water having a German hardness of 1 or less at a maximum absorption wavelength of 630 nm is 16.00 or less, and formic acid Provided is a vivid blue-green dark dyeing method for a synthetic polyamide fiber material, characterized in that exhaust dyeing is performed using a dye bath containing the dye (claim 1).

  In the dyeing method of the present invention, the dye bath of the dye bath for exhausting dyeing synthetic polyamide fiber material has an absorbance at a maximum absorption wavelength of 630 nm of 16.1 with a dye solution of ion-exchanged water or soft water having a German hardness of 1 or less. The dye density is equal to or less than 00. That is, in the present invention, dyeing is performed while keeping the dye concentration of the dye bath below the above value. If the dye concentration exceeds this value, the density of the dyed product will be lowered, and there will be a problem that the portion that is normally dyed becomes very small. As a result of the study, the present inventor is required to make the dye concentration in the unit volume of the dye bath within the limit concentration in order to safely carry out the dense dyeing, so that this limit concentration is not exceeded. In addition, it has been found that it is necessary to set dyeing conditions such as a bath ratio.

  The dyeing method of the present invention is also characterized in that the dye bath composition contains formic acid. In the case of dyeing synthetic polyamide or wool with an acid dye, conventionally, acetic acid has always been used as an organic acid as a dyeing accelerator. However, the dyes used in the present invention, such as C.I. I. In the case of an acid dye such as Acid Blue 279, acetic acid is insufficient in effect as a dyeing accelerator and a sufficient dark color cannot be obtained. In order to increase the effect, the effect cannot be obtained even if the acetic acid concentration in the dyeing bath is increased.

  As a result of the study, the present inventor can use formic acid to obtain a sufficient dark color even when a dye having a density limit is used, and to improve a problem that occurs when a large amount of acetic acid is used. I found out. Even if the acid is stronger than acetic acid, the effects as described above cannot be obtained in cases other than formic acid. Only when formic acid is used, dense dyeing with a dye having a density limit can be obtained.

  By using an organic acid selected from a dibasic acid or a tribasic acid together with formic acid, a thicker dyeing can be obtained than with formic acid alone. Claim 2 corresponds to this preferred embodiment, wherein the dyeing method further comprises at least one acid selected from dibasic acid or tribasic acid, formic acid 95. The present invention provides a vivid blue-green deep dyeing method for synthetic polyamide fiber material characterized by containing 5 to 50 parts by weight with respect to -50 parts by weight.

  A mixed acid of 95 to 50 parts by weight of formic acid and 5 to 50 parts by weight of at least one acid selected from dibasic acid or tribasic acid is considered to act as a dyeing accelerator. That is, in order to obtain a thick dyed product, it is important to promote dyeing as much as possible so that the unstable dye bath state does not become long. Color is considered to be achieved.

  The proportion of formic acid in the total mixed acid is 50 to 95% by weight. When the ratio of formic acid is less than 50% by weight, the effect of promoting dyeing is insufficient and it becomes difficult to obtain a dark color. On the other hand, when the proportion of formic acid exceeds 95% by weight, that is, when the proportion of at least one organic acid selected from dibasic acid and tribasic acid is less than 5% by weight, it is about the same as formic acid alone. Only an effect can be obtained.

  The acid mixed with formic acid is at least one organic acid selected from dibasic acids or tribasic acids, that is, one organic acid selected from the group consisting of dibasic acids and tribasic acids, or selected from this group Two or more organic acids. Examples of the dibasic acid include tartaric acid, malic acid, malonic acid, maleic acid, succinic acid and the like, and examples of the tribasic acid include citric acid. The

  Claim 3 corresponds to this representative aspect, and is the above-described dark dyeing method, in which at least one acid selected from dibasic acid or tribasic acid is tartaric acid, which is a dibasic acid, A vivid blue-green dark-dyeing method for synthetic polyamide fiber material characterized in that it is at least one acid selected from the group consisting of malic acid, malonic acid, maleic acid and succinic acid, and tribasic acid citric acid Is to provide. Among them, a mixed acid composed of 95 to 50% by weight of formic acid and 5 to 50% by weight of succinic acid is most effective. The fourth aspect corresponds to an aspect in which this succinic acid is used.

  The content of formic acid or this mixed acid in the dye bath is preferably 2 to 15 ml / l, more preferably 3 to 10 ml / l, as a 1% aqueous solution thereof.

  The bright blue-green dark dyeing method of the present invention is applied to dyeing synthetic polyamide fiber materials. The synthetic polyamide fiber material is a fiber material made of synthetic polyamide or a composite fiber material of synthetic polyamide and other fibers, and examples of the synthetic polyamide include 6-nylon and 6,6-nylon. In addition, examples of other fibers constituting the composite fiber material with synthetic polyamide include cellulose fibers such as cotton, natural polyamide fibers such as wool, polyester, polyacryl, and the like. The present invention is synthesized with one or more of these fibers. It can be particularly suitably applied to a composite fiber with polyamide.

  According to the vivid blue-green dark dyeing method of the present invention, characterized in that the dye concentration of the dye bath is not more than the above value, and the mixed acid is added to the dye bath. It is extremely useful because a dark color can be obtained using a dye that is difficult to obtain. That is, according to the method of the present invention, while maintaining the dye concentration in the dye bath lower than usual, a dyed product having an L-value by colorimetry (representing darkness, the darker the darker) is 48.00 or less. Obtainable.

  As the bright blue-green dye used in the dyeing method of the present invention, C.I. I. A dye mainly composed of Acid Blue 279 is preferably exemplified. A fifth aspect of the present invention corresponds to this preferred embodiment, and is the above-described deep color dyeing method, wherein the bright blue-green dye is C.I. I. The present invention provides a vivid blue-green dark dyeing method for synthetic polyamide fiber materials characterized by comprising Acid Blue 279 as a main component. C. I. Specific examples of the acid blue 279 dye include Supranol Turquoise GGL (manufactured by Dystar).

  The bright blue-green dye is preferably an acid dye, such as C.I. I. In addition to Acid Blue 279, one or more dyes selected from among acid dyes, acid metal-containing dyes, direct dyes or reactive dyes and a clear yellow, green or blue dye are used as a clear blue-green dye. 0.5 to 5% by weight based on the total amount. By containing a small amount of this clear Yellow, Green or Blue dye, the density of the dyed product can be further greatly improved. For example, these dyes are C.I. I. By blending only 2-3% by weight of Acid Blue 279, it is possible to improve the density of the dyed product by at least 30% while maintaining the sharpness that is a major characteristic of this dye.

  Claim 6 corresponds to this preferred embodiment, and is the deep color dyeing method of claim 5, wherein the clear blue-green dye is C.I. I. 95-99.5 parts by weight of Acid Blue 279, and 0,1 of one or more dyes selected from among acid dyes, acid metal-containing dyes, direct dyes or reactive dyes and a clear yellow, green or blue dye. The present invention provides a vivid blue-green dark dyeing method for a synthetic polyamide fiber material characterized by being a mixed dye in an amount of 5 to 5 parts by weight.

  The dye giving such a special effect is a dye selected from the clear Yellow, Blue or Green dyes, but may be any of acid dyes, acid metal-containing dyes, direct dyes or reactive dyes. Further, a mixture composition of two or more of these dyes may be used. Among these, a clear yellow dye as a reactive dye and a clear yellow dye as an acidic metal-containing dye, or a mixture of a clear blue dye as a reactive dye and a clear blue dye as an acidic metal-containing dye are effective.

  When the content of the bright yellow, green, or blue dye is less than 0.5% by weight based on the total amount of the clear blue-green dye, the effect of improving the dyeing density by this mixing may not be sufficiently obtained. On the other hand, when the content exceeds 5% by weight, although the effect of improving the dyeing density is excellent, the sharpness is lowered, which is not preferable in practice.

  Examples of the clear yellow, green, or blue dye include the following dyes.

Sumifix Supra Brill Yellow 3GF (reactive dye)
Sumifix Yellow 2GL (reactive dye)
Sumifix Brill Blue B (reactive dye)
Sumifix Brill Blue R (reactive dye)
Sumifix Brill Blue GL (Reactive dye)
Sumifix Supra Blue BRF (Reactive dye)
Lanyl Brill Blue G (acidic metal-containing dye)
Lanyl Brill Yellow 3G (acidic metal-containing dye)
Suminol Mill. Brill Green 5G (acid dye)
Suminol Sky Blue SE (acid dye)
(End of Sumitomo Chemical Co., Ltd.)

Realan Blue RC (Reactive dye)
Realan Blue B (Reactive dye)
Levafix Royal Blue E-FR (reactive dye)
Realan Yellow G (Reactive dye)
(End of product made by Dystar)

Cibacron Yellow F-4G (Reactive dye)
Cibacron Blue H-2G (reactive dye)
Cibacron Yellow LS-4G (reactive dye)
(End of the above, manufactured by Ciba Specialty Chemicals)

  The dyeing bath of the vivid blue-green dye used in the vivid blue-green dyeing method of the synthetic polyamide fiber material of the present invention has a dye concentration equal to or lower than a predetermined concentration as described above, and a specific acid or It is characterized by containing a mixed acid, and further, the dyeing bath contains one or two saccharides selected from sucrose, honey and soluble starch, or a mixture of this saccharide and dextrin, thereby allowing dyeing. The concentration can be further improved. The content is preferably 0.5 to 5 times the weight of the dye.

  Claim 7 corresponds to this preferred embodiment, wherein the dyeing bath is one or two kinds of sugars selected from sucrose, honey, and soluble starch, and 0.5 to The present invention provides a vivid blue-green dyeing method for synthetic polyamide fiber material characterized by containing 5 times by weight. Preferable examples of saccharides and the like contained in the dye bath include a mixture of sucrose 70 to 40% by weight and dextrin 30 to 60% by weight and honey.

  The dyeing bath used in the deep color dyeing method of the present invention contains a surfactant, which is a substituted alkylamine polyglycol ether, in an amount of 0.3 to 1.5 times by weight, preferably 0.5 to 1. It is preferable to contain 0 times by weight. By containing these in the dye bath, the dyeing concentration can be further improved.

  Claim 8 corresponds to this preferred embodiment, wherein the dyeing bath contains a substituted alkylamine polyglycol ether surfactant in an amount of 0.3 to 1.5 times by weight of the dye. The present invention provides a vivid blue-green dyeing method for synthetic polyamide fiber materials characterized by the above.

  Examples of the substituted alkylamine polyglycol ether surfactant include Sumipon WA (manufactured by Sumitomo Chemical Co., Ltd.), Albegal B (manufactured by Ciba Specialty Chemical Co., Ltd.) and the like. If necessary, an ethylenediaminetetraacetic acid-based metal sequestering agent is added to the dyeing bath used in the dark color dyeing method of the present invention. The method of adding the substituted alkylamine polyglycol ether surfactant and the ethylenediaminetetraacetic acid sequestering agent to the dye bath is not particularly limited, but these and the dye are dissolved in a solvent (water) and liquid The dye is preferably added to the dye bath.

  If the dye concentration is in a range equal to or lower than the concentration corresponding to the absorbance of 16.00, a higher one is preferable because a dark color can be easily obtained. If the dye concentration exceeds the concentration corresponding to the absorbance of 16.00, the density of the dyed product decreases, and problems such as an abnormal dyeing state in which there are few normally dyed parts occur. If the time is short and the extent of exceeding is small, the above problems are small and the excellent effect of the present invention can be obtained. Therefore, it is desirable that the dye concentration is adjusted to be as high as possible within this range while not exceeding the above range.

  Examples of the method of dyeing while maintaining the dye concentration at a concentration corresponding to an absorbance of 16.00 or less include a method of injecting a dye into a dye bath in accordance with dye dyeing. More specifically, examples of the method of injecting the dye into the dyeing bath in accordance with the dyeing include an automatic injection method of a dye solution, a division injection method, etc., and a simple dyeing method can also be adopted. .

In carrying out the dark color dyeing method of the present invention, inorganic neutral salts such as sodium sulfate are quite unsuitable as diluents. That is, a diluent that contains metal ions in the dye bath is not preferred. Also, the water used is important, and care is required such as using soft water with a German hardness of 1 degree or less, or ion-exchanged water. Here, the German hardness is a hardness in which water containing 1 mg of CaO at 100 cm ³ is 1 degree.

  In the vivid blue-green field of synthetic polyamide fiber materials, the concentration decreases rather when the dye concentration in the dye bath is increased, but the dye concentration in the dye bath is kept relatively low and formic acid is added. According to the method of the present invention, it is possible to make dense dyeing. In particular, by using a mixed acid of formic acid and an acid selected from a dibasic acid or a tribasic acid as an acid, the dyeing density can be greatly improved while maintaining the clearness of the dyeing, which is strongly demanded by the market. It is possible to obtain a dark dyed product that is vivid blue-green and has an L-value of 48.00 or less by colorimetry.

  Further, by using the specific mixed dye, the dyeing bath contains sucrose, honey, etc., and the dyeing bath contains the specific surfactant to improve the dyeing density. be able to. Furthermore, by combining these methods, it is possible to build up (add to) the effect of improving the respective dyeing densities. By this combination, the sharpness and various fastnesses are excellent, and the L-value is high. A dark dyeing of 45.00 or less can be obtained.

  And as a method for this combination, for example, the above-mentioned effective mixed dye component, sucrose and honey, the above-mentioned specific surfactant component, etc. are commercialized in advance and used at a predetermined ratio at the time of dyeing. A method is mentioned.

  Next, the best mode for carrying out the present invention will be described using examples, but the examples do not limit the scope of the present invention.

Experimental Examples 1-7
6 g of nylon jersey (* 70d, 24F, double yarn) and 1 g of unsilqueted cotton knit (* 40d, single yarn) were immersed in hot water of ion exchange water for 10 minutes, and then sufficiently squeezed and drained. Thereafter, 0.5 ml of a 1% aqueous solution of each of the following organic acids (% by weight, hereinafter% of acid aqueous solution means weight percent) and 5 ml of a 0.5% aqueous solution of Supranol Turquoise GGL (manufactured by Dystar) were added. In addition to 40 ml of the contained dye bath, the dyeing was carried out at 95 ° C. for 40 minutes, washed with water, subjected to normal soaping with a polycarboxylic acid surfactant, washed with water and finished. The results are shown in Table 1 together with the pH (20 ° C.) of an aqueous solution obtained by diluting 0.5 ml of each organic acid 1% aqueous solution to 40 ml with water.

＊目視判定で、＋１は約５％の向上、−１は約５％の低下。

* In visual judgment, +1 is about 5% improvement and -1 is about 5% decrease.

Until now, since dyeing in an acetic acid acidic bath is normal, the concentration in Experimental Example 1 was used as a standard. The right column of Table 1 shows the result of comparing the concentration of Experimental Example 1 with the concentration of Experimental Examples using other acids. The following is clear from the results.
1. Formic acid, which is the same monobasic acid as acetic acid, has a low pH and an improved concentration (about 15%).
2. On the other hand, the concentration of maleic acid, which is a dibasic acid and has the lowest pH, decreased. Therefore, the pH and concentration improving effect of the organic acid (aqueous solution) are not related.
3. The concentration improvement effect of tribasic acid (citric acid) is also smaller than formic acid.

Experimental Example 8
Instead of 0.5 ml of a 1% aqueous solution of organic acid, 0.125 ml each of a 1% aqueous solution of formic acid, a 1% aqueous solution of malic acid, a 1% aqueous solution of citric acid and a 1% aqueous solution of succinic acid, each in a total of 0. Dyeing was carried out by adding 5 ml, but the concentration of the dyed product was lower than that in the case of the dyeing bath containing only formic acid having the greatest effect in Example 1 (Experimental Example 2).

Experimental Examples 9-13
Instead of 0.5 ml of 1% aqueous solution of formic acid, 0.25 ml of formic acid and 0.25 ml of malic acid (Experimental Example 9), 0.25 ml of formic acid and 0.25 ml of tartaric acid (Experimental Example 10), respectively, 0.25 ml and 0.25 ml succinic acid (Experimental Example 11), formic acid 0.25 ml and citric acid 0.25 ml (Experimental Example 12), or mixed acid of formic acid 0.25 ml and malonic acid 0.25 ml (Experimental Example 13) As a result of dyeing in the same manner as in Experimental Example 2 except that was used, the concentration was improved from Experimental Example 2 using formic acid alone. In particular, in Experimental Examples 10 to 13, it was confirmed that the formic acid alone was improved by about 5%.

Experimental Example 14
Instead of 0.5 ml of 1% aqueous solution of formic acid, dyeing was carried out in the same manner as in Experimental Example 2, except that a mixed acid consisting of 0.35 ml of 1% aqueous solution of formic acid and 0.15 ml of 1% aqueous solution of succinic acid was used. As a result, the density of the dyed product obtained was determined by colorimetry (SICOMUC-20 system), with the dyeing concentration of the dyeing bath in Experimental Example 2 using 0.5 ml of a 1% aqueous solution of formic acid alone as a standard. Concentration ratio is 127.1%, hue difference is 1.66 (P), sharpness is 0.59 (C) (P is purple, C is clear), L-value is 47.87, the highest The value is shown.

  In Examples 9 to 14, the concentration on the 6-nylon side was clearly improved as compared with conventional ordinary dyeing in which acetic acid was added. In addition, the following experiment was conducted to greatly improve the concentration.

Experimental Example 15
Instead of 5 ml of Supranol Turquoise GGL 0.5% aqueous solution, 5 ml of Supranol Turquoise GGL 1% aqueous solution was used, and the additive dyes shown in Table 2 below were further added, and Experimental Example 2 (0.5 ml of 1% formic acid aqueous solution was used) Dyeed and finished as in. And the density | concentration improvement by the side of 6-nylon was judged visually and the result was combined with the following table 2, and was displayed. The dye on the cotton knit side was removed by washing and soaping.

＊０．１ｍｌの添加は、Ｓｕｐｒａｎｏｌ Ｔｕｒｑｕｏｉｓｅ ＧＧＬに対して１重量％に相当する。
＊＊目視判定で、＋１は約５％の向上。

* Addition of 0.1 ml corresponds to 1% by weight with respect to Supranol Turquoise GGL.
** By visual judgment, +1 is improved by about 5%.

  In both cases, since a considerable density improvement was observed, in Experimental Example 16, Realan Blue B (manufactured by Dystar Co., Ltd.) closest in hue was added in a double amount (0.2 ml) and stained in the same manner, and by colorimetry (SICOMUC -20 system) The concentration was measured. As a result, the density ratio 143.5%, hue difference 5.65 (P), sharpness difference 0.37 (C) (P is purple, C is clear) with respect to the dyed product of Experimental Example 15 (standard). L) value of 45.92 was obtained, a thick dyed material greatly exceeding the target was obtained, and the sharpness could be maintained.

Experimental Example 23
Dye 6-Nylon jersey 2.5g and non-silqueted cotton knit 2.5g used in Experimental Examples 1-7 were immersed in hot water for 10 minutes with ion-exchanged water, then thoroughly squeezed and drained, 1% aqueous formic acid solution 1.25 ml of mixed acid consisting of succinic acid and 1% aqueous solution of succinic acid (formic acid: succinic acid = 70: 30 (weight ratio)) and Supranol Turquoise GGL (manufactured by Dystar) 15 ml of 0.5% aqueous solution, Realan Blue RC (Dystar) 0.3 ml of 0.5% aqueous solution, and Lanyl Brill. Blue G Exta. Conc (Sumitomo Chemical Co., Ltd.) is added to 100 ml of dyeing bath containing 0.3 ml of 0.5% aqueous solution. (Bath ratio 1:20, but 1:40 with respect to 6-nylon).

  Next, after dyeing at 95 ° C. for 40 minutes, it was washed with water, soaped and washed in the same manner as in Experimental Examples 1 to 7.

  The result is that the concentration exceeds 170% and the hue is slightly reddish with respect to the dyed product (6-nylon side) obtained by the ordinary dye bath using the acetic acid of Example 1 and Supranol Turquoise GGL so far. A dense dyeing having the same sharpness was obtained.

Experimental Example 24
Except that the same amount, double amount, and triple amount of each of the dyes used in Experimental Example 23 were added, the same dye composition as in Experimental Example 23 and 2.5 g of 6-nylon jersey used in Experimental Example 23 Was dyed in the same manner at a bath ratio of 1:20 (50 ml of dyeing bath amount). The results showed an abnormal phenomenon that the density of each dyed product was low and the concentration was lowered as the amount of the dye aqueous solution was increased to double and triple.

Experimental Example 25
The bath ratio was set to 1:40 with respect to 2.5 g of 6-nylon jersey used in Experimental Example 23, and a dyeing bath containing the same amount of each of the dyes used in Experimental Example 23 was prepared. It dye | stained for 95 minutes at 95 degreeC with this dyeing bath. As a result, the same density as that of the dyed 6-nylon jersey in Experimental Example 23 was obtained. Subsequently, when the bath ratio was 1:40 and dyeing at 95 ° C. for 40 minutes was repeated with a dye bath containing the same amount of each of the dyes used in Experimental Example 23, the density was further improved, and the dyeing of Experimental Example 23 was performed. A thick dyeing exceeding 140% was obtained.

Experimental Example 26
Instead of 0.5 ml of 1% formic acid aqueous solution, 1.25 ml of mixed acid consisting of 1% formic acid aqueous solution and 1% aqueous succinic acid solution (formic acid: succinic acid = 70: 30 (weight ratio)) is used as a diluent. Dyeing was carried out in the same manner as in Experimental Example 2, except that 3 ml of 1% aqueous solution and 2 ml of 1% dextrin aqueous solution were contained in a 40 ml dyeing bath. Although it is important not to reduce the concentration even when it is added as a diluent, the result is an improvement of about 5% rather than no decrease in concentration.

Experimental Example 27
Supranol Turquoise GGL (manufactured by Dystar) 5% 1% aqueous solution, Suminol Midl. Brill. Green 5G 1% aqueous solution 0.15 ml, Sumipon WA (manufactured by Sumitomo Chemical Co., Ltd.) 2% aqueous solution 5 and ion-exchanged water were added to prepare a total of 10 ml of dye solution. Experimental Example 2 except that 5 ml of this dye solution was used and 0.5 ml of a mixed acid composed of a 1% aqueous solution of formic acid and a 1% aqueous solution of succinic acid (formic acid: succinic acid = 70: 30 (weight ratio)) was used instead of formic acid. In the same manner as above, dyeing with 40 ml of dyeing bath was performed. The resulting 6-nylon jersey dyeing had a high concentration exceeding 180% of the concentration of the dyeing according to Experimental Example 1 (using acetic acid).

Experimental Example 28
Supranol Turquoise GGL (manufactured by Dystar) 5 ml of 0.5% aqueous solution, Lanyl Br. Blue G Ex. A dye solution of 20 ml in total was prepared from 0.1 ml of 0.5% aqueous solution of Conc (manufactured by Sumitomo Chemical Co., Ltd.), 0.1 ml of 0.5% aqueous solution of Realan Blue B (manufactured by Dystar) and ion-exchanged water.

Next, 5 ml of 0.5% aqueous solution of commercially available honey (New Zealand Honey, Manuka, Airborne Honey Ltd.), 5 ml of 0.5% aqueous solution of commercial white sugar, and substituted alkylamine polyglycol ether surfactants Albegal B (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.5 ml of an aqueous solution was added to ion-exchanged water to prepare a solution having a total amount of 20 ml. Both are mixed before dyeing to prepare a 40 ml dye bath, and 0.5 ml of mixed acid composed of 1% aqueous solution of formic acid and 1% aqueous solution of succinic acid (formic acid: succinic acid = 70: 30 (weight ratio)). In addition, the others were stained in the same manner as in Experimental Example 1. As a result, 6-nylon was densely dyed to obtain a very dark dyeing product having an L-value of 44.3 exceeding 190% with respect to the concentration of the dyeing product of Experimental Example 1 (using acetic acid). And the hue was reddish, but the sharpness was the same and the result was very valuable.

Claims (8)

  A dyeing bath for a bright blue-green acid dye having a dye concentration at which the absorbance by ion-exchanged water or soft water having a German hardness of 1 or less at a maximum absorption wavelength of 630 nm is 16.00 or less and containing formic acid A deep blue-green dyeing method for a synthetic polyamide fiber material, characterized in that exhaust dyeing is used.   The dyeing bath further contains 5 to 50 parts by weight of at least one acid selected from dibasic acid or tribasic acid with respect to 95 to 50 parts by weight of formic acid. A deep blue-green dyeing method for the synthetic polyamide fiber material.   At least one acid selected from dibasic acid or tribasic acid is at least selected from the group consisting of dibasic acid tartaric acid, malic acid, malonic acid, maleic acid and succinic acid, and tribasic acid citric acid. The method of claim 2, wherein the synthetic polyamide fiber material is vivid blue-green, which is a kind of acid.   The method of claim 3, wherein at least one acid selected from dibasic acids and tribasic acids is succinic acid.   The clear blue-green acid dye is C.I. I. 5. The method of vivid blue-green dark dyeing of synthetic polyamide fiber material according to any one of claims 1 to 4, characterized by comprising mainly Acid Blue 279.   The clear blue-green acid dye is C.I. I. 95 to 99.5 parts by weight of Acid Blue 279, and one or more dyes selected from the group consisting of acid dyes, acid metal-containing dyes, direct dyes or reactive dyes and a clear yellow, green or blue dye The method of claim 5, wherein the synthetic polyamide fiber material is dyed in vivid blue-green color.   The dyeing bath contains one or two saccharides selected from sucrose, honey and soluble starch, or a mixture of the saccharide and dextrin in an amount of 0.5 to 5 times by weight of the dye. A bright blue-green dyeing method for the synthetic polyamide fiber material according to claim 6. 8. The synthetic polyamide according to claim 1, wherein the dye bath contains a substituted alkylamine polyglycol ether surfactant in an amount of 0.3 to 1.5 times by weight of the dye. A deep blue-green dyeing method for fiber-based fiber materials.