JPS5834597B2 - Level dyeing method for acrylic fiber materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a level dyeing method for acrylic fiber materials, and more specifically, it relates to a level dyeing method for acrylic fiber materials, and more specifically, it relates to an acrylic fiber material containing strong basic group-containing acid dye dyeable acrylonitrile synthetic fibers. The present invention relates to a dyeing method that can provide an excellent level dyed product by adding a predetermined amount of a dyeing aid having a specific structural formula to a dye bath when dyeing with an acid dye.

Traditionally, dye baths have been used as a technical means to uniformly dye acrylic fiber materials containing basic dye-dyeable acrylonitrile synthetic fibers with basic dyes to obtain dyed products with vivid color tones. It is widely known to select and use a method of adding a dyeing aid such as a quaternary amine-containing cationic leveling agent or a pyridine ring-containing cationic dye transfer agent.

On the other hand, there are still various problems (for example, It is no exaggeration to say that this has been a long-standing problem in the dyeing processing industry.

Of course, it is a fact that in this industry, many proposals have been made to attempt level dyeing of acrylic fiber materials as described above.

For example, when dyeing acid dye-dyeable acrylonitrile synthetic fibers with acid dyes, one method is to add a formalin condensate of aromatic sulfonic acid as a leveling agent to the dye bath.

However, this method is very effective because the leveling agent has a high affinity for the acrylonitrile-based synthetic fibers - the effect of replacing the acidic dye with the leveling agent adsorbed on the synthetic fibers, that is, the migration effect. This makes it difficult to produce a level-dyed product that is ultimately satisfactory.

As another method, attempts have been made to dye mixed fiber materials containing acid-dyeable acrylonitrile-based synthetic fibers by using an alkyl betaine type amphoteric activator as a leveling agent in the dye bath. However, this dyeing method has a fatal flaw in that the acid dye and the leveling agent interact to form a dye complex, which significantly contaminates the dye bath. Ta.

As described above, dyeing aids (leveling agents) that can impart a leveling effect to conventional acrylic fiber materials containing acid-dyeable acrylonitrile synthetic fibers are still unsatisfactory in various aspects. The industry has been demanding its development for a long time.

Here, in order to eliminate the above-mentioned defects, the present inventors researched dyeing aids that can impart level dyeing to fiber materials containing strong basic group-containing acid dye dyeable acrylonitrile synthetic fibers, and found that By adding a predetermined amount of a compound (a chemical substance that maintains the number of carbon atoms in the alkyl group and the number of added moles of ethylene oxide within a suitable range) into the dye bath as a leveling agent, it is incomparable compared to conventional products. We have now discovered the fact that the level dyeing properties of acidic dyes can be significantly promoted and contamination of dye baths can be reduced, and we have arrived at the present invention.

The purpose of the present invention is to add a predetermined amount of a specific compound to a dye bath when dyeing an acrylic fiber material containing a strongly basic group-containing acid dye-dyeable acrylonitrile synthetic fiber with an acid dye. Therefore, it is an object of the present invention to provide a method for obtaining a uniformly dyed product with good color development by preventing flickering, irritability, uneven dyeing, and color cracking of the hue without contaminating the dye bath in any way.

The object of the present invention is to use the following compounds (1 ) and/or compound (2) in the presence of 0.002 to 0.05 parts per part of the acid dye-dyeable acrylonitrile synthetic fiber.

(In the formula, R1 has 14 to 18 carbon atoms, and R2 has 12 to 1 carbon atoms.
6 saturated or unsaturated aliphatic hydrocarbon, n+m is 6 to
According to the present invention, the affinity of the leveling agent used for the strongly basic group-containing acid dye-dyeable acrylic synthetic fiber is not so great compared to acid dyes, which is advantageous in dyeing. It can guarantee the slow dyeing effect and also promote the migration of acid dyes, and it shows excellent level dyeing and coloring properties for acrylic fiber materials, preventing unevenness of the hue of dyed products and creating a uniform color. A dyed product with good subdued color development can be obtained.

Furthermore, according to the method of the present invention, no interaction is induced between the leveling agent and the acid dye used (no formation of dye complexes is caused), so that the dye bath associated with the conventional technology is Technical issues such as pollution have also been resolved.

Here, the acrylic fiber material in the present invention is a strong basic group-containing acid dye dyeable acrylonitrile synthetic fiber alone or the acrylonitrile-based synthetic fiber.

A mixed fiber material (blend spun, mixed knitted or woven product) consisting of acrylonitrile-based synthetic fibers and basic dye-dyeable acrylonitrile-based synthetic fibers, which can be used in the present invention in the form of loose hair, sliver, yarn, fabric, etc. It is subjected to such dyeing.

Furthermore, the acid dye-dyable acrylic synthetic fiber containing a strong basic group used in the present invention contains acrylonitrile as a main component (preferably 80% by weight or more), can be copolymerized with acrylonitrile, and is resistant to acid dyes. Known strong basic monomers (for example, dimethylaminoethyl ester, diethylaminoethyl ester, corresponding N-substituted aminopropyl ester, N-substituted aminobutyl ester, etc. of acrylic acid and methacrylic acid) that are dyeable by It can be obtained under normal spinning conditions using the copolymer contained therein.

On the other hand, basic dye dyeable acrylonitrile used in the present invention)
There are no particular restrictions on IJ-based synthetic fibers (acrylonitrile and other vinyl unsaturated compounds that can be copolymerized with acrylonitrile (e.g. acrylic esters, methacrylic esters, acrylamide and its derivatives, vinyl acetate). Acrylic single-component or composite fibers (bimetal type or sheath core type) obtained from acrylonitrile-based copolymers copolymerized with known materials such as vinyl butyrate, vinyl chloride, vinylidene chloride, vinyl bromide, etc.) are used. be done.

Such acrylic fiber materials are then subjected to dyeing in the presence of a specified dyeing aid (leveling agent). In addition, the following compound '111) or compound (2) in which the number of added moles of ethylene oxide was maintained within a predetermined range,
It is important to use each one alone or in combination in order to obtain a level dyed product.

(In the formula, R1 has 14 to 18 carbon atoms, and R2 has 12 to 1 carbon atoms.
6 saturated or unsaturated aliphatic hydrocarbon, n+m is 6 to
(represents an integer of 40) That is, the alkyl group R in the above compound (1) or group 2)
When dyeing is performed using a dye in which the number of carbon atoms in 1 and R2 is less than 14 or 12, it is undesirable because it tends to form a dye complex with the acid dye in the dye bath, and the dye bath is significantly contaminated.

On the other hand, when R1 and R2 have carbon numbers exceeding 18 or 16, the slow dyeing action of acid dyes on acid dye-dyeable acrylonitrile synthetic fibers is extremely reduced, resulting in a level dyed product. This is difficult and undesirable.

Furthermore, even if the number of carbon atoms in the alkyl group satisfies the specified range, if the number of added moles of ethylene oxide (n+m) is less than 6 moles, the dye complex is formed in the dyebath. If the number of moles exceeds 40 moles, it is not preferable because the slow dyeing effect of the dye is significantly reduced.

In addition, the amount of the dyeing aid having the specific structure used in the present invention added to the dye bath is 1% by weight of the strongly basic group-containing acid dye-dyeable acrylonitrile synthetic fiber used.
It is necessary to set the amount within the range of 0.002 to 0.05 parts to
This is undesirable because the dye exhaustion rate decreases and the dyeing time becomes unnecessarily long.

In the practice of the present invention, generally, the dyed object is heated from about 95°C to 120°C after being gradually heated from room temperature in a dye bath in which an ethylene oxide addition compound having the above-mentioned specific structure is present.
Although the dyeing operation is carried out in the temperature range of ℃, in a more preferred embodiment, the object of the present invention can be more effectively achieved by adjusting the H of the dye bath to 2 to 7. can.

Note that, if necessary, other dyeing aids may be added to the dye bath either singly or in combination.

According to the method of the present invention as described above, it is possible to significantly improve the slow dyeing property and migration property during dyeing compared to the dyeing method using a leveling agent that has been used up to now. Excellent level dyeing properties for acrylic fiber materials,
This enabled the industrialization of dyed products with color development and high commercial value.

The examples described below are for specifically explaining the present invention, and are not intended to limit the gist of the present invention or the like.

All parts and percentages shown in the examples are expressed on a weight basis unless otherwise specified.

Example 1 A fiber-forming copolymer obtained by copolymerizing 86% acrylonitrile, 11% vinyl acetate, and 3 parts dimethylaminoethyl methacrylate was dissolved in a 49% rhodan soda aqueous solution to prepare an acrylonitrile-based spinning stock solution. Thereafter, normal spinning conditions were adopted to obtain a single denier acid dye dyeable acrylonitrile synthetic fiber.

The sample fiber thus obtained was then subjected to a known spinning device to form a spun acrylic fiber yarn having a single yarn count of 48.

Thereafter, the spun yarn 500f was supplied to a package dyeing machine and dyed under the following conditions.

Dyeing recipe Dye: C, 1, Ac1dRed 0.01 parts per part) 18 (Spun yarn weight 1 (0.02 parts per 1 part spun yarn weight) Other auxiliaries: Acetic acid pH: 4.0 Temperature 3 minutes after heating from 0℃ to 98℃ Dyeing bath ratio: 1:3
The dyed yarn thus obtained was knitted into a jersey with a 20-gauge pontiloma structure to produce a final product.

The obtained dyed product exhibited excellent color tone without irritation or flicker and was rich in commercial value.

On the other hand, as Comparative Example (A), jersey was dyed with an acid dye using the same conditions as above except that only the leveling agent added to the dye bath was changed.

In addition, comparison f! The leveling agent used in KA) is a formalin condensate of aromatic sulfonic acid (commercial product name: Meditol WL).
; manufactured by Bayer AG, Germany), and the amount used was the same as in this example.

The jersey after dyeing was unevenly dyed with irritation, flickering, and color cracking, which significantly reduced the commercial value.

Furthermore, as a comparative example (B), when dyeing was attempted without adding any leveling agent to the dye bath, poor dyeing spots occurred in the final product, making it impossible to obtain a satisfactory level-dyed product. It was impossible.

※※ In order to understand the above-mentioned relationship more quantitatively, this example and comparative example (for 8 and 1,
The dyeing speed behavior and degree of dye transfer (a measure expressing the level dyeing effect) were measured.

The results are listed in Table 1. In addition, the value calculated by the following measuring method was adopted as the degree of dye migration.

That is, based on the dyeing operation adopted in the above example, the acid dye dyeable acrylonitrile synthetic fiber (
A dyed material I is obtained by dyeing the rose hair-like).

Thereafter, the dyed product (1) and the undyed acrylonitrile synthetic fiber (2) of the same constituent material were separated in equal amounts in the same bath (pH 4, 0, 10) without mixing.
0° C.), and then dyeing was attempted for 30 minutes based on the same dyeing operation as in the example (however, no dye was included).

After the transfer dyeing is completed, take out the dyed products (■ and ■) of the two types of dyed objects (■ and ■) as described above, and measure the spectral reflection density (K/S value) for each sample (using a Shimadzu spectrophotometer). type RC-330), and the degree of dye transfer was calculated based on the following formula.

Dye migration degree (%) = dyed product n (7) K/S value dyed product ■ / 5fifx100 Also, based on the same operation as above, the migration dyeing treatment was also attempted for Comparative Examples A and B. (The difference is that the type of leveling agent used during the dyeing process is different and that no leveling agent is added during the dyeing process.)

Note that the higher the degree of dye migration, the better the dye migration effect can be achieved.

As is clear from the results in Table 1, by dyeing using a leveling agent having a specific structural formula according to the present invention,
It is clearly understood that the moderate slow dyeing action of acid dyes and the migration properties of suitable dyes work synergistically in the dyeing process, thereby producing a satisfactory level dyed product.

Example 2 The same acrylonitrile synthetic fiber as in Example 1 was used to form a 36-count double-thread acrylic spun yarn, and the spun yarn 5002 was fed to a jet bulky dyeing machine and dyed using the following conditions. .

Dyeing recipe dye: C, 1, Ac1d Blue 126 (0.005 parts based on the weight of the spun yarn) Leveling agent: Listed in Table 2 (Additional amount: 0.005 parts per part of acrylonitrile synthetic fiber) Part 03) Other auxiliaries:
Acetic acid ※※pH2 4
．． 0 Temperature near 0℃ → 98℃ 30 minutes after temperature rise Dyeing bath ratio: 1:4
5. Each of the obtained dyed yarns was knitted into a jersey texture using a 12-gauge circular knitting machine to produce a final product.

Table 2 shows the results of visually evaluating the level dyeing properties of each dyed product.

Furthermore, Table 2 also shows the results of staining of the dye bath when each leveling agent was employed.

As is clear from Table 2, the desired effect can be advantageously exerted only when a compound is selected in which the number of carbon atoms in the alkyl group and the number of added moles of ethylene oxide (n+m) are maintained within a suitable range. It's obvious.

Example 3 A blended yarn (number 6 single yarn) was prepared by blending 30 parts of the same acid dye-dyeable acrylonitrile synthetic fiber as in Example 1 and 70 parts of ordinary basic dye-dyable acrylonitrile-based synthetic fiber.
was created.

The blended yarn was tufted onto a cotton base fabric having a basis weight of 250 fI/m to a pile length of 6 cm to produce a tufted blanket.

Thereafter, the tufted blanket was fed to a Wins dyeing machine and dyed under the following conditions.

Dyeing recipe dye: C, 1, Basic Blue 3 (per part of blanket weight (the amount added was varied as shown in Table 3) Other auxiliary agents: acetic acid, cationic slow dye, nonionic activator pH: 4.0 Temperature: normal temperature → 45 minutes after heating to 98°C Dyeing bath ratio: 1:40 The dyed product thus obtained was subjected to napping and tumble processing to produce a sheep blanket.

Table 3 shows the results of observing the level dyeing properties and coloring properties of each of the obtained sheep blankets.

From the results in Table 3, it is clear that by maintaining the amount of the leveling agent according to the present invention within a suitable range, a uniform color tone can be imparted to the final product.

Claims (1)

[Scope of Claims] 1. When dyeing an acrylic fiber material containing a strongly basic group-containing acid dye-dyeable acrylonitrile synthetic fiber with an acid dye without forming a dye complex, Compound (1) and/or shown below
Alternatively, a level dyeing method for an acrylic fiber material, characterized in that compound 1 is present in an amount of 0.002 to 0.05 part per 1 part of the acid dye-dyeable acrylonitrile synthetic fiber. (In the formula, R1 has 14 to 18 carbon atoms, and R2 has 12 to 1 carbon atoms.
6 saturated or unsaturated aliphatic hydrocarbon, n+m is 6 to
(represents an integer of 40). 2. The level dyeing method for acrylic fiber materials according to claim 1, wherein the pH of the dye bath is 2 to 7.