JPH0826486B2 - Composite fiber dyed with cationic dye - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dyed conjugate fiber which is excellent in light fastness and washing fastness of dyeing and can obtain a clear color.

[Prior Art] Polyamide fibers represented by nylon 6 and nylon 66 have been used in many clothing applications due to their excellent strength, abrasion resistance, deep dyeability, and ease of resin processing. ing. Among them, sports outerwear, especially ski wear, where color development and resin processability are particularly required, was the exclusive venue for nylon.

However, with the recent diversification of fashion and the expansion of uses, clear colors are required for ski wear, swimwear, casual wear and the like. The greatest advantage of polyamide is that it can be dyed in deep colors with acid dyes, and it can be dyed in vivid colors.On the contrary, in vivid color dyeing, the discoloration due to light is remarkable and the dyeing fastness is poor. However, it was considered difficult to put into practical use in applications where both vivid color and dyeing fastness are strongly required.

Further, the cationic dye dyeable sulfonated aromatic dicarboxylic acid-modified polyamide disclosed in U.S. Pat.No. 3,389,549 is capable of vivid dyeing close to a fluorescent color, but since the color fading and fading due to washing are severe, It is considered to be difficult to apply to clothing applications where washing resistance is important, and it is only used for a part of carpets.

On the other hand, a polyester represented by polyethylene terephthalate is generally dyed with a disperse dye, and although its coloring property and transfer sublimation property have been improved, there are still many parts which are still inferior to nylon in the depth of vivid color. further,
Due to its molecular structure and chemical structure, polyester is vulnerable to abrasion and resin processability is not sufficient. The dyeability of this polyester can be greatly improved by dyeing the polymer with a sulfonated aromatic dicarboxylic acid-modified polyester and dyeing it with a cationic dye, as described in JP-B-34-10497. The above-mentioned drawbacks inherent to polyester (insufficient abrasion resistance and resin processability) are not improved, but rather tend to be worse.

In addition, many means have been proposed to utilize the advantages of both core-sheath composite spinning of polyamide and polyester. In that case, nylon 6 and nylon 66 are used as the polyamide, and polyethylene terephthalate is used as the polyester. As used, it is used as a combination of homopolymers, and the dyeing is a disperse dye dyeing in which both are dyed together, or a mixed dyeing of an acid dye and a cationic dye or a disperse dye to obtain sufficient color developability. Is needed for. However, the dyed product obtained by the former disperse dyeing has insufficient washing fastness of polyamide and is not at a practical level. Further, the dyed product obtained by the latter mixed dyeing has not been put into practical use because the problem of poor light fastness on the polyamide side, which is clearly dyed with an acid dye, is a problem.

[Problems to be Solved by the Invention] The present invention provides a dyed product that is dyed in a vivid color and is excellent in color development, light fastness, washing fastness and abrasion fastness, and is strong and resin-processed. The main purpose is to provide a dyed composite fiber having good properties.

[Means for Solving the Problems] The present invention provides a sulfonated aromatic dicarboxylic acid-modified polyamide in the sheath portion, a sulfonated aromatic dicarboxylic acid-modified polyester in the core portion, and substantially only a cationic dye as a dye. Is a core-sheath type composite fiber dyed, wherein the dyeing rate of the sheath is 10% or less of the dyeing rate of the core,
In addition, the composite fiber is dyed with a cationic dye, which has a content of 0.2% owf or less.

One of the characteristics of the present invention is a core of a composite structure that covers a sulfonated aromatic dicarboxylic acid modified polyester (hereinafter abbreviated as modified polyester) with a sulfonated aromatic dicarboxylic acid modified polyamide (hereinafter abbreviated as modified polyamide). It is to use a sheath type composite fiber.

Another feature is that the core-sheath type composite fiber is dyed substantially only with a cationic dye, and the dyeing rate of the sheath and the core is a specific value. That is, the dyeing rate of the sheath is 10% or less of the dyeing rate of the core, and
It is important to set it to 0.2% owf or less, preferably 0.1% owf or less.

In order to satisfy this dyeing rate condition, dyeing conditions that allow the modified polyester to be dyed, for example, high temperature dyeing at a temperature of about 100 to 120 ° C may be used. In such high-temperature dyeing, the dye is largely exhausted by the modified polyester, but the amount of exhaustion to the modified polyamide is considerably small, so that the above dyeing rate condition can be satisfied.

And, although the sheath portion (modified polyamide) is scarcely dyed, excellent coloring properties are exhibited as the whole fiber. Moreover, even if a dye is present in the sheath (modified polyamide), the amount thereof (dye dyeing ratio) is suppressed to a specific level, whereby excellent light fastness and washing fastness can be obtained. That is, the dyeing rate of the sheath is 0.2% o
When it exceeds wf, the fastness to washing and the fastness to light are significantly reduced. Even if the dyeing ratio is 0.2% owf or less, if the dyeing ratio of the core is more than 10%, it is difficult to obtain a sufficient level of light fastness.

The dyeing rate of the core may be set to any level according to the desired degree of dyeing. In order to obtain a color development that can be recognized with the naked eye, in the case of a light dyeing product, generally, a dye dyeing rate of 0.01% owf or more should be taken. Further, in the case of a deep dyeing product, a dyeing rate of 50% owf or less is preferable from a practical viewpoint in terms of cost.

The dyeing rate of the sheath or core in the present invention is a value representing the amount of dye dyed to the polymer of the sheath or core as a percentage, and for example, the dyeing rate of the sheath. Is less than 0.2% owf means that the modified polyamide in the sheath
This means that the amount of dye adhering to 1 g is 0.002 g or less.

The dyeing rate of the sheath or core may be obtained by the following method.

Dye-dyeing rate of sheath: Weigh a fixed amount (200 mg) of dyed composite fiber or its fabric, and soak it in 30 ml of 30% formic acid 88% solution for 3 minutes to obtain sheath-modified polyamide and its The dye dyed therein is dissolved, and the absorbance at the maximum absorption wavelength is measured by a colorimeter (U-3400 "Spectro Phometer" manufactured by Hitachi Ltd.). Also, weigh a fixed amount (200 mg) of the sample before dyeing, dissolve it with a predetermined amount (0.25 mg, 0.5 mg, or 1.0 mg) of dye in 30 ml of 30% formic acid 88% solution, and measure the absorbance with a colorimeter. Then, the relationship between the absorbance and the dyeing rate of this dye is plotted as a calibration curve. With this calibration curve, the value of the dyed amount is obtained from the value of the absorbance of the sheath-modified polyamide in the actual dyeing described above.

Dyeing rate of core: First, the sheath-modified polyamide in the composite fiber or its products is dissolved and removed, and then washed with water to obtain a dyed fiber component containing only the core-modified polyester. A fixed amount (100 mg) of the dyed fiber content was weighed, put into 30 ml of a phenol / ethane tetrachloride mixed solution (weight ratio 3: 2) and completely dissolved at about 60 ° C., and then the same colorimeter as described above was used. The absorbance at the maximum absorption wavelength is measured. Further, using a fiber component of only the modified polyester taken out from the sample before dyeing, in the same manner as described above, a calibration curve showing the relationship between the absorbance and the dyeing rate is obtained, and from this calibration curve, the above-mentioned actual dyeing is performed. The value of the dyed amount of the core-modified polyester is determined.

Then, from the values of the dye dyeing amount of the sheath portion and the core portion (a% owf and b% owf, respectively, in order), (a / b) x 1
The dyeing ratio of the sheath to the core is calculated by the formula of 00.

The modified polyamide used for the sheath portion in the present invention is a modified polyamide in which a compound having a sulfone group is bonded to a part of a polyamide chain or a terminal, or a compound having a sulfone group, and a sulfonated aromatic dicarboxylic acid is added during polyamide polymerization. It can be produced by adding and copolymerizing in a free acid state or an alkyl ester state. This sulfonated aromatic dicarboxylic acid is not substantially eluted and removed by washing and washing.

Poly (epsilon) -capramide (nylon 6) and polyhexamethylene adipamide (nylon 66) are typically used as the base polyamide, but other polymerizable monomers such as laurolactam, sebacic acid, A polyamide obtained from paraxylylenediamine, isophthalic acid or the like, or a copolyamide thereof may be used.

Further, as a representative sulfonated aromatic dicarboxylic acid, 5-sulfoxyisophthalic acid represented by the following chemical formula (1) or a salt thereof can be mentioned.

The copolymerization amount of the sulfonated aromatic dicarboxylic acid is preferably about 0.25 to 3 mol% with respect to the monomer of the base polyamide. If this copolymerization amount is too low, the original effect of the modified polyamide is difficult to obtain, and conversely, if it is too large, the effect of the copolymerization of the sulfonated aromatic dicarboxylic acid reaches saturation, and conversely, it is the preferred machine of the base polyamide. Property is impaired.

This modified polyamide may contain a matting agent such as titanium oxide, but in order to sufficiently transmit the color of the core polyester and obtain excellent color development, a matting agent or another pigment is used. Etc. are preferably substantially not included.

Further, these polyamides may contain an antistatic agent, a heat-resistant agent, a light-resistant agent, etc., as long as they do not significantly reduce the light transmittance.

The modified polyester used in the core portion of the present invention is a modified polyester in which a compound having a sulfone group is contained in a part of the chain or terminal of the polyester.
No. 31-10497. This modified polyester is a modified polyester obtained by copolymerizing polyethylene terephthalate, polybutylene terephthalate or a copolymerized polyester containing these as a main component with a sulfonated aromatic dicarboxylic acid or a salt thereof.

Typical examples of the sulfonated aromatic dicarboxylic acid include 5-sulfoxyisophthalic acid represented by the above chemical formula (1) or a salt thereof.

These dicarboxylic acids are added in the state of free acid or in the state of alkyl ester during the polymerization of polyester and copolymerized to form a modified polyester. The copolymerization amount of the sulfonated aromatic dicarboxylic acid is preferably about 0.5 to 6 mol% with respect to terephthalic acid. If this copolymerization amount is too low, it is difficult to obtain the desired effect of the modified polyester. On the contrary, if the copolymerization amount is too high, the crystal structure of the modified polyester is disturbed and undesired phenomena such as a significant decrease in mechanical properties occur.

It should be noted that these modified polyesters may contain an antistatic agent, a light resistance agent, a heat resistance agent, a matting agent and the like.

The core-sheath composite ratio of the modified polyamide and the modified polyester can be arbitrarily set within the range where the effect of the present invention is not lost, but the modified polyamide ratio is preferably 20 to 75% by weight. If the modified polyamide ratio is too low, it is difficult to form a uniform coating, and moreover, the sheath portion is often broken during processing such as knitting, weaving, dyeing, and finishing, and the commercial value is lost. On the other hand, if it is too high, the color of the dyed modified polyester core is interrupted and it is difficult to obtain the desired color developability.

The arrangement of the modified polyamide sheath and the modified polyester core is basically preferably concentric core sheath,
It may be eccentric or multi-core as long as the sheath portion is not too thin and is torn. In addition, if it is possible to cover the modified polyester core portion with the modified polyamide sheath portion, a modified yarn can be used.

This core-sheath type composite fiber may be made into a product by yarn-forming, knitting, weaving, and dyeing by a conventional method.

First, the modified polyamide and the modified polyester are separately melted, introduced into a spinning pack portion, formed into a composite stream so as to have a core-sheath structure by a usual method, and spun from a nozzle.

The spun filament yarn is taken up and oiled at a predetermined speed and then wound up in a package. Next, the wound yarn is stretched by a draw twister in a conventional manner so that desired strength and elongation can be obtained. This drawing may be carried out continuously after winding the spun yarn without winding and then winding.
Further, a method may be adopted in which the desired fiber performance is obtained all at once at a high speed of 4000 m / min or more.

As the direct spinning and drawing method, for example, spun yarn is 1000 to 50
A method of collecting at 00 m / min, followed by stretching, and stretching and heat setting at 3000 to 5500 m / min can be mentioned.

The obtained conjugate fiber is dyed with a cationic dye by an ordinary method at an optional step thereafter.

Examples of this cationic dye include "Aizen Cathlon"
(Hodogaya Chemical Co., Ltd.), "Kayacryl" (Nippon Kayaku Co., Ltd.), "Estrol, Sumiacryl" (Sumitomo Chemical Co., Ltd.), "Diacryl" (Mitsubishi Kasei Co., Ltd.) ),
"Maxilon" (manufactured by Ciba Geigy), "Astrazon"
Examples thereof include dyes having a crown name such as those manufactured by Bayer Japan Co., Ltd., but the dyes are not limited to these, and a dispersion type cationic dye can also be used. Other dyes may be used in combination as long as the amount is within a range that does not impair the effects of the present invention.

The dyed conjugate fiber according to the present invention is particularly suitable for clothing products such as repeated washing, but carpet,
It can also be used for interior goods such as car seats.

[Operation] In the polyester / polyamide core-sheath type composite fiber according to the present invention, the core portion of the modified polyester is sufficiently dyed, and the modified polyamide of the sheath portion is dyeable with a cationic dye, but is dyed very little. There is no state.

However, the dyed composite fiber has sufficient color development although the sheath is dyed very little. This is because the dye molecules are extremely likely to migrate inside the modified polyamide sheath, so even if the dye concentration is the same, even the dye that should originally be dyed on the modified polyamide sheath is exhausted to the modified polyester core and its color is developed. That the color development of the core part is recognized as the color development of the whole composite fiber with almost no inhibition by the sheath part, and as a result, a sufficient level of clear color development is obtained. it is conceivable that.

Further, even when the dye exhaustion rate is such that clear color development is obtained, sufficiently excellent light fastness and washing fastness are exhibited. This is because the dye exhaustion amount in the modified polyamide sheath is very small, the amount of dye loss due to washing is small, and further, a part of the lost dye migrates into the polyester core, which also occurs. It is considered that even a modified polyamide can provide excellent wash fastness. Furthermore, while dyeing the sheath of the modified polyamide, it is possible to obtain almost the same degree of light fastness as polyester fiber, but this is because the UV absorbing effect of the modified polyester core that is present in close contact protects the dye. It is considered that even if a slight amount of dye in the modified polyamide sheath portion causes fading, it hardly affects the color developability of the entire fiber. Therefore, the light fastness and washing fastness in vivid colors can be improved to a level as high as was not possible with the modified polyamide fiber, and the dyeing fastness can be made practical. For example, it is possible to put into practical use even a specific bright color dye which has been difficult to use because it has a serious problem of poor light fastness.

Furthermore, since the low refractive index modified polyamide covers the surface of the modified polyester, there is less surface reflection,
The effect of increasing the color depth is also exhibited.

In addition, the dyed conjugate fiber according to the present invention also has the abrasion resistance and resin processing easiness inherent to polyamide. Further, by having a modulus intermediate between polyamide and polyester, it is possible to impart a favorable tension and stiffness to the fabric, and as a secondary effect, the effect of improving dimensional stability against water, which is a drawback of polyamide, and The wrinkle-proof effect can also be exhibited.

Due to having such characteristics as well, the conjugate fiber according to the present invention exerts a particularly remarkable effect in the cloth for clothes used for repeated washing. Of course, even with car seats and carpets that are washed infrequently, products with excellent color development and vividness that have never been obtained can be obtained. Further, the modified polyamide serves as a sheath, so that a depth of color which is not found in the conventional cationic dyeable polyester can be obtained.

EXAMPLE 1 Example 1 0.5 mol% of 5-sulfoxyisophthalic acid was added to ε-caprolactam and polymerized in a usual manner to give 98% sulfuric acid relative viscosity of 2.6 and substantially no titanium oxide. Modified nylon 6 was obtained.

In addition, as a polyethylene terephthalate raw material consisting of ethylene glycol and terephthalic acid, a catalyst and 5-sulfoxyisophthalic acid (to terephthalic acid
1.5 mol%) and polymerized to obtain a modified polyethylene terephthalate (abbreviated as modified polyester) having an intrinsic viscosity (IV) of orthochlorophenol of 0.64.

The modified nylon 6 and the modified polyester are subjected to an extruder type composite spinning machine, melted separately, and then weighed in equal amounts so that the modified polyester becomes the core and the modified nylon 6 becomes the sheath in the composite spinning pack part. A composite stream is formed and discharged, and it is drawn at a speed of 1500 m / min, then heat-set by a stretching heat roller (160 ° C) and wound at 4000 m / min.
A drawn yarn of 0 denier 24 filament was obtained.

This plain yarn (warp density 11
8 yarns / 2.54 cm, weft density 85 yarns / 2.54 cm) were woven. 2g of this plain weave is "Sandet" G-29 (manufactured by Sanyo Kasei Co., Ltd.)
/ l, soda ash 5g / l, "Detrol" WR-14 (manufactured by Meisei Chemical Industry Co., Ltd.) 2g / l in a treatment bath at 98 ° C for 20 minutes, desizing and scouring, and then drying Then, the intermediate setting was performed at 170 ° C. to obtain a dyed sample cloth.

The sample cloth was treated with a cationic dye: "Diacryl Red GRL-N".
Dyeing was carried out for 30 minutes at 120 ° C. in a bath of 0.5% owf of conc (manufactured by Mitsubishi Kasei Co., Ltd.) and 0.5 cc / l of acetic acid (80%) as an auxiliary agent (Example 1).

As a comparison, the sample cloth was mixed and dyed under the following conditions. Cationic dye "Diacryl Red GRL-N" (manufactured by Mitsubishi Kasei Co., Ltd.) 0.25% owf, acid dye "Diacid Azo.Ru"
biol 3GS "250% (manufactured by Mitsubishi Kasei Co., Ltd.) 0.25% owf,
"OSPIN 700-CD" (manufactured by Tokai Oil Co., Ltd.) as an auxiliary agent.
It was dyed in a bath of 5% owf and 0.5 cc / l of acetic acid at 120 ° C. for 30 minutes (Comparative Example 1).

From the obtained dyed fabric, the dye dyeing ratio of the sheath portion or core portion of the constituent composite fiber was measured under the condition of the maximum absorption wavelength of 537 nm, and the coloring property, light fastness and washing fastness were also measured.

 The results are shown in Table 1.

Coloring property: A multi-light source spectrocolorimeter (manufactured by Suga Test Instruments Co., Ltd.) was used to measure the color under the condition of a C light source of 65 ° and the L value was displayed.
When the color developability is poor, the color is whitish and the L value is high.

Lightfastness: Measured by the method of JIS L0842, and the degree of discoloration was classified by grade.

Washing fastness: measured by the method of JIS L0844. However,
The discoloration was measured by grading the degree of discoloration by comparing with the difference in color observed between the color charts of the staining gray scale.

As shown in the results of Table 1, the dyed core-sheath type composite fiber according to the present invention was excellent in dyeing fastness and excellent in color development despite the presence of the polyamide layer on the fiber surface. . On the other hand, in the case of Comparative Example 1 by the mixed dyeing, the dyeing fastness, especially the color fading at the time of washing was poor, and the product did not satisfy the practical level.

-Example 2 With respect to the dyed fabric obtained by dyeing the sample fabric for dyeing obtained in Example 1 under the following conditions, the dye dyeing ratio of the sheath portion and the core portion of the constituent composite fiber was maximized. Absorption wavelength
It was measured under the condition of 632 nm, and its color developing property, light fastness and washing fastness were also measured in the same manner as in Example 1, and the results are also shown in Table 1 as Example 2.

Cationic dye "Kayaryl Black R-ED" (manufactured by Nippon Kayaku Co., Ltd.) 10% owf, acetic acid (80%) 0.5cc / l, 45 at 120 ° C
Stain for minutes, then "Luckor PSK" (Meisei Chemical Co., Ltd.)
Made): anionic activator) 0.5g / l, acetic acid (80%) 0.2g /
l, soaping for 20 minutes at 60 ℃, washed with water and dried.

In addition, as a comparison, a sample fabric for dyeing was manufactured by melt spinning using only the same modified polyester as used in Example 1 and directly spinning, weaving and scouring in the same manner as in Example 1, and using the same cation as above. Dyeing and soaping were performed to manufacture a dyed fabric. The dyeing characteristics were measured in the same manner as in Example 1, and the results are also shown in Table 2 as Comparative Example 2.

As shown in the results of Table 2, the dyed core-sheath type composite fiber according to the present invention has a smaller L value than that of Comparative Example 2,
A deep dyed product was obtained. Moreover, the dyeing fastness was excellent despite the presence of the polyamide layer on the fiber surface.

Example 3 The same method as in Example 1 was used except that the same modified nylon 6 and modified polyethylene terephthalate as in Example 1 were used and the composite ratio of modified nylon 6 was changed to 10, 25, 50, 75 and 90% by weight, respectively. Melt spinning and direct spinning drawing were performed to obtain a 40 denier 12 filament composite fiber yarn. After knitting these fiber yarns into a 28-gauge half tricot, as in Example 1, "Diacryl Red GRL-N" (Mitsubishi Kasei Kogyo Co., Ltd.)
Manufactured) and the dyeing characteristics were measured in the same manner as in Example 1.

The film breakage of the sheath nylon was determined by taking a photograph of the surface of the fibers constituting the dyed fabric and enlarging the sheath nylon layer.

The results obtained were as shown in Table 3. Both the wash fastness and light fastness were at practical levels,
Color development was insufficient when the nylon 6 ratio exceeded 75% by weight. Further, when the nylon 6 ratio was less than 20% by weight, it was difficult to uniformly cover the modified polyester in the core portion with the nylon sheath, and there was a phenomenon that the sheath was broken during the spinning drawing and knitting finishing.

When the fabric tension and waist are compared, the sheath nylon ratio is
When the content was 20 to 75% by weight, the result was good, and the hand was more preferable than the nylon 6 alone cloth and the polyethylene terephthalate alone cloth.

EFFECTS OF THE INVENTION The dyed conjugate fiber according to the present invention makes it possible to obtain an excellent fiber product having a clear color and excellent light fastness and washing fastness. That is, this dyeing fastness is so excellent that it cannot be obtained with a bright color fiber product comprising polyamide fibers or modified polyamide fibers.

Moreover, since the modified polyester layer is present in the core portion, it is excellent in dimensional stability and wrinkle resistance, and has appropriate tension and elasticity. In addition, the drawbacks such as the abrasion resistance and the resin processability which are found in the cloth composed only of the modified polyester fiber are improved by arranging the modified polyamide layer in the sheath portion, and the depth of color is also improved.

Since it has these characteristics, the composite fiber according to the present invention can be suitably used for sportswear, outerwear and the like, which are required to have excellent vivid colors and dyeing fastness.

Claims (2)

[Claims] 1. A core-sheath composite in which a sulfonated aromatic dicarboxylic acid-modified polyamide is arranged in a sheath portion, a sulfonated aromatic dicarboxylic acid-modified polyester is arranged in a core portion, and substantially only a cationic dye is dyed as a dye. A fiber, wherein the dyeing rate of the sheath is 10% or less of the dyeing rate of the core,
Also, the composite fiber dyed with a cationic dye is characterized in that it is 0.2% owf or less. 2. The composite fiber dyed with a cationic dye according to claim 1, wherein the polyamide sheath has a composite ratio of 20 to 75% by weight.