JPH1096179A - Different color dyeing of fiber composite material comprising modacrylic fiber and acrylic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dyeing method capable of dyeing a fiber composite material comprising an acrylic fiber and a modacrylic fiber to be dyed by using the same dye and different in dye absorbing ability in the same bath in different colors and making the fiber composite material excellent in design. SOLUTION: This method for dyeing comprises dyeing both a modacrylic fiber and an acrylic fiber in different colors by adding 0-60wt.% of an inorganic salt and 0-60wt.% based on the fiber weight of an organic compound having swelling action on fibers to a dyeing bath in dyeing a fiber composite material of the modacrylic fiber and the acrylic fiber with a cationic dye. A monovalent or a divalent alkali metal such as sodium sulfate, sodium chloride, magnesium sulfate, magnesium chloride, potassium sulfate or potassium chloride is used as the inorganic salt. An alkyl-phthalimide such as N-butylphthalimide or an aromatic ether compound such as benzyl aminoethyl ether is used as the organic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a flame-retardant or self-extinguishing garment by blending modacrylic fiber, which is a flame-retardant fiber, with acrylic fiber, which is a flammable fiber, and using it as a fiber composite. When commercializing textile products such as toys, interiors and bedding products, the modacrylic fiber and acrylic fiber having different dyeing properties constituting the fiber composite are dyed in different colors in the same bath to provide a fiber having a design property. The present invention relates to a method for obtaining a complex.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for flame retardancy in daily necessities both in Japan and overseas, and legislation is being developed around the world. Under these circumstances, in the field of textiles,
In various product fields such as curtains, carpets, stuffed toys, and clothing, flame-retardant acrylic fiber is combined with flame-retardant modacrylic fiber in a ratio that can meet the flame-retardant standards of each product, and the product is flame-retardant Product planning for realization is increasing.

Usually, both modacrylic fiber and acrylic fiber are most commonly dyed with a cationic dye, and both are actually dyed with a cationic dye.
That is, since both are dyed using the same dye,
In the dyeing in the same bath, it is difficult to obtain a heterochromatic property between the two fibers that exceeds the color difference caused by the difference in the dyeing behavior of the polymer constituting each of the modacrylic fiber and the acrylic fiber. It has been difficult to obtain a so-called high-dyed product having a so-called yarn-dyed tone, as in the case of blended cotton or cross-woven yarns dyed in different colors.

[0004] As described above, when dyeing yarns, raw fabrics, woven or knitted fabrics which are intermediate products for composing these products, the acrylic fiber and the modacrylic fiber are dyed with the same dye, and the dye-absorbing ability is also high. Dyes in the same bath because of the similarity, and dyes the hue of acrylic fiber and modacrylic fiber in a different color with a design that exceeds the color difference due to the difference in the dyeing behavior of both fibers, giving a more luxurious first-dye In order to develop a color tone, there are limitations on the dyeing conditions, and there is no large difference in hue density between the two fibers dyed in the same bath, so that the range of product planning is limited.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber composite composed of acrylic fiber and modacrylic fiber which are dyed using the same dye and have similar dye-absorbing ability in the same bath. It is an object of the present invention to provide a dyeing method which can dye both fibers in different colors even by dyeing, and can produce a fiber composite having excellent design properties.

[0006]

Means for Solving the Problems The present inventors have made a subtle difference between the acrylic fiber and the modacrylic fiber in the dye absorption mechanism, the dyeing behavior, and the dyeing behavior received from inorganic compounds and organic compounds added to the dye bath. As a result of repeated investigations, the inventors have found a method of utilizing these differences to control the final amount of dye absorbed and to develop a different color having a design.

That is, according to the present invention, when a fiber composite comprising modacrylic fiber and acrylic fiber is dyed using a cationic dye or a disperse dye, at least one kind of inorganic salt and / or fiber is added to the dye bath. This is a dyeing method characterized by dyeing both fibers with different colors by adding an organic compound having a swelling action. In the present invention, the fact that the modacrylic fiber and the acrylic fiber are different colors is a concept that includes the difference in shades of color.

As described above, the present invention finds that the action of a drug such as a swelling agent composed of an inorganic salt or an organic compound is different for the above two types of fibers. By controlling the action of the agent on the fibers under suitable conditions, the fiber composite of acrylic fiber and modacrylic fiber can be dyed in different colors in the same bath.

The following characteristics are clear when the dyeing behavior of the above-mentioned allyl fibers and modacrylic fibers and the effects of the drugs are arranged. Absorption speed and absorption amount of cationic dye: Modacryl fiber <Acrylic fiber Absorption speed, absorption amount of disperse dye: Modacryl fiber>
Acrylic fiber Absorption rate of cationic dye when inorganic salts are present in the dyeing bath: a large dyeing effect is obtained for modacrylic fiber, and a slow dyeing effect is obtained for acrylic fiber. Strength of the swelling effect when an organic compound which swells the fiber, such as an aromatic ether compound or an alkyl-phthalimide compound, is present in the dyeing bath ... modacrylic fiber> acrylic fiber Slowing agent such as quaternary ammonium salt Effect of a slow dye in the presence of a dye in a dye bath: modacrylic fiber> acrylic fiber More importantly, the dye (or fiber) migration effect,
The leveling effect that the dye moves through the fiber and the dyeing bath during the boiling dyeing and the dye density in the fiber is averaged is almost nonexistent for modacrylic fiber, and acrylic fiber is large.

By dyeing these behavioral features singly or in combination, it is possible to control the hue of acrylic fibers and modacrylic fibers within a considerable range.

Hereinafter, the present invention will be described in more detail. Monovalent and divalent alkali metal salts, for example, salts such as potassium chloride, sodium chloride, magnesium chloride, potassium chloride, potassium sulfate, sodium sulfate, and magnesium sulfate have different effects when added to a dye bath. However, the acrylic fibers have a gentle slow dyeing action. Although this effect has not been clarified theoretically, these salts neutralize the surface potential of the acrylic fiber, prevent the cationic dye from assembling on the fiber surface, and reduce the chance of contact between the fiber and the dye. According to the description. In addition, as for modacrylic fiber, in contrast to acrylic fiber, which is mostly dyed by ionic bonds, the dye is directly dissolved into the fiber and diffuses, so-called a solid-dissolution dyeing mechanism is relatively large, and the dyeing bath contains The presence of salts reduces the solubility of the dye and promotes the dyeing by a solid dissolution mechanism. Therefore, it is considered that the salts have a promoting action on modacrylic fiber. The amount of the inorganic salt used varies depending on the dyeing concentration, but is usually used in the range of 0 to 60%, preferably 5 to 40% based on the fiber weight. It is possible to use more than 60%, but in the case of the scale of the present production, the dye is tarred, which causes problems such as contamination of the material to be dyed and the dyeing machine. On the other hand, alkyl-
Phthalimide compounds, aromatic ether compounds such as N
-Butyl phthalimide, benzyl cyanoethyl ether, etc. have a swelling effect on both acrylic fiber and modacrylic fiber, but the degree of swelling of both is different, and when compared in the same amount, stronger swelling action on modacrylic fiber. The acrylic fiber has a remarkable migration effect. Therefore, it can be said that the same action as that of the inorganic salts is exerted more strongly than the inorganic salts. As described above, the action of the inorganic salt on the acrylic fiber and modacrylic fiber can be further promoted by using the swelling agent in combination, and the dyeing time can be shortened. The amount of the swelling agent to be used is adjusted according to the dyeing concentration in the range of 0 to 10%, preferably 0 to 8%, based on the weight of the fiber composite. Depending on the color tone or color density to be dyed, it may not be necessary to use it. However, when it is used in excess of 10%, shrinkage and hardening of the dyed product may be caused to impair the merchantability.

In addition, a quaternary ammonium salt-based cationic dyeing agent generally used has a slow dyeing effect in a dyeing bath of about 3 times that of modacrylic fibers on acrylic fibers.
It is twice as effective, and it is possible to dye both fibers in different colors by allowing the release agent to be present in the dye bath in a large amount and dyeing almost only the acrylic fibers.

Acrylic fiber is currently produced by seven companies in Japan, for example. However, the amount of the third component copolymerized for dyeing differs depending on the fiber manufacturer. Therefore, the dye absorption speed and the saturated absorption amount are different, and these are usually expressed by half-dyeing time, F value, etc., and are used as a measure of the balance between the dye to be used and the slow dye. Therefore, it is necessary to adjust the addition amount of the metal salts and the swellable organic compound used in the present invention according to the F value different for each acrylic fiber manufacturer, the brand of acrylic fiber combined with modacrylic fiber, or the ratio of mixing both. Needless to say, there is. The actual prescription examples are shown in Table 1 below.

[0014]

[Table 1]

The modacrylic fiber used in the present invention is a fiber comprising a copolymer containing 40 to 50% by weight of a halogen-containing vinyl compound and 50 to 40% by weight of an acrylic compound and a third component.

The acrylic fiber used in the present invention is a fiber made of a polymer containing 50% by weight or more of an acrylic compound.

The fiber composite comprising modacrylic fiber and allyl fiber is, for example, one fiber of both fibers.
A woven or knitted fabric obtained by mixing specialty yarns spun using 00%, or a mixed spun yarn obtained by mixing and spinning both fibers, a woven or knitted fabric using the mixed spun yarn, a string or the like, a fabric of a mixed spinning weave, or the like.
A mixture of filaments may be used in place of the spun yarn.

[0018]

【Example】

(Example 1) A spun yarn 10/100% using modacrylic fiber 1.5d (denier) x 51 mm 100% as the warp yarn of a commercially available 30/2 cotton count acrylic spun yarn (F value 3.2).
1 was used as a weft to obtain a plain-woven fabric. This fabric,
Set in a small Wins type dyeing machine, pH about 3.
Tailoring the dyeing bath adjusted to 5 and running the dyeing machine to 50
The temperature was raised to ° C. Subsequently, a quaternary ammonium salt-based cationic dyeing agent 1.5% owf (Astragal PAN: B
ayer) and after 5 minutes the dye concentration is 1.0% o
Cationic dye (Max)
ilon Blue and Red; Ciba-Geigy
Was dissolved in acetic acid and hot water, and then diluted with hot water and added. The temperature of the dyeing bath was raised from 50 ° C. to 85 ° C. at a rate of 1 ° C. for 1 minute, and then the temperature was raised from 80 ° C. for 2 minutes at a rate of 1 ° C., and the dye was boiled to continue dyeing for 60 minutes. Normal flexible processing,
Dehydration drying-width setting was performed. The obtained fabric was a yarn-dyed fabric in which the warp yarn was dyed dark blue and the weft yarn was dyed pale yellowish blue, and corresponded to Category 1 of the flammability test of JIS L-1091. .

Example 2 Acrylic Shrinkable Fiber 3d ×
V (bias cut) (hot water shrinkage 23%, F value 2.
2) 40% and modacrylic flat fiber 7d × 127mm
(Hot water shrinkage 3%, F value 1.4) 60% were mixed and spun with a worsted spinning machine, and a 2/28 (28th twin yarn) was obtained through a twisting step. 30 kg of this yarn is set in a bulky injection type skein dyeing machine, and ultraphosphoric acid (Ultra MT-11) is used.
0: manufactured by Otashima Chemical Co., Ltd.), a dyeing bath adjusted to about pH 3.5 was prepared, and the temperature was raised to 50 ° C. while operating the dyeing machine. Furthermore, the cationic three primary colors (Maxilon: Cib) prepared so as to be gray at a total dye concentration of 0.25% owf.
a-Geigy) was dissolved in acetic acid, diluted with hot water and added. Then benzyl cyanoether (Theonol A
T: Meisei Chemical Industry Co., Ltd.), 6% owf based on the weight of the yarn, and 20% owf based on the weight of the anhydrous sodium sulfate, and the temperature was raised to 85 ° C. at a rate of 1 ° C. per minute, and then 0%. The mixture was heated to a boiling point of 5 ° C./min until boiling, and further subjected to boiling dyeing for 30 minutes, followed by ordinary washing-softening treatment-drying to obtain a marbled gray bulky yarn. Using a normal pile knitting machine (manufactured by Kubo Tekko), the yarn is piled at a height of 11 mm.
mm web was knitted down. This was back coated as usual, and a bore knitting pile was created through the usual finishing process of brushing-polishing-shirring, the modacrylic fiber of the guard hair was gray,
This was a so-called two-stage pile in which acrylic shrink fibers of down hair were dyed in a very light gray color, which was a highly productive pile product.

Example 3 Worsted yarn 5 used in Example 2
0 kg was set in a bulky injection type dyeing machine of a considerable capacity, and a dyeing bath was prepared to prepare ultraphosphoric acid (Ultra MT-
110: manufactured by Otajima Chemical Co., Ltd.), and then adjusted to a pH of about 3.5, and then a cationic dye solution (Aizen Cath) formulated to have a medium brown color at a dye concentration of 1.0% owf.
ilon DP three primary colors: Hodogaya Chemical) 1.5ow in total
f and a yellow disperse dye solution (Kayalon Fast)
Yellow G: Nippon Kayaku) 0.5% owf is added, and anhydrous potassium chloride 10 g / L and N-butyl phthalimide (Levegal PEW: Baye) are further added.
0.5 g / L was added, and the temperature was increased from 60 ° C. to 90 ° C. at a rate of 1 ° C. per minute, and kept at 90 ° C. for 15 minutes. Then, bring to a boil at a rate of 1 ° C. for 2 minutes.
Stained for 0 minutes. After normal softening-drying, the resulting yarn was a brown and tan marbled, bulky yarn. When this was finished into a knitted pile in the same manner as in Example 2, a pile product having a two-stage pile in which stab hair (guard hair) was tan and fluff (down hair) was brown was obtained.

Example 4 One skein 25 used in Example 2
After 100 kg of the worsted yarn of No. 0 was hung on a dyeing frame and subjected to a pre-bulky treatment, the dyeing bath adjusted to a pH of about 3.5 with the ultraphosphoric acid used in Example 3 was applied to a rotating back type dyeing machine of a considerable capacity. Set after tailoring. The temperature of the dyeing bath was raised to 40 ° C., and the cationic dye (Astragal PA) was used.
N: 0.5% owf (manufactured by Bayer), 20 g of crystalline sodium sulfate, and a cationic dye (Cathilon T series, three primary colors of dye: Hodogaya Chemical Industry Co., Ltd.) blended so as to be gray in total 0.6% owf was dissolved in hot water and charged. Subsequently, the dyeing bath was heated to 90 ° C. at a rate of 1 ° C. per minute and brought to a boil at a rate of 1 ° C. for another 2 minutes to dye for 30 minutes. After that, once dye bath is 8
The temperature was lowered to 0 ° C., and 5% owf of benzyl cyanoethyl ether (Theonol AT: manufactured by Meisei Chemical Industry Co., Ltd.) and a total of 0.3% owf of a disperse dye (Paranil E type three primary colors: manufactured by Basf) blended to be brown. It was brought to a boil again in 15 minutes after being charged, and dyed for another 30 minutes. Subsequently, through ordinary softener treatment-dehydration-drying, the obtained yarn was dyed in a dark gray color and a slightly light brown mixed tone. Using this yarn, the same knitting finish as in Example 2 was performed, and the down hair (acrylic fiber) became dark gray and the guard hair (modacrylic fiber)
It was a pile product with a two-color, two-tier pile that was slightly tinted brown.

[0022]

As described above, according to the present invention, a fiber composite consisting of acrylic fiber and modacrylic fiber which are dyed using the same dye and have similar dye-absorbing ability is dyed in the same bath. Thus, both fibers can be dyed in different colors, and a fiber composite having excellent design properties can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06P 1/673 D06P 1/673

Claims (10)

[Claims] When a fiber composite comprising modacrylic fiber and acrylic fiber is dyed in the same bath using a cationic dye or a disperse dye, at least one inorganic salt and / or fiber is swollen in the dye bath. A dyeing method characterized in that both fibers are dyed in mutually different colors by adding an organic compound having an effect of causing the fibers to have a different color. 2. The dyeing method according to claim 1, wherein the dye used for dyeing is a general cationic dye, an anionic coating cationic dye, or a disperse dye. 3. The dyeing method according to claim 1, wherein the inorganic salt added to the dyeing bath is a monovalent or divalent alkali metal salt. 4. A monovalent or divalent alkali metal salt,
Sodium sulfate, sodium chloride, magnesium sulfate,
The dyeing method according to claim 3, which is at least one selected from magnesium chloride, potassium sulfate, and potassium chloride. 5. The dyeing method according to claim 1, wherein the amount of the inorganic salt added to the dyeing bath is 0 to 60% based on the weight of the fiber. 6. The method according to claim 1, wherein the organic compound added to the dyeing bath is at least one of an alkyl-phthalimide compound and an aromatic ether compound. 7. The method according to claim 7, wherein the alkyl-phthalimide compound is N-
The dyeing method according to claim 6, wherein the dye is butylphthalimide. 8. The method according to claim 6, wherein the aromatic ether compound is benzyl cyanoethyl ether. 9. The dyeing method according to claim 1, wherein the amount of the organic compound added to the dyeing bath is from 0 to 60% by weight of the fiber. 10. A quaternary ammonium salt-based cationic dyeing agent is added to a dyeing bath when a fiber composite comprising modacrylic fiber and acrylic fiber is dyed in the same bath using a cationic dye or a disperse dye. Dyeing both fibers in mutually different colors.