JP3312938B2 - Method for producing animal hair fiber product having different color effect - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing animal hair fiber products having a different color effect, such as a heather or marbling effect, by a single bath dyeing method using a cationic dye and a wool dye in combination.

[0002]

2. Description of the Related Art Conventionally, when producing animal hair fiber yarn or woven or knitted fabric having a different color effect such as heather tone, marbling tone, or the like, rose hair,
The so-called dyeing method of dyeing slivers and spinning, twisting or weaving the dyed products is generally practiced. However, in the pre-dying method, after dyeing, processes such as spinning, twisting, and knitting are required, so that it takes a lot of time to produce heather-like or marbling-like yarns and woven / knitted fabrics, and furthermore, during the manufacturing process. , It is necessary to switch the machine for each color,
In addition, the production efficiency is extremely low, such as the generation of debris during production, and the so-called production yield is reduced. Therefore, the above-described yarn-dying method is compatible with the short cycle, small-quantity, and multi-product varieties currently required most. It is difficult.

As a method for addressing the above problems in the pre-dyeing method, there is a single-bath multi-color dyeing method, for example, in which animal hair fibers pretreated with a metal salt mordant and untreated animal hair fibers are mixed. Multi-chromium method, a method of mixing densely-treated animal hair fibers into which cationic groups are introduced, and an untreated animal hair fiber, and a method of mixing shrink-proof treated animal hair fibers and untreated animal hair fibers. This is a method of dyeing a yarn or knitted fabric mixed with animal hair fibers having different dye affinities depending on whether the same dye is treated or untreated in a single bath.

[0004]

The one-bath multicolor effect dyeing method which has been conventionally performed is, as described above, a method in which two or three types of animal hair fibers having different affinities for wool dyes are mixed. Yes, these products have a two-color or three-color heather or marbling effect due to wool dye, but the color tone can only be obtained as a multicolor effect heather or marbling effect by shading of similar colors. It has not been possible to obtain an animal hair fiber product having an excellent heterochromatic effect with different hues such as the dyeing method.

The present invention has been made in view of such circumstances, and has as its object to obtain an animal hair fiber product having a different dyeing hue and a superior dyeing effect by a single bath dyeing method. It is.

[0006]

The present invention achieves the above object and has the following constitution. That is, the present invention relates to "animal hair fibers that have been anionized with a polyhydric phenol compound, sulfamic acid, an aminochloroallyl compound, or the like, a polyamide epichlorohydrin resin, an aminoacrylic copolymer, or the like, by an oxidizing agent treatment or after an oxidizing agent treatment. Animal hair fiber,
Starting dyeing of animal hair fiber products consisting of untreated animal hair fibers at room temperature using a combination of cationic dye and wool dye
And producing the animal hair fiber product having a different color effect, characterized in that the temperature is raised at a rate of 1 ° C./min or less up to 70 ° C. and dyed in a single bath ”.

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

The animal hair fiber referred to in the present invention means natural keratinous fiber obtained from animals such as wool, cashmere, mohair, angora, camel, alpaca, etc. Yarn, woven fabric, knitted fabric, non-woven fabric, or sewn product containing at least 15% or more of animal fiber alone or animal hair fiber.

In the method of the present invention, an animal hair fiber which has been subjected to an anionization treatment based on the above-mentioned animal hair fiber and an oxidizing agent treatment, or a polyamide epichlorohydrin resin, an aminoacrylic copolymer or the like after the oxidizing agent treatment, An animal hair fiber that has been subjected to a shrink-proof treatment is prepared.

Examples of anionizing agents for anionizing animal hair fibers include polyhydric phenol compounds, sulfamic acid, aminochloroallyl compounds and the like. Examples of polyhydric phenol compounds include gallic acid, tannic acid, and the like. Synthetic tannins and the like are preferred. In the treatment of the anionizing agent, these anionizing agents should be 80 to 80% with 5 to 30% owf.
After treating animal hair fiber at 100 ° C. for 30 to 60 minutes, 3 to 10% owf of an inorganic metal compound such as stannous chloride, aluminum hydroxide, chromium, copper, cobalt, and antimony.
And fixing at 80 to 100 ° C. for 30 to 60 minutes to obtain an anionized animal hair fiber.

The animal hair treated with the anionizing agent reacts with the amino group, which is the dyeing seat of the wool dye, and the amino group is blocked to form an anionized animal hair fiber, and the wool dye is not dyed. Although a white residue is left, dyeing of the cationic dye becomes possible.

Examples of the oxidizing agent used for subjecting the animal hair fiber to the oxidizing agent treatment include hypochlorite, chlorite, dichloroisocyanurate, potassium permanganate, and monopersulfuric acid. Can be.

The oxidizing agent treatment conditions should be adjusted depending on the animal hair fiber and usually vary depending on the type of the oxidizing agent. Generally, the oxidizing agent is used at room temperature at 1 to 8% of the fiber weight.
use. After the oxidizing agent treatment, wash thoroughly with water and then remove the oxidizing agent remaining inside the fiber using a reducing agent. The reducing agent used at this time is sodium bisulfite, sodium sulfite, sodium metabisulfite, etc. A suitable amount is 2 to 10% owf. In the present invention, the animal hair fiber which has been subjected to the shrink-proofing treatment in this state may be used. However, the animal hair fiber which has been subjected to the reduction-neutralization treatment is washed with water, and furthermore, a cationic polyamide epichlorohydrin resin or aminoacrylic resin is used. It may be treated with a copolymer or the like and used as animal hair fiber subjected to a shrink-proof treatment. The amount of resin used at this time is 0.5% in pure amount for polyamide epichlorohydrin resin.
２2.0% owf, and in the case of aminoacrylic copolymer, 0.4 to 1.0% owf in a pure amount is appropriate. To exhaust for 2 to 15 minutes. The animal hair fibers from which the resin has been exhausted are dried at a temperature of 80 ° C. for 5 to 30 minutes. In general, the use of shrink-proof animal hair fibers with an oxidizing agent-reduction-resin has a higher affinity for the dye than that of the oxidizing agent-reduction-treated fiber, so that an excellent different color effect can be obtained.

The above-mentioned anionization treatment with a polyhydric phenol compound or the like and shrink-prevention treatment by applying an oxidizing agent or a resin after the treatment with the oxidizing agent can be performed in the form of loose hair, sliver, or yarn, if necessary. . When the above treatment was performed with roses or slivers, both and untreated slivers were mixed at a predetermined ratio, respectively,
The yarn obtained by spinning in a conventional manner, or a knitted or woven fabric knitted and woven using the yarn, and a sewn product are formed. Further, for the yarn, a twisted yarn of the above-mentioned treated yarn, or a knitted woven fabric obtained by interweaving the two treated yarns and the untreated yarn is formed, and further, a sewn product is formed. The dyeing is performed in a single bath using a combination of a cationic dye and a wool dye. The staining method is
In contrast to the normal dyeing method, which has a starting temperature of about 50 ° C., in the method of the present invention, dyeing is started at room temperature, and the temperature rise is a constant distribution ratio of the dye between the shrink-proof treated animal hair fiber and the untreated animal hair fiber. Up to 70 ° C at a rate of 1 ° C / min or less.
Otherwise, dyeing is carried out in the same manner as for dyeing of ordinary acrylic / animal mixed fiber.

In the present invention, the dyeing is carried out in the same bath using a cationic dye and a wool dye. The cationic dye is a dye having an onium group as a color difference cation. There are gold dyes, acid dyes, and acid mordant dyes. Among them, gold-containing dyes have poor compatibility with cationic dyes and are not suitable for use. There are various types of acid dyes such as leveling type, fast type and milling type, and any type can be used. However, it is preferable to use a milling type acid dye from the viewpoint of color fastness.

[0016] The wool dye has a higher affinity for animal hair fibers treated with an oxidizing agent or shrink-proofed with a polyamide epichlorohydrin resin or an aminoacrylic copolymer after the oxidizing agent treatment as compared with untreated animal hair fibers. The high affinity with the wool dye is due to the reactivity dye>
Acid dye> gold-containing dye. For example, as a reactive dye, lanazole blue 3G (manufactured by Ciba Geigy) 1.0%
owf, 1.0% owf of Irganol Brilliant Blue RLS (manufactured by Ciba Geigy) as an acid milling dye, and the dyeing ratio for untreated and shrink-proof wool fibers when dyed at each temperature for 30 minutes. It looks like 1.

[0017]

[Table 1]

As is clear from Table 1, among the dyes for wool, the reactive dyes particularly start to exhaust the dye at about 30 ° C. with respect to the shrink-proof animal hair fiber, and almost at 80 ° C. It can be seen that the more completely exhausted, the higher the affinity. In addition, acid dyes have a higher affinity for shrink-treated animal hair fibers than untreated animal hair fibers. There is a considerable difference in the amount of dyeing, which is low. Therefore, if untreated animal hair fibers and shrink-reduced animal hair fibers are used as the objects to be dyed in the same dyeing bath and a reactive dye and an acid dye are used simultaneously as dyes, first, the reactive dyes have a lower temperature range than the shrink-treated animal hair fibers. The dyeing is started at about 80 ° C and the dyeing is almost completed. The untreated animal hair fibers have a low exhaustion rate of about 10% or less of the whole, This results in significant shading differences.

On the other hand, the acid dye has a slightly higher affinity with the shrink-treated animal hair fiber, but is much lower than the affinity of the reactive dye, and as a result, the dye is almost equivalent to both of the coexisting animal hair fibers. Will show you the clothes. Therefore, when untreated animal hair fibers and non-shrink-treated animal hair fibers are used in the same bath and dyed with reactive dyes and acid dyes having different hues, different color effects are exhibited due to the difference in affinity between the respective dyes.

As the amount of the reactive dye and the amount of the acid dye used are larger, the ratio of mutual dyeing between the two fibers is higher, so that the different color effect is reduced. Of the animal hair fiber, so that the unique color effect is high.

[0021]

[Action] As in the present invention, animal hair fibers anionized with a polyhydric phenolic compound or an aminochloroallyl compound and shrink-proofed by applying an oxidizing agent or a polyamide epichlorohydrin resin after the oxidizing agent treatment. Animal hair fiber products such as yarn, woven fabric and knitted fabric formed by mixing animal hair fiber and untreated animal hair fiber are combined with three kinds of dyes of cationic dye, reactive dye and acid dye.
When dyed in one bath, positively charged cationic dyes are converted to negatively charged anionized animal hair fibers, reactive dyes are mainly shrink-reduced animal hair fibers with high affinity, and acid dyes are shrink-reduced. Since it is exhausted by both animal hair fibers and untreated animal hair fibers, by using three types of dyes with different hues, each product has a three-colored effect, a dye-dyed tone, heather tone or marbling tone. Can be obtained, and it is superior to conventional products composed of shades of similar colors.
It has a heather or marbling tone.

[0022]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The performance of the samples in the examples was measured by the following method. (1) Light fastness JIS L-0842 (Carbon arc light irradiation for 20 hours) (2) Washing fastness JIS L-0844 (A-2 method) (3) Sweat fastness JIS L-0848 (Alkaline sweat A method)

Example 1 Wool top was tannic acid 15% using a closed type dyeing machine.
owf, formic acid 3% owf in an aqueous solution having a bath ratio of 1:15, 96
The mixture was treated at 60 ° C. for 60 minutes, washed with water, and treated with tartarite 7% owf in an aqueous solution adjusted to pH 5 with acetic acid at 90 ° C. for 60 minutes to obtain an anionized wool top. To the same wool top as above, add 5.0% ow of sodium dichloroisocyanurate to an aqueous solution adjusted to pH 4 with formic acid.
f, immersion at 25 ° C for 25 minutes, washing with water, adding 8.0% owf of sodium sulfite, treating at 35 ° C for 15 minutes, and washing thoroughly with water to obtain a shrink-prevention top treated with an oxidizing agent. Was. Furthermore, after performing an oxidizing agent treatment in the same manner as described above, Hercoset 57 (manufactured by Dick Hercules Co., Ltd., polyamide epichlorohydrin resin) was added at 16%.
owf, add the diluted solution to a treatment bath adjusted to pH 8 with sodium bicarbonate, and treat at 40 ° C. for 20 minutes.
An oxidizing agent-resin treated shrink-proof top was obtained by drying at ℃.

Here, 30% of the anionized wool top obtained by the above-described method, 30% of the shrink-proof top treated with the oxidizing agent,
And take the untreated wool top 40% and mix,
Separately, take 30% of anionized wool top, 30% of oxidizer-resin treated shrinkproof top, and 40% of untreated wool top and mix them. A knitted fabric X and a knitted fabric Y were prepared.

The obtained two types of knitted fabrics were dyed at room temperature using a win dyeing machine in dyeing baths of the following formula 1, respectively, and then heated (1 ° C./min) and heated at 98 ° C. for 60 minutes. Staining was performed.

Formulation 1 Maxilon Blue GRL (Ciba-Geigy, cationic dye) 0.4% owf Lanazol Red B (Ciba-Geigy, reactive dye) 0.4% owf Irganol Yellow 4GL (Ciba-Geigy, acidic) Dye) 0.4% owf Albegar B (Ciba-Geigy, leveling agent) 0.6% owf Albegal A (Ciba-Geigy, leveling agent) 0.5% owf 0.8% acetic acid

When the constituent fibers of the obtained knit were decomposed, the hue of each fiber was as shown in Table 2.

[0028]

[Table 2]

As is apparent from Table 2, marbled knitted fabrics having different color effects with three different hues were obtained for both the knitted fabrics X and Y. The dyeing of the reactive dye on the shrink-prevention-treated wool top is more beautiful with the oxidizer-resin-treated shrink-proof wool top of the knitted fabric Y than in the case of only the oxidizing agent treatment of the knitted fabric X. It was a marbled knit. When the dyeing fastness of the knitted fabric X and the knitted fabric Y was measured, as shown in Table 3, both were very fast.

[0030]

[Table 3]

Example 2 An anionization treatment and an oxidizing agent-resin shrinkage treatment were respectively performed on a cheese dyeing machine under the same processing conditions as in Example 1 using a 2 / 48-count worsted knitted yarn. Untreated yarn was added to the treated yarn and the non-shrink-treated yarn, and three types of yarns were twisted to produce three heather yarns.

This heather yarn was dyed by a cheese dyeing machine in the dyeing bath of the following formula 2 in the same manner as in Example 1.

Formulation 2 Sumiacryl Red N-RL 0.3% owf (manufactured by Sumitomo Chemical Co., Ltd., cationic dye) Ranasol Yellow 4G 0.4% owf (manufactured by Ciba Geigy, reactive dye) Spranol Brilliant Sky Blue RLW 0 0.4% owf (manufactured by Bayer AG, acid dye) Albegar SET (manufactured by Ciba Geigy, leveling agent) 1.0% owf Albegar A (manufactured by Ciba Geigy, leveling agent) 0.4% owf 0.4% acetic acid 5% owf ammonium acetate 1g / liter

The dyed yarn obtained was such that the anionized yarn was red,
The shrink-proof yarn was dyed yellow-green, and the untreated yarn was dyed blue, and the three heat-treated yarns had different colors and different color effects. The dyeing fastness of the obtained three heather yarns was measured, and as shown in Table 4, it was very fast.

[0035]

[Table 4]

[0036]

According to the method of the present invention, an animal hair fiber product having a different color, such as a pre-dyed tone, having a different color effect can be obtained by a post-dyeing single bath dyeing method. In addition, since it is post-dyed, it is possible to supply short cycle, small lot, and various types of products in response to consumer needs.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-163379 (JP, A) JP-A-1-3144791 (JP, A) JP-A-2-84594 (JP, A) JP-A-62-162 263389 (JP, A) JP-A-6-2286 (JP, A) JP-A-5-222634 (JP, A) JP-B-35-13744 (JP, B1) JP-B-42-23620 (JP, B1) JP-B-42-18421 (JP, B1) JP-B-44-29552 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06P 5/00 D06P 3/87 D06P 3/14

Claims (1)

(57) [Claims] 1. An animal hair fiber which has been anionized with a polyhydric phenol compound, sulfamic acid, aminochloroallyl compound or the like, and is shrunk by an oxidizing agent treatment, or by a polyamide epichlorohydrin resin, an aminoacrylic copolymer or the like after the oxidizing agent treatment. Treated animal hair fiber,
Starting dyeing of animal hair fiber products consisting of untreated animal hair fibers at room temperature using a combination of cationic dye and wool dye
A method for producing an animal hair fiber product having a different color effect , wherein the temperature is raised to 70 ° C. at a rate of 1 ° C./min or less and dyed in one bath.