JP2004091963A - Cellulosic fiber dyeable with a cationic dye and its woven or knitted fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain cellulosic fiber dyeable with a a cationic dye which develops dyeing having resistance to wet-heat treatment even in a processing process adopting the wet-heat treatment. <P>SOLUTION: The cellulosic fiber dyeable with the cationic dye contains 1-30 wt.% of a sulfonate group-containing surfactant which has <10% eluted amount from the fiber based on the amount of the surfactant added in a wet-heat treatment at 120-135°C for 30 minutes. <P>COPYRIGHT: (C)2004,JPO

Description

【００４８】
【発明の効果】
本発明によれば、湿熱処理に耐性のある染色発現を達成する、すなわち湿熱処理を採用する加工工程を行っても実用上満足できるカチオン染料染色特性および染色濃度を有するカチオン染料可染性セルロース系繊維及びその織編物が得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a cellulosic fiber having dyeability of a cationic dye and a woven or knitted fabric thereof.
[0002]
[Prior art]
In recent years, in the field of textile fibers for clothing, various modifications and improvements have been made to various natural and chemical fibers due to diversification of consumer needs and the trend toward higher grades.
[0003]
Conventionally, the dyeing characteristics of cellulosic fibers are difficult to modify and improve because natural cellulose is used as a raw material, and it has been attempted to introduce ionic reactive groups into cellulose. There was a problem with the mechanical properties.
[0004]
For this reason, a compound that binds to an ionic dye as an auxiliary is added to the dyeing bath to form a complex, and then fixed to the fiber, which is a dyeing technique by a so-called complex dyeing method. Several techniques have been disclosed, such as a technique for imparting anionic or cationic dye dyeability by adding a compound that binds to an ionic dye. In particular, cellulose acetate fibers are widely used in the field of women's clothing because of their excellent color development, silky glossiness and dryness that are not found in synthetic fibers such as polyester fibers and polyamide fibers, and are widely used in the field of women's clothing. Quality and improvements have been made.
[0005]
As a technique for dyeing acetate fibers, a method in which a dyeing agent is added to the latter fiber material dope is preferable, and as an additive which becomes dyeable to a cationic dye, JP-B-46-41473 discloses the method. Are surfactants derived from sulfur-containing acidic groups typified by sodium dihexyl sulfosuccinate, and JP-A-2000-45123 discloses dibasic fatty acid esters containing metal sulfonate groups.
[0006]
In recent years, the use of cellulosic fibers mixed with versatile polyester fibers for clothing has been increasing. Polyester fibers require a wet heat treatment at 100 ° C. to 130 ° C., but conventional dyeing agents for cellulosic fibers are easily eluted from the fibers by the wet heat treatment, and are obtained with different dyeing densities between fiber bundles. Practically satisfactory dyeing characteristics, such as greatly impairing the quality of the woven or knitted product, have not been obtained.
[0007]
In particular, in a mixed fiber material of cellulosic fiber and cationic dye-dyeable polyester, the dyeing rate of the cellulosic fiber is reduced due to elution of the dyeing agent, and most of the dye is dyed into cationic dye-dyeable polyester fiber. For this reason, the dyeable polyester fiber dyeable with a cationic dye is dyed in a very dark color, and one of the cellulosic fibers is dyed only in a very light color.
[0008]
[Problems to be solved by the invention]
The present invention solves the conventional problems and achieves dyeing development resistant to wet heat treatment, that is, has a cationic dye dyeing property and dye concentration that are practically satisfactory even when a processing step employing wet heat treatment is performed. An object of the present invention is to provide a cationic dyeable cellulosic fiber and a woven or knitted fabric thereof.
[0009]
[Means for Solving the Problems]
A first gist of the present invention is characterized in that, in a wet heat treatment at 120 to 135 ° C., 1 to 30 wt% of a sulfonate group-containing surfactant whose elution amount from a fiber is less than 10% of the added amount is contained. In the cellulosic fiber dyeable with a cationic dye.
[0010]
A second aspect of the present invention resides in a woven or knitted fabric containing the cationic dye-dyeable cellulosic fiber of the present invention.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, preferred embodiments of the present invention will be specifically described.
[0012]
The cationic dye-dyeable cellulosic fiber of the present invention contains a sulfonate group-containing surfactant whose elution amount from the fiber is less than 10% of the added amount in wet heat treatment at 120 to 135 ° C. for 30 minutes. is necessary.
[0013]
In the present invention, by adding a sulfonate group-containing surfactant, cellulosic fibers are imparted with cationic dyeability by a sulfonate group. Although the amount of the sulfonate group-containing surfactant present on the fiber surface affects the cationic dyeability, the sulfonate group-containing surfactant is uniformly dispersed in the fiber. It is thought that it is eluted from those near the surface.
[0014]
For this reason, when the sulfonate group-containing surfactant elutes from the cellulosic fiber in an amount exceeding 10% of the amount added in the wet heat treatment at 120 to 135 ° C. for 30 minutes, which is the processing condition of the polyester fabric, the fiber Since the amount of the surfactant existing near the surface is reduced, the dyeing density of the cellulosic fiber itself varies when dyeing with a cationic dye, and the dyeing density difference between the cellulosic fiber and the polyester fiber occurs.
[0015]
In addition, the content of the sulfonate group-containing surfactant needs to be 1 to 30 wt%. In order to strongly express the coloring by the cationic dye, it is preferable to include as much as possible. However, if it exceeds 30 wt%, spinning stability becomes poor and fiber properties such as strong elongation also deteriorate. On the other hand, if it is less than 1 wt%, the dyeing concentration of the cationic dye becomes insufficient, and the dyeing effect cannot be obtained.
[0016]
In addition, as a preferable sulfonate group-containing surfactant in the present invention, a sulfonate group-containing surfactant having a tristyrylphenyl structure is exemplified. The surfactants are compared with conventionally known anionic group-containing surfactants such as sodium dihexylsulfosuccinate and sodium dioctylsulfosuccinate, or sodium dodecylbenzenesulfonate and sodium alkanesulfonate. Very low elution volume. This is probably because the tristyrylphenyl group is present in the cellulosic fiber in a more stable state than the alkyl group, alkane group or alkylbenzene group.
[0017]
Further, in the present invention, from the viewpoint of imparting hydrophilicity to the cellulosic fiber and increasing the dyeing speed and improving the dyeability to a dark color, the sulfonate group-containing surfactant has an oxyethylene unit having a repeating unit number of 30 or less. Preferably, the polyoxyethylene tristyryl phenyl ether sulfate is contained.
[0018]
Further, when the number of repeating units of oxyethylene units exceeds 30, even if the number of ionic functional groups is the same, the weight fraction of the additive with respect to the weight of the fiber increases, so that the fraction of the cellulosic component forming the fiber decreases, The fiber-forming ability, that is, spinning stability, tends to be poor, and the fiber properties tend to decrease.
[0019]
Further, the cellulosic fiber of the present invention is preferably a cellulose acetate fiber having excellent color developability, silky glossiness and dryness. The cellulose acetate fiber may be a cellulose acetate fiber in which 74% or more and less than 92% of the hydroxyl groups are acetic acid, or a cellulose triacetate fiber in which 92% or more of the hydroxyl groups are acetic acid.
[0020]
Next, an example of the method for producing the cationic dye-dyeable cellulosic fiber of the present invention will be described below by taking cellulose acetate fiber as an example.
[0021]
The stock solution for spinning used for spinning is prepared by dissolving cellulose acetate in a single solvent such as acetone or methylene chloride or a mixed solvent such as methylene chloride / methanol to a cellulose acetate concentration of 15 to 35 wt%, preferably 18 to 30 wt%. A sulfonate group-containing surfactant is added to the stock solution and mixed, or a solution in which the sulfonate group-containing surfactant is dissolved in a single solvent such as acetone, methylene chloride, methanol, or a mixed solvent such as methylene chloride / methanol is added to the stock solution. Add and mix to adjust the sulfonate group-containing surfactant to a predetermined concentration.
[0022]
The addition amount of the sulfonate group-containing surfactant at this time is adjusted so as to be 1 to 30% by weight, preferably 4 to 15% by weight, based on the total solid content of the spinning dope.
[0023]
The spinning is preferably performed by a dry spinning method in which a spinning solution is supplied to a spinneret and discharged from a spinning nozzle into a high-temperature atmosphere, but by a wet spinning method in which a non-solvent of cellulose acetate is discharged from the spinning nozzle during coagulation. May go. Also, at the time of spinning, a spinning stock solution with no surfactant added or a spinning stock solution with a different addition amount, or an acetate spinning stock solution with a different degree of substitution or a spinning stock solution with a different solid content as a spinning stock solution, are used in combination, a side-by-side type, Composite spinning may be performed in a core-sheath type or the like. Further, the cross-sectional shape of the fiber may be any of a circular shape and an irregular shape, and the fiber shape may be any of a staple and a filament.
[0024]
Further, as the woven or knitted fabric comprising the cationic dye-dyeable cellulosic fiber of the present invention, it is preferable to dispose the fiber in the woven or knitted fabric so that the coloring of the fiber can be sufficiently visually recognized. Are suitable. In addition, the fiber can be used as a composite yarn such as a covering yarn arranged outside the fiber bundle, a turbulent flow processed yarn arranged in a loop shape, a loop yarn, a molding yarn, etc. The content of the fiber is preferably 5% or more. If it is less than 5%, even if it is dyed dark, the expression of different colors and shades tends to be insufficient as a woven or knitted fabric.
[0025]
【Example】
Hereinafter, the present invention will be described with reference to examples. The evaluation was performed by the following method.
[0026]
(Quantification of activator addition amount before wet heat treatment)
{Circle around (1)} A sample is dissolved in methylene chloride to prepare a solution having a concentration of 0.1 wt%.
[0027]
(2) Weigh 10 g of the 0.1 wt% solution into a test tube.
[0028]
{Circle around (3)} Further, an aqueous methylene blue solution (concentration: 0.4695 × 10 ⁻⁶ mol / 5 g) is added (upper layer: aqueous solution, lower layer: methylene chloride), and the mixture is stirred with a shaker.
[0029]
At this time, the amount of methylene blue added was changed, and the amount of methylene blue, which makes the upper layer almost transparent from blue, that is, the amount of consumed methylene blue, was used to determine the amount of the surfactant present in the fiber before the wet heat treatment (to the fiber). Is calculated.
[0030]
(Quantitative determination of additive elution amount during wet heat treatment)
{Circle around (1)} A 10 g sample is immersed in 300 ml of distilled water, charged in a sealed pressure vessel, and subjected to a wet heat treatment with stirring at a predetermined temperature for 30 minutes.
[0031]
{Circle around (2)} To the test tube, 5 g of the residual liquid from the wet heat treatment and 5 g of an aqueous methylene blue solution (concentration: 0.4695 × 10 ⁻⁶ mol / 5 g) were added.
[0032]
{Circle around (3)} 10 g of chloroform is further added (upper layer: aqueous solution, lower layer: chloroform) and stirred by a shaker.
[0033]
{Circle around (4)} The presence or absence of the complex is examined by coloring the chloroform layer.
[0034]
(5) The amount of methylene blue is changed, and the amount of surfactant in the moist heat treatment residue is calculated from the amount of methylene blue in which the upper layer becomes almost transparent from blue, that is, the amount of methylene blue consumed.
[0035]
The calculation of the elution fraction relative to the amount of addition is expressed by (amount of elution of additive during wet heat treatment / amount of activator added before wet heat treatment) × 100 (%).
[0036]
(staining)
The fibers are placed in a dyeing bath (closed pressure vessel) with a bath ratio of 1:40 and dyed with stirring at a temperature of 120 ° C. for a time of 30 minutes.
[0037]
Preparation of dyeing bath-Cationic dye: 1% owf (Cathilon Blue CD-FBLH Hodogaya Chemical Industry Co., Ltd.)
Auxiliary agent: 0.5 g / L (Ultra MT N2 manufactured by Daiwa Chemical Industry Co., Ltd.)
(Examples 1 and 2)
Cellulose triacetate in which 97% of hydroxyl groups were acetic acid was dissolved in a mixed solvent of methylene chloride / methanol (mixing ratio: 91/9) to prepare a spinning dope having a concentration of 21.9 wt%. Based on the total solid content, as a sulfonate group-containing surfactant, polyoxyethylene tristyryl phenyl ether sulfate (manufactured by Toho Chemical Co., Ltd., SM-210, the number of repeating oxyethylene units = 15 to 16, active ingredient 100) %) Was 5 wt% in Example 1 and 10 wt% in Example 2, and the mixture was stirred and mixed with the spinning dope to prepare a spinning dope. Using this spinning dope, it was wound by dry spinning at a spinning speed of 500 m / min to obtain a cellulose triacetate fiber of 84 dtex / 20 filaments. The obtained fibers were used to form a tubular knit, and the amount of the additive eluted during the wet heat treatment at 80 to 140 ° C. was quantified. The results of the elution percentage with respect to the added amount are shown in Table 1.
[0038]
Further, the obtained fiber was formed into a tubular knit, subjected to a wet heat treatment at 130 ° C., and the tubular knit not subjected to the wet heat treatment was put into the same dyeing bath and dyed at 120 ° C. with a cationic dye. There was almost no difference, and a clear dyeing characteristic of cationic dyeing was obtained.
[0039]
Further, the obtained fiber and the cationic dye-dyeable polyester fiber 56dtex / 24f obtained by copolymerizing 5-sodium sulfoisophthalic acid are interlaced, 1200 t / m twisted, and steam setting at 80 ° C. × 40 minutes, followed by knitting. (28G smooth). After this was subjected to relaxing wet heat treatment at 130 ° C. for 30 minutes, cationic dyeing was performed at 120 ° C. The obtained product was able to obtain a product of uniform color.
[0040]
(Example 3)
As a sulfonate group-containing surfactant, polyoxyethylene tristyryl phenyl ether sulfate (manufactured by Toho Chemical Co., Ltd., trade name: SM-210 exp-3, number of repeating oxyethylene units = 8, active ingredient 100%) was 3 A cellulose triacetate fiber having 84 dtex / 20 filaments was obtained under the same conditions as in Example 1 except that 0.6 wt% was added. The obtained fibers were used to form a tubular knit, and the amount of the additive eluted during the wet heat treatment at 80 to 140 ° C. was quantified. The results of the elution percentage with respect to the added amount are shown in Table 1.
[0041]
(Comparative Example 1)
A cellulose triacetate fiber having 84 dtex / 20 filaments was obtained under the same conditions as in Example 1 except that polyoxyethylene tristyryl phenyl ether sulfate was not added as a sulfonate group-containing surfactant.
[0042]
The obtained fiber was not stained with the cationic dye.
[0043]
(Comparative Example 2)
Spinning was performed under the same conditions as in Example 1 except that 35% of polyoxyethylene tristyryl phenyl ether sulfate was added as a sulfonate group-containing surfactant. However, thread breakage occurred frequently, and stable spinning was difficult. Was.
[0044]
(Comparative Example 3)
As a surfactant, 84 dtex / 20 filaments under the same conditions as in Example 1 except that a methanol solution of sodium dioctyl sulfosuccinate (manufactured by Toho Chemical Co., Inc., Anstex AF-80) was added at 3.6 wt%. To obtain cellulose triacetate fiber. The obtained fibers were knitted into a tube, and the amount of the additive eluted during the wet heat treatment at 80 to 140 ° C. was quantified. The results of the elution percentage with respect to the added amount are shown in Table 1.
[0045]
The obtained fiber was used to form a tubular knit, subjected to a wet heat treatment at 130 ° C., and the tubular knit not subjected to the wet heat treatment was placed in the same dyeing bath and subjected to cationic dyeing at 120 ° C. The tube knitted was deeply dyed, and the tube knit which had been subjected to the moist heat treatment at 130 ° C. was dyed only in a very light color, resulting in a large difference in dyeing density between the two.
[0046]
Further, the obtained fiber and the cationic dye-dyeable polyester fiber 56 dtex / 24f obtained by copolymerizing 5-sodium sulfoisophthalic acid are interlaced, 1200 t / m twisted, and steam knitting after 80 ° C. × 40 minutes steam setting. (28G smooth). This was subjected to relaxing wet heat treatment at 130 ° C. for 30 minutes, and then cationic dyeing was performed at 120 ° C. The obtained product was a blue knitted fabric dyed with a cationic dye-dyeable polyester fiber, but was a product in which undyed cationic dye-dyeable cellulose triacetate fiber was mixed to give a feeling of heat.
[0047]
[Table 1]

[0048]
【The invention's effect】
According to the present invention, a cationic dye-dyeable cellulosic system which achieves dye development resistant to wet heat treatment, that is, has a practically satisfactory cationic dye dyeing property and dye concentration even when a processing step employing wet heat treatment is performed. A fiber and its woven or knitted fabric are obtained.

Claims (5)

In a heat treatment at 120 to 135 ° C. for 30 minutes, a cationic dye containing 1 to 30% by weight of a sulfonate group-containing surfactant having an elution amount from the fiber of less than 10% of the added amount. Dyeable cellulosic fiber. 2. The cationic dyeable cellulosic fiber according to claim 1, wherein the sulfonate group-containing surfactant has a tristyrylphenyl structure. The cationic dye-dyeable cellulose-based fiber according to claim 2, wherein the sulfonate group-containing surfactant having a tristyrylphenyl structure is a polyoxyethylene tristyrylphenyl ether sulfate containing oxyethylene units having 30 or less repeating units. The cellulosic fiber dyeable with a cationic dye according to any one of claims 1 to 3, wherein the cellulosic fiber is a cellulose acetate fiber. A woven or knitted fabric containing the cationic dye-dyeable cellulosic fiber according to any one of claims 1 to 4.