JPH064940B2 - Cationic dye continuous dyeing method for dyeable fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to a continuous dyeing method for cationic dyeable fibers. More specifically, the present invention provides a cationic dye-dyeable polyacrylonitrile-based synthetic fiber, a cationic dye-dyeable polyester-based synthesis, which contains an acidic end group capable of binding with a cationic dye such as a sulfonic acid group or a carboxylic acid group. 100% of each of fibers that can be dyed with a cationic dye (hereinafter simply referred to as a cationic dyeable fiber), a mixture thereof, or a cationic dyeable fiber, and a fiber that is generally not dyed with a cationic dye , For example, by dyeing a dyeing material consisting of a mixture of wool, cotton, and polyamide-based synthetic fiber in a cationic dye-containing pad dyeing solution, squeezing it, and then heat-treating, the cationic dyeable fiber is continuously dyed. It is about the method.

The present invention therefore uniformly dyes continuous dyeing objects such as tops, tows, spun yarns, false-twisted yarns, and knitted fabrics containing cationic dyeable fibers, especially thick knitted fabrics, large tows of total denier, etc. at high speed. It is about how to do it.

<Prior Art> Conventionally, a pad of a dyeing liquid for a cationic dyeable fiber is a cationic dye, an acid, a pH stabilizer, a sizing agent, and if necessary, a quick dyeing agent, a dye dissolving agent, a reduction inhibitor (oxidizing agent). It was dipped in a pad dye solution containing an antifoaming agent and squeezed with a mangle (Textile Science, August 1976 issue, page 39). In this method, in addition to the complicated processing method, by adding a sizing agent to the dyeing solution, an ending (tailing) caused by adsorption of the cationic dye from the dyeing solution to the fiber at low temperature (20 to 30 ° C.) is added. It imparts viscosity to the dyeing liquor, which controls the migration of the dye in the pad dyeing liquor to the fibers during padding and prevents ending.

However, since this method uses a viscous dyeing liquid, the dyeing liquid does not expel the air between tissues of the dyeing dye to the dyeing dye that moves at high speed in the dyeing dye. The dyeing liquid was not sufficiently impregnated with the dyeing liquid even when the mangle was squeezed without penetrating into the tissue gap, resulting in stain stains, which was insufficient.

On the other hand, in order to prevent ending, it is also effective to reduce the amount of dyeing solution in the pad bath. The dyeing solution is held in the gap between the two horizontal rolls, the material to be dyed is passed between them, and the roll is squeezed. A method was developed and IRGA Pad (IRGA-PA
D) Method, "Fiber" Vol. 17, No. 3, page 74 (1
965). According to this method, the distance that the article to be dyed is immersed in the pad dye solution is less than the radius of the roll, the amount of dye solution held between both rolls is small, and the amount of dye solution carried out by the article to be dyed is sequentially. This method is effective for preventing the ending because it can be replenished newly and therefore there is almost no change in the dye concentration of the dye liquor. However, in this method, a locust bean-based sizing agent or the like is added to the dye liquor to prevent the marbling defect, and the viscosity of the dye liquor is maintained at 40 to 50 CP. Like this way,
When the viscosity of the dyeing degree is as high as 40 to 50 CP, in this method, the length of immersion of the dyeing liquid to be dipped in the dyeing liquid is short and the dyeing liquid cannot be sufficiently penetrated into the dyeing liquid, so that partial dyeing is not performed. Spots occur.

<Problems to be Solved by the Invention> As described above, in the prior art, when the dyeing object is continuously and rapidly dyed with a pad, the end phenomenon is prevented and the dyeing solution is uniformly and quickly applied. There was no method of infiltrating into it to produce a spot-free dyeing.

The present invention is a thick knitted fabric made of cationic dyeable fiber, when continuously dyeing a dyeing object such as a large tow of total denier at a high speed with a pad, a drawback that causes an ending phenomenon that a conventional technique has, and a dyeing solution The present invention is intended to solve the drawback that the material to be dyed does not permeate quickly and uniformly.

<Means for Solving Problems> The above-mentioned drawback is that a quaternary ammonium salt is used, and a cationic surfactant commonly referred to as PAN type (hereinafter referred to as PAN type cationic surfactant) is 2.0 × 10. -10 mol of cation dyeable fiber in 100 cc of a cationic dye-containing dye liquor adjusted to pH 3.5 and a temperature of 30 ° C. with ^-3 mol / acetic acid.
The concentration change in the dye liquor before and after the immersion in the dye liquor contained in 95 cc of the residual liquid when squeezing so that the water content of the cationic dyeable fiber becomes 50% after dipping the gr for 60 seconds is ± 1.
A cationic dye having a content of 5% or less (hereinafter referred to as a selected cationic dye) and 0.5% of a PAN type cationic surfactant are used.
× 10 ⁻³ mol / mol or more, pH 2 to 5.5, temperature 0
This is solved by a continuous dyeing method which comprises immersing a material to be dyed containing a cationic dyeable fiber in a pad dyeing solution adjusted to 50 ° C to 50 ° C and a viscosity of 0.5 to 3 CST, squeezing the solution, and then heat-treating it.

As the PAN type cationic surfactant, those represented by the following general formula are preferable.

In the above formula, R is a C ₁₀ -C ₁₈ alkyl group, or C ₁₀
To C ₁₈ alkyl group and a group containing a benzene ring, a naphthalene ring, an ether bond, an ester bond or an acid amide bond, R ₁ and R ₂ each represent a methyl group or an ethyl group, and R ₃ represents a methyl group or an ethyl group. Represents a group or a benzyl group.

Hereinafter, the configuration of the present invention will be described in detail.

The PAN-type cationic surfactant represented by the above general formula is
It is necessary that the dye liquor contains 0.5 × 10 ⁻³ mol / mol or more. When the amount is less than 0.5 × 10 ⁻³ mol / mol, the cationic dye is adsorbed by the cationic dyeable fiber from the dyeing solution, and the dye concentration is lowered to cause the ending.
When it is 0.5 × 10 ⁻³ mol / or more, the adsorption of the dye to the cationic dyeable fiber is remarkably suppressed, and it is preferably 2.0 × 10 ⁻³ mol / or more. It is immutable. However, it is 10 × 10 ⁻³ mol / or less because of the foaming property of the surfactant, the economical efficiency, and the reason that it becomes difficult to obtain a deep color by depriving the cationic dye dyeing seat of the cationic dyeable fiber. Is preferred.

The adsorption phenomenon becomes more severe as the temperature of the dyeing liquid rises.
Above ℃, it becomes difficult to prevent ending. The dyeing liquid temperature is preferably 40 ° C. or lower. When the temperature is 0 ° C or lower, the pad of the dyeing liquid cannot be formed due to freezing, and 15 ° C or higher is preferable from the viewpoint of dye solubility.

The pH of the dye liquor is preferably pH 2 or more, preferably 3 or more and 5.5 or less in view of the durability of the rubber roller for the printing liquid used in the pad method. When the pH is 5.5 or more, the cationic dye is easily decomposed in the heat treatment which is a step of absorbing and fixing the cationic dye to the cationic dyeable fiber after the pad squeezing liquid, which is not preferable.

The viscosity of the dye liquor is preferably as low as possible in order to improve the penetration of the dye liquor into the cationic dyeable fiber.
At ST or higher, when the speed of the material to be dyed is high, the permeation of the dyeing solution between the fibers of the cationic dyeable fiber is poor, causing partial dyeing spots. However, in the present invention, the viscosity of the dye liquor is
As a matter of course, the viscosity of water at 50 ° C. is 0.55 CST or more.

In the present invention, the selected cationic dye contains a PAN type cationic surfactant in an amount of 2 × 10 ⁻³ mol / pH,
5.5, a cationic dye-containing pad dye solution adjusted to a temperature of 0 ° C. to 50 ° C. is a dye in which the cationic dye is not substantially selectively adsorbed on or removed from the cationic dyeable fiber, and the measuring method is As described above. Incidentally, the dye concentration at the time of measurement is preferably two concentrations of 0.03 gr / and 0.3 gr / for any cationic dye. This is because the adsorption behavior on the cation dyeable fiber differs depending on the dye concentration of each cationic dye, and a dye concentration of 0.03 g / corresponds to the case of ultra-light color.

In the present invention, a PAN type cationic surfactant is used in order to suppress the adsorption of the cationic dye to the cationic dyeable fiber at a low temperature. In the above measurement, the cationic dyeable fiber is immersed in the pad dye solution. By
The concentration of the cationic dye in the dye liquor may increase. The reason for this is not clear, but it is presumed that the PAN-type cationic surfactant selectively eliminates the dye, thereby increasing the concentration in the dye liquor.

When a cationic dye not selected in the above measurement method, that is, a cationic dye having a cationic dye concentration change of more than ± 1.5% is used, it is easy to cause an ending phenomenon due to a change in pad dyeing liquid concentration, It is difficult to control the dye concentration. Within ± 1.5%, a stable dye liquor concentration can be maintained only by continuously adding the same dye liquor amount of the same concentration brought out by the material to be dyed, and the ending phenomenon does not occur. These specific results are also described in the examples.

In the present invention, as the cationic dye, those satisfying the above conditions are selected and used.Specific dyes include, for example, Color Index Basic (hereinafter, C.
Abbreviated as I.Ba.) yellow (hereinafter abbreviated as Y.) 2
3, 36, 40, 45, red (hereinafter abbreviated as R.)
14, 27, 29, 46, blue (hereinafter abbreviated as B.) 1, 54, 67, 141, C.I. 1. Fluorescent Br
ightener 257 (hereinafter abbreviated as CIF B.257)) and the like.

The method for padding the dyeing solution to the article to be dyed according to the formulation of the present invention may be a conventional padding method such as 1 dip, 1 nip or 2 dip, 2 nip, etc. In the case of tows, tops, etc., it is possible to use the conventional method of uniformly spreading. The water content after squeezing with the mangle is 100% or less, preferably 75% or less so that the dyeing liquid does not drip off, and 40% or more so that the dyed product is not damaged by excessive squeezing liquid. preferable.

The article to be dyed, which is continuously dipped in the dyeing solution and squeezed, is then heat-treated. The heat treatment method is roughly classified into a dry heat method and a wet heat method. In the case of cationic dyeable fibers, generally, moist heat is used, and usually 100 to 110 is 2
It is processed for 10 minutes. In the present invention, the padding method, the water content, and the heat treatment method themselves are the same as those conventionally used. It should be noted that adding an appropriate defoaming agent to the pad dye solution is effective in suppressing foaming by the cationic surfactant, and for this purpose, silicone-based, modified silicone-based emulsion, various nonionic surfactants are used. Agents can be used.

<Examples> Hereinafter, the present invention will be further described with reference to Examples.

Reference Example 1 This example shows a method for measuring whether or not various cationic dyes are adsorbed on cationic dyeable fibers.

0.03 gr / or 0.3 gr / of various cationic dyes
, Trimethylcetylammonium chloride (compound represented by the above general formula) 2 × 10 ⁻³ mol / as a PAN-type cationic surfactant, pH was adjusted to 3.5 with acetic acid, and dye solution (A) 100 cc at a temperature of 30 ° C. 10 gr of acrylonitrile-based synthetic fiber (manufactured from a copolymer of 93.5% by weight of acrylonitrile, 6% by weight of methyl acrylate, and 0.5% by weight of sodium allylsulfonate) capable of being dyed with a cationic dye was immersed therein for 60 seconds, and then, The fibers were squeezed to obtain 95 cc of residual dyeing liquid (B). The dye concentration in this residual dyeing product was measured. The results are shown in Table 1.

Example 1 Each dye of Reference Example 1 and trimethyl cetyl ammonium chloride 3 × 1 as a PAN-type cationic surfactant
0 ^-3 mol /, silicone anti-foaming agent (ANTIFLOSS S
110: Daiichi Kogyo Seiyaku Co., Ltd. (trade name) 0.1 gr / was prepared, and the pH was adjusted to 3.5 with acetic acid to prepare a dye liquor having a temperature of 20 ° C. and a viscosity of 1 CST.

The acrylonitrile-based synthetic fiber tow (single yarn 3 denier, total denier 900,000 denier) used in Reference Example 1 was spread in these dye liquors to a width of 20 cm and passed at a speed of 75 m / min to obtain a water content of 50% wf. And processed continuously. During the processing of the tow, the dye liquor brought out by the tow was added in sequence. The dye concentration in the dye liquor did not change before and after the tow treatment. Then, the tow impregnated with the dye liquor is heated to 105 ° C.
Steam for 15 minutes and then dried.

As a result of observing the dyed tows thus obtained, as shown in Table 2 below, for the dyes of Experiment Nos. 1 to 13, all the tows were dyed uniformly,
Dye spots were observed for the dyes of o.14 to 15.

Example 2 CIBa.B. 6710.0 gr /, trimethylcetyl ammonium chloride was used as a PAN-type cationic surfactant, and 0.1 gr / of a silicone type defoaming agent (the one used in Example 1) was added, and acetic acid was added. A dye liquor adjusted to pH 3.5 with a temperature of 20 ° C. and a viscosity of 1 CST was prepared.

To this dye liquor, a fiber tow (single yarn 2. was used) consisting of a copolymer of 95% by weight of acrylonitrile, 4.4% by weight of methyl acrylate and 0.6% by weight of sodium methallylsulfonate.
5 denier, total denier 900,000 denier) is spread to a width of 20 cm and continuously dipped at a speed of 70 m / min to obtain a moisture content of 5
It was processed by squeezing it to 0%. The dyeing process was carried out while continuously adding the amount of dyeing liquid brought out by the tow. The resulting dye liquor containing tow was then treated in steam at 108 ° C. for 10 minutes and then dried.

The dyed spots of the obtained dyed tow were observed. The result is the third
Shown in the table.

Example 3 0.03 gr / and 0.3 gr / of CIBa.B.67, CIBa.Y.45, and CIBa.R.29, respectively, and trimethylcetylammonium chloride 2.0 × 10 ⁻³ as a PAN-type cationic surfactant. Mol / mol, pH 3.
It was confirmed that when the pad dye solution adjusted to 5 and having a temperature of 30 ° C. was used, the cationic dye did not substantially adsorb the cationic dye. That is, a pad dye solution of the following method was prepared using the above-mentioned selected cationic dye.

CIBa.B.67 0.60gr / CIBa.Y.45 1.40gr / CIBa.R.29 0.10gr / Trimethylcetyl ammonium chloride 3.0 × 1
0 ^-3 gr / silicone anti-foaming agent (ANTIFLOSS S110; manufactured by Daiichi Kogyo Seiyaku Co., trade name) 0.1gr / pH3 with acetic acid.
5, temperature 20 ℃, viscosity 1.0 CST.

The above-mentioned pad dyeing solution was dipped in a length of 2.0 m, a capacity of 80, 2 dips, and a nip pad tank with 3.0 d of cationic dyeable fibers (polyacrylonitrile-based synthetic fibers) in total 90
Spread 10,000 denier tow evenly in width of 20 cm, high speed 70 m
The solution was passed at a flow rate of 5 minutes / minute and squeezed so that the water content was 50%. Pad dye liquor brought out by the tow was added in sequence to treat 80 kg of tow. The initial dye concentration and the final dye concentration of the pad dye liquor did not change. After padding, perform steam treatment at 105 ℃,
When the tow was observed after drying, it was dyed in a uniform greenish gray color.

Comparative Example 1. As a result of the same treatment as in Example 1 except that the PAN-type cationic surfactant was not contained at all, after 10 minutes (about 12.9 kg of the cationic dyeable fiber), the dye concentration of the pad dyeing liquid as a whole was The color decreased to 90%, the initial tow was dark, and after 10 minutes, it was lightly stained.

Comparative Example 2 Same as Example 1 except that each of PAN-type cationic surfactants such as trimethylcetyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride or methyl dodecyl benzyl trimethyl ammonium chloride was contained in an amount of 0.4 × 10 ⁻³ mol / each. Processed. Although the result is a good result as compared with Comparative Example 1, the ending was not completely prevented.

Comparative Example 3. C. I. BA. B. 67 in place of the cationic dye C.I. I. Ba. B. The same treatment as in Example 1 was performed except that No. 45 was used. as a result,
Only the blue dye was selectively adsorbed, and it was strongly bluish at the initial stage, and after 10 minutes, it was dyed in a gray color having a less bluish tone.

Comparative Example 4 C.I. which is a selected cationic dye. I. Ba. B. 67 to 1.
0 gr / and unselected cationic dye C.I. I. B
a. R. The same treatment as in Example 1 was carried out except that 54 was used at 1.0 gr. As a result, C.I. I. Ba. R. 54 was selectively eliminated, showing an ending that changed from an initial purple color to a reddish purple color after 10 minutes.

Example 4 Selected cationic dye C.I. I. Ba. B. 5460gr /,
Stearyl trimethyl ammonium chloride 0.6 ×
A pad was prepared in the same manner as in Example 1 except that a pad dye solution containing 10 ^-3 mol / pH adjusted to pH 2.5 with formic acid and having a temperature of 35 ° C. and a viscosity of 0.8 CST was squeezed to a water content of 70%. Then, steam treatment was performed at 110 ° C. for 10 minutes, followed by washing with water and drying. When the obtained tow was observed, it had a deep blue color, with no ending phenomenon or partial spots being observed.

Example 5 and Comparative Example 5 Example 2 except that 4.0 gr / (Example 5) and 7.0 gr / (Comparative Example 5) of Maypro gum (locust bean gum manufactured by Mayhole Chemical Co., Ltd.) was added as a sizing agent. The same process was carried out. The viscosity of Example 5 is 2.2 CS
The viscosity of T and Comparative Example 5 was 6.0 CST. The results were as good as in Example 2 in Example 5, but in Comparative Example 5, pale bluish spots having a diameter of about 3 cm were observed inside the tow at a rate of about 3 per 1 m of tow.

Example 6 CIBa.Y.873 containing the following three types of selected cationic dyes
gr /, CIBa.R. 1093 gr /, C.I. I. Ba. B. 693 gr / and octadecyldimethylethylammonium chloride 1.5 × 10 ⁻³
The treatment was performed in the same manner as in Example 1 with a dye liquor containing mol / mol and adjusted to pH 3.2 with acetic acid and having a temperature of 40 ° C. and a viscosity of 0.66 CST. As a result, good results were obtained as in Example 1.

According to the present invention, as described in Examples 1 to 6 and Comparative Example 5, when the viscosity is 3.0 CST or less, the penetration of the dye liquor into the material to be dyed is good, and the high speed which cannot be achieved by the prior art is achieved. Below, a large tow of total denier could be dyed uniformly. As shown in Comparative Example 5, the conventional viscosity (40 to 50 C.
P., specific gravity of 1.0, even at 6.0 CST of 40 to 50 C.S.T) or less, at a speed of 70 m / min, insufficient results were obtained.

On the other hand, when the PAN-type cationic surfactant is not included as shown in Comparative Example 1 and when the amount of the PAN-type cationic surfactant is not sufficient as shown in Comparative Example 2, ending is caused, and as shown in Comparative Examples 3 and 4, When using dyes not selected according to the invention, insufficient results are obtained, in other words PA
Satisfactory results have been obtained with N-type cationic surfactants and with selected dyes.

<Effect of the Invention> In the method of the present invention, since the sizing agent is not contained in the dye liquor as in the prior art, the pad dye liquor has a low viscosity,
This facilitates the permeation of the pad dyeing solution into the material to be dyed, and the material to be dyed can be uniformly and quickly impregnated with the dyeing liquid, so that partial dye unevenness is prevented. On the other hand, as the viscosity of the pad stain decreases, the adsorption of the cationic dye from the pad dye solution to the cationic dyeable fiber increases, but in order to suppress this adsorption, the PAN-type cationic surfactant and the above-mentioned cationic dye selection method. The cationic dye selected by

By using this PAN-type cationic surfactant and a specially selected cationic dye, the cationic dye in the pad dyeing liquid or the selected cationic dye in the pad dyeing liquid can be selectively dyed into a selective dyeing object in the pad dyeing liquid. Adsorption does not occur. Therefore, the ending does not occur because the concentration of the dye in the pad dye liquor does not change.

Also, to prevent ending, it is not necessary to make the pad dyeing tank small, and it is possible to use a sufficient dipping length, and in combination with the decrease in the viscosity of the dyeing liquid, it is easy for the pad dyeing liquid to permeate into the article to be dyed sufficiently uniformly. Can be

Claims (1)

[Claims] 1. A PAN-type cationic surfactant is added in an amount of 2 × 10.
After immersing 10 gr of the cationic dye dyeable fiber in 100 cc of the cationic dye-containing dye liquor adjusted to pH 3.5 and temperature of 30 ° C. with ^-3 mol / acetic acid for 60 seconds, the water content of the cationic dye dyeable fiber is 50. A PAN-type cationic surfactant and a cationic dye whose concentration change in the dye liquor before and after immersion of the dye contained in 95 cc of the residual liquid when squeezed so as to be 0.5 x 10
^-3 mol / mol or more, pH 2 to 5.5, temperature 0 ° C to 5
A continuous dyeing method comprising immersing an article to be dyed containing a cationic dyeable fiber in a pad dyeing solution adjusted to 0 ° C. and a viscosity of 0.5 to 3 CST, squeezing the solution, and then heat-treating it.