KR101896967B1 - Uniformity agent compositions for dipdyeing-continuous sulfur dyes, Uniformity agent using the same and Manufacturing method thereof - Google Patents

Abstract

The present invention relates to a dispersion leveling agent, a composition used for the production thereof, and a method for producing the dispersion leveling agent using the same. Of dyeing methods to dye based on chemical bonds on polyamide fibers, the continuous dip dyeing type sulfur dyeing increases physical dispersibility and chemical dispersibility of dyeing components, thereby uniformly improving dyeing properties of the dyeing components for polyamide fibers.

Description

TECHNICAL FIELD [0001] The present invention relates to a dispersion leveling agent composition for continuous dyeing of sulfidation, a dispersion leveling agent using the same, and a method for producing the same,

The present invention improves physical dispersion and chemical dispersibility of a dyeing component simultaneously during dyeing by continuous dyeing in a dyeing method in which dyeing is carried out by chemical bonding to polyamide fibers, thereby improving uniformity of dyeability on dyeing component polyamide fibers And a method for producing a dispersion leveling agent using the same.

Acid staining, which is currently practiced, is a staining method in which an anionic acid dye is chemically bonded to a cationic polyamide fiber. In this staining method, an ionic dispersing leveling agent is used for uniform dyeing. The cationic dispersion leveling agent is a dye-friendly type, and achieves a leveling effect by controlling the rate of dyeing by approaching an anionic acid dye. On the other hand, since the anionic dispersing leveling agent is a fiber-affinity type, it approaches the fiber and interferes with the dyeing of the dye, thereby achieving the leveling effect through the complete salt. However, such an inexpensive method using the acid staining method has a problem of generating a large amount of wastewater and generating a high processing cost.

In order to improve the staining method of existing polyamide fibers, there has been developed a sulfation method using a sulfide dye. The purpose of the sulfide dyeing is to simplify the process to reduce the waste water and increase the fastness by using the sulfide dye.

In sulfidation, when the insoluble sulfide dye is reduced by a reducing agent, it becomes a Leuco compound, and the Luco compound is converted into a sodium derivative (> CONa) which is a water soluble substance in the presence of an alkali. The sodium derivative penetrates into the fiber at a high temperature and is oxidized again to convert it to an insoluble state for the first time.

In addition, since the dyeing method of the continuous salt sulfide dye in the sulfidation dyeing method is not a salt method commonly used in polyamide dyeing, the development of the related preparation is insufficient. In particular, since a sulfide dye has both characteristics of a disperse dye and an ionic dye, a dispersion leveling agent having different physical properties from a commercially available disperse leveling agent or an acidic dispersion leveling agent is required.

Korean Patent Registration No. 1986-0000204 (Mar. 23, 1983) Korean Patent Publication No. 1998-024724 (Jul. 1998)

The present invention can physically disperse insoluble dyes in consideration of the characteristics of a reducing dye, chemically react with a sodium derivative which has become a water-soluble state, And to provide a method for dyeing polyamide fibers or the like by a continuous salt-type sulfidation dyeing method.

The present invention for solving the above-mentioned problems relates to a dispersion leveling agent composition for dyeing continuous sulfide salt, which comprises a polyalkylene oxide-based modifier, an alkali catalyst, an acid and a nonionic emulsifier.

The present invention also relates to a dispersion leveling agent for dyeing continuous salt-type sulfidation, which comprises a nonionic ionic emulsifier modified with a polyalkylene oxide-based modifier, wherein the modified nonionic emulsifier comprises a functional group.

The present invention also relates to a method for producing the above-mentioned dispersed leveling agent, comprising the steps of: mixing and stirring a nonionic emulsifier, a polyalkylene oxide-based modifier, and an alkali catalyst to prepare a mixed solution; A step of raising the temperature of the mixed solution in a nitrogen atmosphere, followed by performing a polymerization reaction and then cooling to prepare a solution containing the polymerization reaction product; Adding an acid to the cooled solution, raising the temperature, performing stirring and reaction, and then cooling; And neutralizing the resulting solution with a base to produce a dispersion leveling agent. The dispersion leveling agent for continuous salt-in-salt type sulfidation dyeing can be prepared.

The present invention also relates to a method of dyeing a continuous salt-in-water type sulfide, comprising the above-described dispersion leveling agent; ≪ / RTI > and sulfide dyes, can be used to carry out continuous dyeing of the polyamide fibers by dip dyeing.

The dispersant leveling agent of the present invention increases the physical dispersibility and the chemical dispersibility of the dyeing component simultaneously when the dyeing agent is applied to the continuous salt dyeing of the dyeing salt so as to uniformly improve the dyeing property of the dyeing component polyamide fiber, Can be improved and activated, thereby replacing the existing cost-effective method which causes a problem of generating a large amount of wastewater and high processing cost.

Figs. 1A and 1B show the results of the dispersion test conducted in Experimental Example 1. Fig.
Fig. 2 shows the results of the dyeability test conducted in Experimental Example 2. Fig.

Hereinafter, the present invention will be described in more detail with reference to a method for producing the continuous leveling dispersion stabilizing agent for dyeing sulfide of the present invention.

The dispersion and leveling agent for dyeing continuous salt-type sulfidation of the present invention comprises a first step of preparing a mixed solution by mixing and stirring a nonionic emulsifier, a polyalkylene oxide-based modifier, and an alkali catalyst; A step of raising the temperature of the mixed solution in a nitrogen atmosphere, followed by performing a polymerization reaction and then cooling to prepare a solution containing the polymerization reaction product; Adding an acid to the cooled solution, raising the temperature, performing stirring and reaction, and then cooling; And neutralizing the mixture with a base to produce a dispersion leveling agent.

The nonionic emulsifier in the first stage may be selected from the group consisting of benzyl benzoate, trioleate, castor oil, sorbitan olivate, polyoxyethylene tridecyl ether, polyoxyethylene lauryl ether, lauryltrimethylammonium chloride, polyoxyethylene stearyl ether , Polyoxyethylene trimethylnonyl ether, and polyoxyethylene dodecyl ether, and may preferably include at least one selected from castor oil, triolate, and benzyl benzoate, and more preferably, And preferably one or more selected from castor oil and triolate.

The polyalkylene oxide-based modifier in the first step may be a poly (C2-C4 alkylene) oxide, preferably polyethylene oxide represented by the following formula (1).

[Chemical Formula 1]

In the general formula (1), n is an integer of 5 to 200, preferably n is an integer of 20 to 50, and more preferably n is an integer of 30 to 50. If n is more than 200, hydrophilicity may be increased and the function as an emulsifier may be deteriorated. If n is less than 5, hydrophilicity may be lowered, which may act as oil rather than emulsifier.

The amount of the polyalkylene oxide-based modifier may be 50 to 75 parts by weight, preferably 55 to 70 parts by weight, and more preferably 56 to 62 parts by weight, based on 100 parts by weight of the nonionic emulsifier. If the amount of the polyalkylene oxide modifier is less than 50 parts by weight, the dispersibility of the final dispersion leveling agent may deteriorate. If the amount of the polyalkylene oxide modifier exceeds 75 parts by weight, unreacted polyalkylene There may be a problem that an excess amount of the oxide-based modifier is present.

The alkali catalyst of the first stage plays a role of promoting the nucleophilic substitution reaction and may include at least one selected from potassium hydroxide, sodium hydroxide, magnesium hydroxide, sodium hydroxide and calcium hydroxide, preferably potassium hydroxide, sodium hydroxide And magnesium hydroxide, and more preferably at least one selected from the group consisting of potassium hydroxide and sodium hydroxide. In this case, the amount of the alkali catalyst to be used may be 2.5 to 18 parts by weight, preferably 3 to 10 parts by weight, more preferably 4 to 8 parts by weight, based on 100 parts by weight of the nonionic emulsifier. If the amount of the alkali catalyst used is less than 2.5 parts by weight, there may be a problem that the reaction conversion rate is lowered. If the amount of the alkali catalyst is more than 18 parts by weight, excessive by-products may be generated during neutralization. It is good.

Next, in the second step, the mixture of the first step is heated to 180 to 210 ° C, preferably 185 to 200 ° C, more preferably 185 to 195 ° C, and the polymerization reaction is carried out for 18 to 24 hours . If the polymerization temperature is lower than 180 ° C, the reaction conversion rate may be lowered. If the polymerization temperature is higher than 210 ° C, there may be a problem of oxidation due to heat.

Then, the reacted solution is cooled to 80 캜 or lower, preferably to 75 캜 or lower. At this time, if the cooling temperature exceeds 80 ° C, there may be a problem due to heat generation in the next step of the acid addition.

Next, in step 3, in order to introduce a functional group, an acid is added to the cooled solution, and then the temperature is raised to 140 to 145 DEG C, followed by stirring and reaction at this temperature, followed by cooling to 50 DEG C or less. At this time, if the temperature rise and the reaction temperature are less than 140 캜, there may be a problem that the conversion rate of the ionization reaction is lowered.

The acid in step 3 may include at least one selected from sulfuric acid, phosphoric acid, and benzoic acid, preferably sulfuric acid. The acid may be used in an amount of 4 to 13 parts by weight, preferably 5 to 10 parts by weight, more preferably 5 to 9 parts by weight, based on 100 parts by weight of the nonionic emulsifier. If the amount of the acid used is less than 4 parts by weight, there may be a problem that the reaction conversion rate is lowered.

Next, Step 4 is a step of preparing a dispersion leveling agent by adjusting the pH to 5 to 8, preferably pH 5 to 7 by adding and neutralizing a base to a solution which has been reacted and cooled with an acid in Step 3. At this time, the base may be a base commonly used in the art, preferably a base containing at least one selected from NaOH, aqueous ammonia, and KOH. If the pH of the dispersing leveling agent exceeds the range, there is a problem that pH is affected when the pH is applied to the salt solution. Therefore, it is preferable to drop the base into the pH range.

The dispersion leveling agent of the present invention prepared by performing such a process includes a nonionic ionic emulsifier modified with a polyalkylene oxide-based modifier, and the modified nonionic emulsifier contains a functional group. At this time, the functional group may include at least one selected from a sulfonic acid group, a cyano group, and a benzyl group.

Generally, in sulfidation, when the insoluble sulfide dye is reduced by a reducing agent, it becomes a Leuco compound, while a leuco compound is converted into a sodium derivative (> CONa), which is a water soluble impurity in the presence of an alkali.

The dispersing leveling agent of the present invention can improve the physical and chemical dispersibility of the sulfide dye in the insoluble state of the lucoric compound and chemically react with the sulfide dye converted into the sodium derivative in the water-soluble state to impart a full-salt effect.

The polyamide fibers can be dyed continuously with sulfite by using the dyeing including the dispersed leveling agent and the sulfide dye of the present invention thus prepared.

Hereinafter, the present invention will be described in detail with reference to examples. However, the scope of the present invention should not be construed as being limited by the following examples.

[Example]

Example 1: Preparation of a dispersion leveling agent

100 parts by weight of a castor oil as a nonionic emulsifier, 60 parts by weight of polyethylene oxide represented by the following formula 1 as a modifier, and 6 parts by weight of potassium hydroxide as an alkali catalyst were added and stirred to prepare a mixture.

Next, the mixture was heated to 190 DEG C under nitrogen, then reacted at 190 DEG C for 20 hours, and then cooled to 70 DEG C. Then,

Next, 8 parts by weight of sulfuric acid (based on 100 parts by weight of castor oil) was added to the cooled solution at 70 占 폚, and then maintained at 140 to 145 占 폚. The reaction was carried out for 5 hours and then cooled to 70 ° C.

Next, the cooled solution was neutralized by adding NaOH as a base to prepare a dispersion leveling agent having a pH of 5. At this time, the dispersant leveling agent is a modified nonionic emulsifier and includes a sulfonic acid group.

[Chemical Formula 1]

In the formula (1), n is 45.

Example 2

The dispersing leveling agent was prepared in the same manner as in Example 1, except that polyethylene oxide having an n value of 200 in Formula 1 was used as a modifier.

Example 3

A dispersion leveling agent was prepared in the same manner as in Example 1, except that 70 parts by weight of polyethylene oxide (n value 45 in the above formula (1)) as a modifier was used.

Example 4

A dispersion leveling agent was prepared in the same manner as in Example 1, except that 50 parts by weight of polyethylene oxide (n value 45 in the above formula (1)) as a modifier was used.

Example 5

A dispersion leveling agent was prepared in the same manner as in Example 1 except that phosphoric acid was used instead of sulfuric acid to introduce a functional group.

Comparative Example 1

The dispersing leveling agent was prepared in the same manner as in Example 1, except that polyethylene oxide having an n value of 300 of the above formula (1) was used as a modifier.

Comparative Example 2

A dispersing leveling agent was prepared in the same manner as in Example 1, except that polyethylene oxide having an n value of 3 in the above formula (1) was used as a modifier.

Comparative Example 3

A dispersing leveling agent was prepared in the same manner as in Example 1 except that nitric acid was used instead of sulfuric acid when an acid was used for introducing a functional group. At this time, the dispersant leveling agent is a modified nonionic emulsifier, which includes a nitro group

Comparative Example 4

A dispersion leveling agent having a pH of 8.5 was prepared by the same method as in Example 1 except that the amount of the base NaOH was varied

Comparative Example 5

The dispersion leveling agent was prepared in the same manner as in Example 1, except that the amount of the base NaOH was varied to prepare a pH level 4.5 dispersion leveling agent.

Production Examples 1 to 5

A salt solution was prepared by adding 0.3 wt% of a dispersion leveling agent prepared in Examples 1 to 5 to 0.3 wt% of a sulfide dye, 0.01 wt% of soda ash, and 99.61 wt% of DI water (distilled water) .

Comparative Production Examples 1 to 5

Comparative Examples 1 to 5 were prepared by preparing sulfide dyes in the same manner as in Preparation Example 1 except that each of the dispersing leveling agents prepared in Comparative Examples 1 to 5 was used instead of the dispersing leveling agent of Example 1, Respectively.

Experimental Example 1: Dispersibility Test

Each of the sulfide dyes prepared in Preparation Examples and Comparative Examples was immersed in a dyeing pot of 300 ml in size and then heated in an IR stainer at 70 ° C. for 15 minutes and then 0.15 wt% Then, a tarring test was performed on the sulfide dye.

The control (blank) was subjected to a taring test without using a dispersant.

Referring to FIG. 1B, when the n value of Formula 1 is higher than or less than 5 or less than 5 as in Comparative Preparation Example 1 and Comparative Preparation Example 2, the problem of dye aggregation due to failure of dispersing function when a dispersing leveling agent is used .

In Comparative Production Example 3, it was confirmed that the introduction of the nitro group had no effect of improving the dispersibility.

Compared with Comparative Preparation 4 and Comparative Production Example 5, the color of the filter paper was partially reduced due to improvement in dye aggregation, but it was difficult to achieve sufficient performance as a dispersion and leveling agent

In comparison between Production Example 1 and Production Example 2 in FIG. 1A, when the n value of the polyethylene oxide as the modifier increases from 45 to 100, the dispersibility of the dye decreases and the color of the filter paper becomes darker Respectively.

Further, when Production Example 1, Production Example 3 and Production Example 4 were compared, when the weight ratio of polyethylene oxide as a modifier was 60 to 60, 70 and 60, the effect of improving the dispersibility was the most excellent. In addition, as the functional group in Production Example 5, when the popularization was introduced in Production Example 1, the dispersibility was more excellent than when the popularization was introduced.

Experimental Example 2: Dyeability test

(1) 0.5% by weight of soda ash, 0.75% by weight of an antioxidant, 0.15% by weight of a dispersion leveling agent of Example 1 and 83.6% by weight of DI water were added to a 15% by weight sulfide dye salt solution and the salt solution was stirred at 70 캜 for 30 minutes. After that, 0.75 wt% of a reducing agent was added and stirred for 15 minutes, and then padded to the polyamide fabric. At padding, the mangling speed was 10 m / min and the pick up rate was over 70%.

Thereafter, the steam was steamed for 15 minutes in a steam machine at 100 ° C, the dyed fabric was washed with 2 g / l of fruit juice, the water was removed by mangling, and curing was carried out at 150 ° C for 3 minutes in a tenter curing. A photograph of the cured polyamide fabric is shown in Fig.

The fabric was made of PU / Nylon nonwoven fabric Rima 0854 manufactured by Jungsan International.

(2) The dyability test was carried out by the same method, except that the dispersing leveling agents of Examples 2 to 5 were used in place of the dispersing leveling agent of Example 1, and the results were shown in Fig.

(3) As a control group, a dyeing test was conducted without using a dispersing leveling agent, and the results are shown in FIG.

In the control group, it was confirmed that unevenness occurred partially due to unevenness, and Examples 1 to 5 were relatively uniformly stained.

In addition, the colorimetry was carried out in order to confirm the uniformity of the dyed fabric using the examples 1 to 5 numerically, and the results are shown in Table 1 below. At this time, the colorimetry was performed using x-rite spectrophotometer color i5. Based on the central part of the dyed fabric, upper and lower portions 50 cm away from the upper and lower sides were colorimetrically scanned as upper and lower portions, respectively.

The upper (E) Central (E) Lower (E) Production Example 1 0.11 0 -0.16 Production Example 2 0.17 0 -0.21 Production Example 3 0.15 0 -0.22 Production Example 4 0.21 0 -0.34 Production Example 5 0.22 0 -0.37

As a result of the measurement, the E value indicating the color difference was measured to be the smallest in Production Example 1, and it can be confirmed that when the Example 1 is dyed using the dispersion leveling agent, the E value is most uniformly stained.

Claims (10)

delete delete delete delete delete delete delete A step of mixing and stirring a nonionic emulsifier, a polyalkylene oxide-based modifier, and an alkali catalyst to prepare a mixed solution;
A step of raising the temperature of the mixed solution to 180 to 210 ° C in a nitrogen atmosphere, followed by performing a polymerization reaction and cooling to prepare a solution containing a polymerization reaction product;
Adding acid to the cooled solution, raising the temperature to 140 to 145 캜, stirring and reacting, and then cooling to 50 캜 or lower; And
Neutralizing with a base to prepare a dispersion leveling agent having a pH of 5 to 8;
Wherein the method comprises the steps of: 10. The dispersion leveling agent for continuous dyeing of sulfidation according to claim 8, wherein the dispersion leveling agent comprises a nonionic ionic emulsifier modified with a polyalkylene oxide-based modifier, and the modified nonionic emulsifier comprises a functional group. Gt; delete

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