JPH0822977B2 - Dye for undiluted solution of acrylic synthetic fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a colorant that can be preferably used in uncoloring an acrylic synthetic fiber with an undiluted solution.

<Prior Art> A conventional spinning dope is a method for spinning colored fibers by dissolving a synthetic resin, which is a raw material of the fiber, in a solvent to prepare a spinning dope, and then adding a coloring pigment or dye to the spinning dope and spinning it. A wet spinning method in which a liquid is passed through a metering pump and a spinning nozzle and then coagulated in a coagulation bath is widely used.

In addition, to enable efficient color switching using a single spinning machine, prepare a colorant stock solution in which a dye is dissolved in a solvent of synthetic resin, and use this colorant stock solution with a spinning metering pump and a spinning nozzle. A spinning method has also been proposed in which the spinning dope is colored by injecting and mixing it in the spinning dope (JP-A-56-12).
No. 8308).

Acrylic fibers are a representative of the above-mentioned undiluted solution coloring fibers, and in this case, as the coloring agent for undiluted solution coloring, cationic dyes having excellent coloring properties and light resistance to acrylic fibers are generally used. .

 This cationic dye is an amine salt or quaternary ammonium
It is a water-soluble dye with a group, and dye ion and ion pair in the molecule.
Cl to form Etc. and is also a zinc chloride double salt
Some are.

<Problems to be Solved by the Invention> However, when the undiluted solution-colored spinning of acrylic fiber is performed using the cationic dye as described above, a phenomenon in which white crystals are precipitated in the spinning nozzle of the spinning machine is observed. If such crystals are deposited, the spinning nozzle will be clogged and the spinning stock solution transfer system will be pressurized. Therefore, the spinning machine must be stopped and the nozzle replaced every half day to one day. Will reduce the rate.

 When the cause of crystal precipitation as described above was investigated,
In addition to the inorganic salts contained in Pairs of etc.
Ion-forming fiber-forming polymer has -SO₃ Na When
Ion exchange reaction forms an inorganic salt such as NaCl.
It was found to precipitate in the spinning dope.

In order to prevent the precipitation of such an inorganic salt, it is necessary to remove the inorganic salt from the cationic dye. As a means for removing the inorganic salt, a method in which a cationic dye is made into a base and then washed with water is conceivable. However, with respect to a cationic dye which cannot be made as a base, the removal of the inorganic salt becomes extremely difficult.

A method has already been proposed in which even a cationic dye which cannot be made into a base is laked with a sulfuric acid ester of a higher aliphatic alcohol to make it water-insoluble and then washed with water to remove inorganic salts (JP-A-62-104874). However, the laked product of the cationic dye and the higher aliphatic alcohol sulfate ester is extremely fluid at room temperature, and there is a problem in that it is industrially very difficult to separate it from the aqueous layer after washing with hot water. Further, this lake compound has a property of being easily dispersed in water, and if it is vigorously stirred with hot water to remove an inorganic salt, the lake compound is finely dispersed and the lake does not settle, resulting in a markedly poor yield.

Therefore, according to the present invention, the laked dye has a high viscosity, and
It was made for the purpose of providing a lake dye that does not disperse in an aqueous layer.

<Means for Solving Problems> The present inventors have used as a laker, an alkylnaphthalene sulfonate, a dialkyl sulfosuccinate, or
By using an alkyl diphenyl ether disulfonate, the laked product has a high viscosity and can be easily separated from water, and since it does not disperse in water, the laked cationic dye can be obtained without lowering the yield. Obtained and
The present invention has been completed by finding that the lake dye is also soluble in acetic acid, which is a solvent for the dye, and acetone, which is a solvent used for spinning modacrylic fiber.

That is, the present invention is a dye for undiluted solution of synthetic fiber, which comprises a laked cationic dye represented by the following general formula (I), (II) or (III).

 In the above formula, D Is a cationic dye residue, R is the number of carbon atoms
It represents each of 8 to 18 aliphatic alkyl groups.

 The original cationic dye is a cationic dye residue D To this
Cl forms an ion pair with Etc. are combined, but this
The light dye can also be found from the above formulas (I), (II) and (III).
As, alkyl naphthalene sulfonate, dialkyl
Sulfosuccinate or alkyl diphenyl ether
By laking with ludisulfonate,
Thione dye residue D IsOrAnd is in the form of forming an ion pair.

In the present invention, it is necessary to use a surfactant such as alkylnaphthalenesulfonic acid, dialkylsulfosuccinate or alkyldiphenyl ether disulfonate as a lake dyeing agent for the cationic dye. This gives a laked dye which is soluble in acetic acid and acetone. Other surfactants, such as
Formalin condensate of naphthalene sulfonate, or
The N-methyl-N-undecyltaurine laked dye is insoluble in acetone and the dodecylbenzene sulfonate or dialkyl phosphonate salt does not completely precipitate the dye and cannot be separated from the aqueous layer and It was

As the laking agent that can be preferably used in the present invention,
Examples thereof include octylnaphthalene sulfonate, decylnaphthalene sulfonate, dodecylnaphthalene sulfonate, dioctyl sulfosuccinate, or dodecyl diphenyl ether disulfonate.

The dye which is laked by the above-mentioned lake agent may be any cationic dye, for example, di- and triallylmethane dyes, pyronin dyes, rhodamine dyes, acridine dyes, safranine dyes, oxazine dyes, quinoline dyes, Examples thereof include thiazole dyes, basic azo dyes, azomethine dyes and polymethine or azopolymethine dyes, basic anthraquinone dyes, quinophthalone dyes and phthalocyanine dyes.

In the production of the lake dye of the present invention, a cationic dye is dissolved in water or hot water to prepare an aqueous dye solution, and the aqueous lake solution is slowly added to the aqueous dye solution while stirring to precipitate the solution. Add until no longer generated. After leaving this solution overnight, decanting the supernatant liquid is repeated to remove inorganic salts such as NaCl, and then glacial acetic acid is added to the obtained tar-like substance, rice cake-like substance, or crystals. The laked dye of the present invention can be obtained by dissolving it and then diluting it with water if desired.

In general, the amount of the laking agent used is preferably about 70 to 100% of the theoretical amount (the amount of one sulfonic acid group in the laketing agent per one cationic group in the dye). If an excessive amount is used, the lake compound will start to dissolve, and the yield tends to decrease.

As the solvent for the lake dye, there are many kinds of solvents such as alcohols or polyacrylonitrile other than acetic acid and acetone, such as dimethylformamide, ethylene carbonate and dimethyl sulfoxide.

The laked dye of the present invention thus obtained can be preferably used as a coloring dye for a spinning dope in a spinning dope coloring process for acrylic fibers, like the conventional cationic dyes. As acrylic fiber that can be dyed,
In addition to polymers of acrylonitrile, acrylonitrile and vinyl chloride, vinyl fluoride, vinylidene chloride,
Examples thereof include vinyl acetate or vinyl propionate, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl alcohol, copolymers with vinyl compounds such as acryl- or methacrylic acid ester or acrylamide.

When the dyeability and fastness of the colored acrylic fiber dyed with the lake dye of the present invention were examined, both showed the same degree as in the case of using the conventional cationic dye, and the adverse effect of the lake agent was recognized. It turns out not.

<Example> The present invention will be further described with reference to the following examples.

<Production of lake dye> Example 1 The following structural formula The concentration is 39.4% with respect to the malachite green oxalate, which is the oxalate salt of this dye (the dye concentration is that the dye is dissolved in a mixed solvent of 450 parts by weight of acetone, 547 parts by weight of water, and 3 parts by weight of acetic acid). Shimadzu Digital Autograph Spectrophotometer UV-220) was used to dissolve 50 g of the dye solution in 200 ml of hot water at 70 ° C. A solution prepared by dissolving 22.6 g of sodium dodecylnaphthalenesulfonate as a laker in 130 ml of hot water at 70 ° C was gradually added to this solution while stirring at 70 ° C. After stirring for 1 hour, the mixture was left standing and cooled to room temperature. The supernatant was decanted and removed. 200m of boiling water at 70 ℃ on the settled rice cake
l was added, stirred for 1 hour, allowed to stand and cooled to room temperature, and the supernatant was again decanted and removed. 200 ml of hot water at 70 ° C. was added again to the settled dough-like substance, and the mixture was stirred for 1 hour, allowed to stand and cooled to room temperature, and the supernatant was decanted and removed. 40 g of glacial acetic acid was added to and dissolved in the thus obtained washed rice cake, and the following structural formula was used. 71.6 g of the laked green dye of the present invention represented by The laked dye had a concentration of 27.0% with respect to malachite green oxalate.

Example 2 Using a solution prepared by dissolving 25.3 g of sodium dioctylsulfosuccinate in 130 ml of boiling water at 70 ° C. as a laking agent, the same operation as in Example 1 was carried out, and the following structural formula was used. 72.0 g of a laked green dye represented by This lake dye has a concentration of 2 with respect to malachite green oxalate.
It was 6.9%.

Example 3 As a laking agent, a solution prepared by dissolving 15.4 g of sodium dodecyl diphenyl ether disulfonate in 130 ml of hot water at 70 ° C. was used and operated in the same manner as in Example 1 to obtain the following structural formula. 71.8 g of a laked green dye represented by This lake dye has a concentration of 2 with respect to malachite green oxalate.
It was 7.2%.

Comparative Example 1 16.4 g of sodium lauryl sulfate was used as a laking agent.
Using the solution dissolved in 130 ml of hot water at 0 ° C., the same operation as in Example 1 was carried out, and the following structural formula There was obtained 70.4 g of the laked green dye represented by JP-A-62-104874. The laked dye had a concentration of 26.0% with respect to malachite green oxalate.

Next, the state of the laked dye when separated from the aqueous layer, the dispersed state of the laked state in the separated liquid after washing with water, and the yield with respect to the dye used are shown.

When the laker of the present invention is used, the laked dye is dough-like at room temperature and does not flow out even when the beaker is tilted during decanting. However, in the case of sodium lauryl sulfate of Comparative Example 1, the laked dye was fluid, and when the beaker was tilted, it flowed out together with water, so that it was extremely difficult to separate water.

When the laker of the present invention is used, the dye does not finely disperse even if it is washed with hot water, and all settle if left stationary. However, in the case of sodium lauryl sulfate, a part of the lake dye was in a finely dispersed state, and did not completely settle even after standing overnight. Therefore, there is a drawback that the yield decreases when washing with water is repeated, and as shown in the table, the yield is lower than that of the lake dye of the present invention.

Example 4 The following structural formula Is represented by 70 g of 100 g of dye diluted with dextrin.
It was dissolved in 1500 ml of boiling water at ℃. The maximum absorption wavelength of this dye is
It was 526 nm and had an absorbance of 0.84 (measurement condition: a dye was dissolved in a mixed solvent of 450 parts by weight of acetone, 547 parts by weight of water, and 3 parts by weight of acetic acid to make a 0.002% solution, and Shimadzu Digital Autograph Spectrophotometer UV It was measured at -220.

As a lake agent, a solution of 30.4 g of sodium dodecylnaphthalene sulfonate dissolved in 200 ml of boiling water at 70 ° C was added to 70 ° C.
The dye solution was gradually added while stirring. The mixture was allowed to stand and cooled to room temperature. The supernatant was decanted and removed. Hot water 1 at 70 ° C. was added to the settled rice cake, and the mixture was stirred for 1 hour, allowed to stand, and cooled to room temperature. The supernatant was decanted and removed. 50 g of glacial acetic acid was added to and dissolved in the thus obtained washed rice cake, and the following structural formula was used. 11.6 g of the laked red dye of the present invention represented by This laked dye had a concentration of 85.3% with respect to the dye used as a raw material (the concentration of the dye was measured by the method described above). Yield to original dye is 9
It was 8.9%.

Example 5 As a laking agent, a solution prepared by dissolving 33.9 g of sodium dioctylsulfosuccinate in 200 ml of boiling water at 70 ° C. was used,
Operating in the same manner as in Example 4, the following structural formula 121 g of laked red dye having This laked dye had a concentration of 81.8% with respect to the dye used as a raw material. The yield based on the original dye was 99.0%.

Example 6 As a laking agent, a solution prepared by dissolving 20.7 g of sodium dodecyldiphenyl ether disulfonate in 200 ml of hot water at 70 ° C. was used, and the same operation as in Example 4 was conducted. 114 g of a laked red dye represented by This laked dye had a concentration of 87.0% with respect to the dye used as a raw material. The yield based on the original dye was 99.2%.

<Spinning of Colored Acrylic Fiber> A copolymer of 48% acrylonitrile and 52% vinyl chloride was dissolved in acetone to prepare a spinning dope having a copolymer concentration of 25%. On the other hand, the laked red dye obtained in Example 4 was dissolved in acetone to prepare a dye stock solution having a dye concentration of 5.0% (the dye of Example 4 was 5.86%). The spinning stock solution is quantitatively sent at 200 ml / min by a spinning metering pump, separately from this, the dye stock solution is quantitatively sent at 20 ml / min by a gear pump, and is mixed by a mixer installed immediately before the spinning nozzle holder. After uniformly mixing the spinning solution and the dye solution, the pore size should be 0.
It was passed through a spinning nozzle having a diameter of 08 mm and a hole number of 6000 H, and this was coagulated in an acetone / water coagulation bath. Next, drying, drawing and heat treatment were performed so that the final single yarn fineness was 3 denier, and a colored filament having a total denier of 18,000 denier was obtained.

Even after the spinning machine was continuously operated for 48 hours by the above operation, no crystal precipitation was observed in the spinning nozzle, and the nozzle was not clogged.

The laked dyes of Examples 5 and 6 were used for the same operation, but after the spinning machine was continuously operated for 48 hours in the same manner, no crystal precipitation was observed in the spinning nozzle and the nozzle was not clogged.

 However, it contains an inorganic salt and the counter ion is Cl. And
When using non-laked ordinary red dye
In 10 hours, the crystals of the inorganic salt precipitate on the spinning nozzle,
It became impossible to continue.

When the fastness of the obtained colored fiber was tested, it was similar to the fastness of the dye before lake as shown in the following table, and the use of the lake dye did not adversely affect the fastness.

Examples of the laked dye of the present invention produced in the same manner as in Example 1 above are shown by the structural formulas in Examples 7 to 21 below.

Example 7 Laked yellow dye Example 8 Laked yellow dye Example 9 Laked red dye Example 10 Laked yellow dye Example 11 Laked blue dye Example 12 Laked yellow dye Example 13 Laked red dye Example 14 Laked yellow dye Example 15 Laked blue dye Example 16 Laked yellow dye Example 17 Laked red dye Example 18 Laked yellow dye Example 19 Laked blue dye Example 20 Laked yellow dye Example 21 Laked yellow dye <Effects of the Invention> As can be seen from the above description, the laked dye of the present invention is extremely easy to separate the aqueous layer, and does not have the property of dispersing in water, so that it can be produced in high yield. . Then, when undiluted colored spinning of acrylic synthetic fibers is performed using the laked dye of the present invention, clogging of the spinning nozzle due to crystal precipitation of inorganic salts such as that observed when using a conventional cationic dye is performed. As a result, the operating rate of the spinning machine can be significantly improved.

Claims (1)

[Claims] 1. The following general formula (I), (II), or (II
I) (However, D Is a cationic dye residue, R is the number of carbon atoms
Each of 8 to 18 aliphatic alkyl groups is shown. )
Dye for stock solution coloring of acrylic synthetic fibers.