JP3083403B2 - Dyeing method for polyamide fiber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing polyamide fiber products.

[0002]

2. Description of the Related Art Polyamide fibers are dyed by reactive dyes,
The dyeing is carried out using an acid dye or a gold-containing acid dye.In such dyeing, it is firstly necessary to adsorb a larger amount of the dye. In addition, it is common to adjust the dyeing bath.

[0003] However, the primary purpose of dye adsorption is to adjust the pH.
In dyeing baths, the adsorption of the dye is large even during the dyeing process, so that the final dyed product is often unevenly dyed.

[0004] As a method for preventing this, a method of making the rate of temperature rise extremely slow is performed, but this method is still insufficient to obtain a high-quality dyed product. This method goes against the recent trend of energy saving and labor saving.

On the other hand, various methods using a pH-lowering agent for dyeing polyamide fibers have been tried (for example, JP-A-53-126394, JP-A-57-16979, and JP-A-60-16979). 17183, JP-A-2-25
1675, JP-A-3-40868 and JP-A-4-11083).

However, the compounds used in these methods have a large hydrolysis even at 20 to 25 ° C., which is the initial stage of dyeing, so that it is difficult to obtain an initial slow dyeing effect. Even at ℃ C, hydrolysis is large, so even if an alkaline agent is used in combination to enhance the slow dyeing effect, it is difficult to maintain the pH of the initial dyeing bath on the highly alkaline side, and the solubility in water is low. Poor workability, poor storage point due to low flash point of compound,
All of these were not always satisfactory for dyeing due to problems such as low pH drop performance and inability to apply to a wide range of dyeing.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the conventional method and to provide a polyamide-based fiber product,
Providing a method that can be dyed very efficiently and always uniformly and with good quality, that is, as a pH adjuster, (1) stable at room temperature, little decrease in pH, and (2) combined use with an alkaline agent In, can maintain a high pH in the initial stage of staining,
(3) To provide a highly practical method for dyeing polyamide-based fiber products by using a compound having high solubility in water and (4) a compound capable of increasing the difference in pH drop between the initial dyeing and the final dyeing. As an issue.

[0008]

According to the present invention, a polyamide fiber product is prepared by using a dyeing bath having an initial pH of 5 to 13.
When dyeing at a temperature of 60 ° C. or more,
The problem has been solved by incorporating at least one compound represented by the following formula (1), whereby the pH of the dye bath is naturally lowered during the dyeing step.

[0009]

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As described above, polyamide fibers are generally dyed with a reactive dye, an acid dye, a gold-containing acid dye, and the like. From a relatively low pH acidic bath. However, the relationship between the pH of the dye bath and the amount of dye adsorbed not only determines the amount of dye adsorbed in the final stage, but also in the entire dyeing process, the lower the dye bath pH, the greater the amount of dye adsorbed. Therefore, when dyeing is carried out by adjusting the pH at the initial stage of the dyeing to be low, the dyeing speed is increased, and problems such as uneven dyeing and color breakage are likely to occur, and it has been difficult to carry out uniform dyeing.

However, in the method of the present invention, the initial stage of the dyeing bath is
The pH can be adjusted to basic by using a neutral or alkaline agent in combination, and the temperature can be raised. Therefore, in the stages from the initial stage to the middle stage of the dyeing process, the pH of the dyeing bath is basic to neutral, so that the rapid adsorption of the dye to the material to be dyed is suppressed, and the dye is adsorbed at an average speed. , It is possible to prevent uneven dyeing. In such a dyeing method that imparts a moderate slow dyeing power, the dyeing speed between dyes is made uniform even for dyeing with a dye compound having a different dyeing speed (dyeing foot) as a method of preventing the color breakup phenomenon. Is also effective.

Subsequently, in the final stage of the dyeing process of the present invention, the dyeing bath changes from neutral to acidic, which is effective for the final dyeing amount, due to the free acid gradually and continuously generated.

In the present invention, since the dyeing bath can be naturally adjusted to a preferable pH at each temperature stage of the dyeing process, dyeing with less dye residue and excellent levelness can be performed.
In addition, for dyeing conditions with a faster heating rate than normal,
Since high level dyeing properties can be obtained, it is very effective as a measure for energy saving and labor saving.

Further, in the present invention, since the pH of the dyeing bath can be spontaneously changed by raising the temperature, single bath scouring dyeing of a polyamide fiber product can be carried out very efficiently.

[0015] Polyamide-based fibers or blended, interwoven or knitted products of polyamide-based fibers and other fibers are top-shaped,
Depending on the form of thread, woven, knitted,
The types of deposits such as knitting oils, sizing agents, waxes and the like are different, but stain substances are adhered to dyeing, and therefore, they are generally removed in a pre-dyeing process.

The removal of these oils and sizing agents is carried out in a neutral to basic bath. That is, in the one bath scouring dyeing same bath processing,
The initial pH of the treatment bath was made basic, and at a relatively early stage of dyeing, washing was terminated while a part of the dye to be adsorbed was adsorbed on the material to be dyed. Most or all of the dye must be adsorbed on the material to be dyed.

The compound represented by the formula (1) of the present invention is treated with a scouring agent such as an alkali agent and a nonionic or anionic surfactant.
When added together with the dyeing bath, such a one-bath scouring dyeing process becomes possible, which is very effective as an energy saving and labor saving measure.

The present invention can also be used very effectively in a one-bath dyeing method of a blended, cross-woven or cross-knitted product of polyamide fibers and cellulosic fibers.

Polyamide fibers have a relatively large adsorption of dye in an acidic bath, whereas cellulosic fibers have a large dye absorption in a neutral to basic bath. These suitable dyeing bath pH
In order to effectively dye different fibers in the same bath, it is necessary to adjust the time of the dyeing process to a neutral to basic bath, and then to convert the other time to an acidic bath.

Therefore, it is difficult to dye a single bath of polyamide fiber and cellulosic fiber in a single bath by the ordinary method. However, in the present invention, the compound of the formula (1) is present in a dye bath together with an alkali agent. This enables such a one-bath dyeing method.

In such an application example, dyeing (processing)
The rate of decrease in the pH of the bath and the accuracy of keeping the pH of the dyeing (treatment) bath constant depend on the type of the compound of formula (1) used, its concentration,
The temperature is determined by the temperature of the dyeing (treatment) bath, the rate of temperature rise, the type of alkaline agent used in combination, the amount used, and the like.

Next, the compound of the formula (1) used in the present invention and the alkaline agent, nonionic surfactant and anionic surfactant used together with the compound will be described in detail. The compound of the formula (1) used in the present invention is an ester compound comprising a dicarboxylic acid and an alcohol, and the dicarboxylic acid used here is malic acid and / or tartaric acid. Representative examples of alcohol include methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, and pentaerythritol. Further, an esterification reaction product with epichlorohydrin or 2,3-epoxypropanol is also effective.

Examples of the alkali agent for adjusting the initial pH of the dyeing bath include an alkali metal hydroxide such as sodium or potassium hydroxide, an alkali metal carbonate such as sodium or potassium carbonate, and borax. Alkali metal borates, such as tertiary sodium or potassium phosphate, sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium metaphosphate, sodium or potassium metasilicate; Alkali metal silicates, alkali metal lower carboxylate salts such as sodium or potassium formate, sodium or potassium acetate, and the like can be used, and these may be used alone or in combination of two or more.

Further, examples of the pH buffering agent used in combination with the alkali agent include ammonium sulfate, ammonium acetate, ammonium phosphate, sodium acetate and the like. When the water used for the treatment liquid is hard water containing a large amount of magnesium sulfate, calcium sulfate, magnesium carbonate, calcium carbonate and the like, a chelating agent such as ethylenediaminetetraacetic acid tetrasodium salt may be used in combination.

Finally, for application to one-bath scouring and dyeing, the nonionic surfactant or anionic surfactant used in combination is lauric acid, ricinolenic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid. Acids, oleic acid, decyl alcohol, isodecyl alcohol, lauryl alcohol, oleyl alcohol, octyl phenol, dinonyl phenol, higher fatty acids such as benzylated phenol, styrenated phenol, alkylene oxide adducts such as higher alcohols, phenol derivatives, etc. And sodium polyacrylate and sodium polymaleate.

The amount of each drug used, the staining conditions, and the like in practicing the present invention are as follows. formula
The amount of the compound (1) and alkaline agent used depends on the type of dyeing solution, the type of fiber to be dyed, and the purpose of the dyeing bath.
Since the pH is different, the kind and amount of an alkaline agent effective for the purpose are determined in advance, and the adjusted initial dyeing bath pH is adjusted to a desired desired dyeing bath pH in the middle to final stages of the dyeing. The amount of the required amount of the compound of formula (1) is determined, but generally, the compound of formula (1) is 0.1 to 100 g / l.
It can be used at a rate of about 0.1 to about 10 g / l.

The amount of the alkali agent can be used at about 0.1 to 50 g / l, preferably about 0.1 to 10 g / l.

Next, the dyeing conditions vary depending on the type of the fiber to be dyed, but generally the treatment is performed at a bath ratio of 1: 5 to 1: 100 at 60 ° C. to 130 ° C. for about 30 minutes to 5 hours. . It is usual that the object to be dyed may be immersed in a dye bath near normal temperature and gradually heated to a predetermined bath temperature. The addition of the compound of the formula (1) may be carried out at any time near the beginning to the end of the dyeing, but it is generally preferred to carry out the addition at the beginning to the middle.

The polyamide fiber product to which the method of the present invention can be applied may be any one containing polyamide fiber, and may be polyamide fiber alone or other fiber (cellulose fiber, semi-synthetic cellulose fiber, polyester fiber). , Acrylic fibers, etc.), cross-woven or cross-knitted products, and may be any of top-shaped, thread-shaped, woven, knitted and non-woven fabrics.

[0030]

Next, the present invention will be described in more detail with reference to Examples. The following three compounds of the formula (1) are used in Examples. Compound A: Diester of malic acid and ethylene glycol Compound B: Diester of tartaric acid and propylene glycol Compound C: Diester of malic acid and epichlorohydrin Example 1 {pH drop test} pH adjuster as shown in Table 1 Were prepared, and a nylon jersey was treated with these baths (bath ratio 1:15). Table 1 shows the change in pH with increasing temperature of each bath.

[0031]

[Table 1]

Example 2 << Dyeing Test >> 10 g of a nylon jersey which had been scoured in advance was subjected to a bath ratio of 1: using a minicolor type 12 dyeing tester (manufactured by Texam Giken).
15. Staining was performed at 100 ° C. for 45 minutes (heating rate 2 ° C./min). In addition, as a dye, the following two types of compounds are used,
Five kinds of pH adjusters shown in Table 2 were used. Dye (1) Leveling type blending Suminol Fast Navy Blue R 0.5% (owf) Suminol Fast Yellow R Conch 0.5% (owf) (2) Milling type blending Nairosan Blue N-BLN 0.4% (owf) Nairosan Table 3 shows the results of the red F-BRN 0.4% (owf) Nirosan Yellow N-4RN 0.4% (owf) staining test.

[0033]

[Table 2]

As shown in Table 2, in the dyeing test according to the present invention (Nos. 3 to 6), the dyeing property during heating was relatively small, and the dye residue after dyeing was small. , And efficient dyeing with levelness was possible.

[0035]

According to the present invention, since the pH of the dyeing bath can be naturally lowered with the progress of the dyeing, the dyeing of the polyamide fiber product is always performed very efficiently and with high quality. Is possible.

Continuation of the front page (72) Inventor Kasumi Nebu 1 Nakazawa-cho, Nishikyogoku, Ukyo-ku, Kyoto-shi, Japan Inside Meisei Chemical Co., Ltd. (56) References JP-A-3-40868 (JP, A) JP-A-62- 28483 (JP, A) JP-A-63-197883 (JP, A) JP-A-60-17183 (JP, A) JP-A-4-11083 (JP, A) JP-A-60-224884 (JP, A) JP-A-55-62046 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06P 3/24 D06P 1/38 D06P 1/39 D06P 1/651 CA (STN) REGISTRY (STN )

Claims (1)

(57) [Claims] 1. A polyamide fiber product having an initial pH of 5
When dyeing at a temperature of 60 ° C. or higher using a dyeing bath of ~ 13, the pH of the dyeing bath is dyed by adding at least one compound represented by the following formula (1) to the dyeing bath. A method for dyeing a polyamide fiber product, wherein the polyamide fiber product is naturally dropped during the process. Embedded image