JP2021021073A - Basic dye composition, and dyeing method and dyed article using the same - Google Patents

Abstract

To provide a basic dye composition that can dye an acryl fiber, a CDP fiber, or a blended/cowoven fabric thereof uniformly with good reproducibility, and with high color development and high fastness, and a dyeing method using the same.SOLUTION: A blue basic dye composition contains, for example, a monoazo dye having a thiazolium cation part, and at least one basic dye of C.I. basic blue 162, C.I. basic blue 54, and C.I. basic blue 3.SELECTED DRAWING: None

Description

The present invention relates to a basic dye composition suitable for dyeing acrylic fiber or a basic dye dyeable synthetic fiber (Cation Dyable Polyester; CDP) (hereinafter, also referred to as "CDP fiber"), a dyeing method using the same, and a dyeing method using the same. Regarding dyed products.

In dyeing acrylic fibers or CDP fibers using basic dyes, it is known to use dyes for the three primary colors of yellow, red, and blue, and to mix and dye them in various ratios (for example, Patent Documents). See 1-5).

Regarding the basic dyes used for the three primary colors, the build-up properties of each dye are excellent, the dyeing speeds of the three primary colors are almost equal, and the temperature dependence is uniform, and the color development properties and various fastnesses of the three primary colors are excellent. Is needed.

By the way, in recent years, with an emphasis on moisture absorption and heat generation as fashionability and functionality, blended spinning and mixed weaving of acrylic fibers and CDP fibers have been expanding.

The basic dyes used for the conventional three primary colors have not been regarded as a problem with acrylic fibers alone or CDP fibers alone, but the dyeing behavior is different due to the difference in affinity between acrylic fibers and CDP fibers in blending and weaving. Unlike this, there is a problem that dyeing cannot be performed uniformly, resulting in poor reproducibility. Therefore, the three primary colors that can be uniformly dyed and have excellent reproducibility are strongly desired.

Various studies have been made to solve such a problem, but satisfactory results have not yet been obtained (see, for example, Patent Document 1).

Tokukousho 51-012754 U.S. Pat. No. 4638053 Special Fair 03-074707 Special Publication No. 57-054594 Special Publication No. 55-043022

The present invention is a basic dye composition capable of uniformly dyeing acrylic fibers, CDP fibers, or blends, mixed fabrics, or mixed knits thereof with good reproducibility and high fastness, and a dyeing method using the same. And to provide a dyed product.

As a result of diligent studies to solve the above problems, the present inventors have conducted a basic study that contains a specific blue basic dye and optionally further contains a specific red basic dye and / or a specific yellow basic dye. We have found a dye composition and a dyeing method using the same, and have completed the present invention.

That is, the present invention relates to the following 1) to 9).
1) With the basic dye represented by the following formula (1),
A blue basic dye composition containing at least one basic dye represented by the following formulas (2) to (3).

[In formula (2), R ¹ represents an (C1 to C3) alkyl group or a cyano (C1 to C3) alkyl group. In formula (3), R ² represents a hydrogen atom or an alkoxy group (C1 to C3). In formulas (1) to (3), X ⁻ represents OH ⁻ , CH ₃ SO ₄ ⁻ , or a halide ion. ]
2) The content of the basic dye represented by the formula (1) is 50 to 95% by mass.
The blue basic dye composition according to 1), wherein the total content of the basic dyes represented by the formulas (2) to (3) is 5 to 50% by mass.
3) The blue basic dye composition according to 1) or 2), wherein X ⁻ is Br ⁻ or Cl ⁻ in the above formulas (1) to (3).
4) The blue basic dye composition according to any one of 1) to 3) and
A yellow basic dye composition containing a basic dye represented by the following formula (4), and a red basic dye composition containing at least one basic dye represented by the following formulas (5) to (6). A basic dye composition containing at least one of the above compositions.

[In formula (4), R ³ represents a hydrogen atom, (C1 to C3) alkyl group, or (C1 to C3) alkoxy group. In formulas (4) to (6), X ⁻ represents OH ⁻ , CH ₃ SO ₄ ⁻ , or a halide ion. ]
5) The content of the blue basic dye composition is 30 to 60% by mass.
The content of the yellow basic dye composition is 35 to 60% by mass.
The content of the red basic dye composition is 5 to 20% by mass.
The content of the basic dye represented by the formula (1) in the blue basic dye composition is 60 to 80% by mass.
The basic dye composition according to 4), wherein the total content of the basic dyes represented by the formulas (2) to (3) in the blue basic dye composition is 20 to 40% by mass.
6) The basic dye composition according to 4) or 5), wherein X ⁻ is Br ⁻ or Cl ⁻ in the above formulas (4) to (6).
7) A step of dyeing a fiber material using the blue basic dye composition according to any one of 1) to 3) or the basic dye composition according to any one of 4) to 6). Dyeing method including.
8) The dyeing method according to 7), wherein the fiber material includes acrylic fiber, basic dye dyeable synthetic fiber (CDP), or a blend of them, a mixed fabric, or a mixed knit.
9) Acrylic fibers and bases dyed with the blue basic dye composition according to any one of 1) to 3) or the basic dye composition according to any one of 4) to 6). A dyed product containing a sex dye dyeable synthetic fiber (CDP) or a blended fabric thereof, a mixed fabric, or a mixed knitted fabric.

According to the present invention, an acrylic fiber, a CDP fiber, or a blended fabric, a mixed fabric, or a mixed knitted fabric thereof can be dyed uniformly with good reproducibility and with high fastness, and a basic dye composition using the same. A dyeing method and a dyed product can be provided.

[Blue basic dye composition]
The blue basic dye composition (B) according to the present embodiment contains a basic dye represented by the following formula (1) and at least one basic dye represented by the following formulas (2) to (3). contains.

In the above formula (2), R ¹ represents an (C1 to C3) alkyl group or a cyano (C1 to C3) alkyl group. Examples of the (C1 to C3) alkyl group include a methyl group, an ethyl group, an n-propyl group and the like. Examples of the cyano (C1 to C3) alkyl group include a cyanomethyl group, a cyanoethyl group, and a cyanopropyl group. As R ¹ , a methyl group or a cyanoethyl group is preferable.

In the above formula (3), R ² represents a hydrogen atom or an alkoxy group (C1 to C3). Examples of the (C1 to C3) alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group and the like. As R ² , a hydrogen atom or an ethoxy group is preferable.

In the above formulas (1) to (3), X ⁻ represents OH ⁻ , CH ₃ SO ₄ ⁻ , or a halide ion, and preferably Br ⁻ or Cl ⁻ .

The basic dye represented by the above formula (1) is described in Patent Document 1 and the like. The basic dye represented by the above formula (2) is described in Patent Document 2 and the like, and for example, C.I. I. Basic Blue 162 (R ¹ in formula (2) is a cyanoethyl group, X ⁻ is CH ₃ SO ₄ ⁻ ) and C.I. I. Basic blue 54 (R ¹ in the formula (2) is a methyl group and X ⁻ is CH ₃ SO ₄ ⁻ ) can be mentioned. The basic dye represented by the above formula (3) is described in JP-A No. 10-3183 and the like. Examples of the basic dye represented by the above formula (3) include C.I. I. Basic blue 3 (R ² in the formula (3) is a hydrogen atom and X ⁻ is Cl ⁻ ) can be mentioned. The basic dyes represented by the above formulas (1) to (3) are commercially available.

The blue basic dye composition (B) according to the present embodiment contains a basic dye represented by the above formula (1) and at least one basic dye represented by the above formulas (2) to (3). Since it is contained, the dyeing rate on acrylic fibers and CDP fibers can be approximated, and the dyeability of dyed products including blended fabrics, mixed fabrics, or mixed knitted fabrics of these fibers is visually uniform. can do.

The blue basic dye composition (B) according to the present embodiment has a content of the basic dye represented by the above formula (1) of 50 to 95% by mass, and is represented by the above formulas (2) to (3). The total content of the basic dyes is preferably 5 to 50% by mass, and the content of the basic dye represented by the above formula (1) is 50 to 80% by mass, and the above formulas (2) to (2) to It is more preferable that the total content of the basic dyes represented by (3) is 20 to 50% by mass. By setting the content of the basic dye in the above range, the dyeing rate on the acrylic fiber and the CDP fiber tends to be more approximate.

Further, the blue basic dye composition (B) according to the present embodiment is described in C.I. I. Basic blue 35 may be contained. C. I. The content of Basic Blue 35 can be appropriately adjusted according to the desired color tone.

[Basic dye composition]
The basic dye composition according to the present embodiment includes the above blue basic dye composition (B), a yellow basic dye composition (Y) containing a basic dye represented by the following formula (4), and a yellow basic dye composition (Y). It contains at least one composition of the red basic dye composition (R) containing at least one basic dye represented by the following formulas (5) to (6). By further containing a yellow basic dye and / or a red basic dye in addition to the blue basic dye, a basic dye composition having a desired color tone can be obtained. The content of each of the blue basic dye composition (B), the yellow basic dye composition (Y), and the red basic dye composition (R) can be appropriately adjusted according to the desired color tone.

In the above formula (4), R ³ represents a hydrogen atom, an (C1 to C3) alkyl group, or a (C1 to C3) alkoxy group. Examples of the (C1 to C3) alkyl group include a methyl group, an ethyl group, an n-propyl group and the like. Examples of the (C1 to C3) alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group and the like. As R ^3, a hydrogen atom or a methoxy group is preferable.

In the above formulas (4) to (6), X ⁻ represents OH ⁻ , CH ₃ SO ₄ ⁻ , or a halide ion, and preferably Br ⁻ or Cl ⁻ .

The basic dye represented by the above formula (4) is described in Patent Document 5 and the like, and for example, C.I. I. Basic Yellow 51 (R ³ in equation (4) is a hydrogen atom, X ⁻ is CH ₃ SO ₄ ⁻ ), C.I. I. Basic Yellow 29 (R ³ in formula (4) is a methyl group, X ⁻ is Cl ⁻ ), and C.I. I. Examples thereof include Basic Yellow 28 (R ³ in the formula (4) is a methoxy group and X ⁻ is CH ₃ SO ₄ ⁻ ). The basic dye represented by the above formula (5) is described in Patent Document 4 and the like, and for example, C.I. I. Basic red 46 (X ⁻ in equation (5) is Br ⁻ ) can be mentioned. The basic dye represented by the above formula (6) is described in Patent Document 5 and the like, and for example, C.I. I. Basic red 29 (X ⁻ in formula (6) is Cl ⁻ ) can be mentioned. The basic dyes represented by the above formulas (4) to (6) are commercially available.

The basic dye composition according to the present embodiment may be a basic dye composition for black. The basic dye composition for black has a content of the blue basic dye composition (B) of 30 to 60% by mass and a content of the yellow basic dye composition (Y) of 35 to 60% by mass. The content of the red basic dye composition (R) is preferably 5 to 20% by mass. Further, the blue basic dye composition (B) has a content of the basic dye represented by the above formula (1) of 60 to 80% by mass, and is represented by the above formulas (2) to (3). The total content of the dyes is preferably 20 to 40% by mass, and the content of the basic dye represented by the above formula (1) is 70 to 80% by mass, and the above formulas (2) to (3). More preferably, the total content of the basic dyes represented by is 20 to 30% by mass. By setting the content of the basic dye composition of each color in the above range, the dyeing rate on the acrylic fiber and the CDP fiber tends to be more approximate.

As described above, the blue basic dye composition (B) is described in C.I. I. Basic blue 35 may be contained. C. I. The content of Basic Blue 35 can be appropriately adjusted according to the desired color tone.

[Blue basic dye composition, method for preparing basic dye composition, etc.]
In the preparation of the blue basic dye composition and the basic dye composition, the blending method of each basic dye is not particularly limited. For example, a method in which each basic dye is synthesized separately and then blended; a method in which a dye solution containing each basic dye produced during synthesis is mixed and then dried to form a composition; in a dyeing bath. A method of dissolving each dye to have the same composition as each composition in a dyeing bath; etc. can be adopted. At that time, the mixing ratio of each basic dye is appropriately determined according to the desired color tone.

The blue basic dye composition and the basic dye composition may be prepared from known additives such as concentration modifiers, dispersants, leveling agents, precipitation inhibitors, sequestrants, reduction inhibitors and the like, if necessary. May be contained.
The form of the blue basic dye composition and the basic dye composition is not particularly limited, and may be, for example, powdery, granular, or liquid.

A blue basic dye composition or each basic dye constituting the basic dye composition, and if necessary, the above additives and the like are added to a dyeing bath, a padding bath, or a printing paste to prepare a dyeing bath and the like. In the case of dyeing, the order of dissolving each basic dye, additive and the like may be arbitrary. The amount of each component to be used may also be determined with reference to a known method.

The blue basic dye composition and the basic dye composition according to the present embodiment are useful for dyeing a fiber material containing acrylic fiber or CDP fiber, and in particular, a blended blend of acrylic fiber and CDP fiber, a mixed fabric, or It is suitable for dyeing textile materials including mixed knitted fabrics. The proportions of acrylic fibers and CDP fibers in the blended fabric, the mixed fabric, and the mixed knitted fabric can be arbitrarily adjusted according to the desired properties. Further, the dyeable fiber material includes a blended or mixed fiber of these fibers or mixed fibers with other fibers (for example, cotton, rayon, polyester fiber, acetate fiber, wool, silk, polyamide fiber such as nylon). Examples include textiles and mixed knitted fabrics.

Examples of the CDP fiber include acid-modified polyester fiber. The acid-modified polyester fiber is, for example, a fiber modified by using sulfoisophthalic acid as a part of the isophthalic acid component of the polyester fiber and introducing a sulfonic acid group into the fiber molecule so that it can be dyed with a basic dye. ..

According to the blue basic dye composition and the basic dye composition according to the present embodiment, uniformly dyed dyed products such as acrylic fibers, CDP fibers, or blends thereof, mixed fabrics, or mixed knitted fabrics are used. A dyed product containing the dye can be produced, and the reproducibility is also excellent. Further, the blue basic dye composition and the basic dye composition according to the present embodiment can dye acrylic fibers, CDP fibers, or blends, mixed fabrics, or mixed knits thereof with high fastness. It also has excellent color development.

[Dyeing method using a blue basic dye composition or a basic dye composition]
The dyeing method according to the present embodiment includes a step of dyeing a fiber material using the blue basic dye composition or the basic dye composition. As the fiber material, the above-mentioned fiber material in which dyeing with a blue basic dye composition or a basic dye composition is useful can be used.

The step of dyeing the fiber material using the blue basic dye composition or the basic dye composition can be carried out according to, for example, the following known methods, but is not limited thereto.
In the dyeing step, for example, a blue basic dye composition or a basic dye composition according to a desired hue and concentration is added to the dyeing bath, and an acid solution regulator is added. Examples of the acid solution adjusting agent include organic acids such as formic acid, acetic acid, citric acid and malic acid and salts thereof; inorganic acids such as hydrochloric acid and sulfuric acid and salts thereof; One type of these acidic liquid adjusting agents may be used alone, or two or more types may be used in combination. The amount of the acidic solution preparation used is appropriately adjusted and is not particularly limited.
After the dyeing step is completed, after washing with water or hot water, washing is performed in a soaping bath containing a commercially available soaping agent, or reduction washing using hydrosulfite, thiourea dioxide or the like is performed to complete the dyeing.

The amount of the blue basic dye composition or the basic dye composition used is usually preferably about 0.0005 to 15% by mass with respect to the mass of the fiber material.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.

As the basic dyes represented by the above formulas (1) to (7), the following basic dyes (a) to (i) were used. C. I. Basic is a color index generic name. The blending ratio of the basic dye is shown in Table 1. In the text, "part" represents a mass part unless otherwise specified.

(A) Dye in which X ⁻ in the formula (1) is Cl ⁻ (b) C.I. I. Basic Blue 162 (corresponds to the basic dye of formula (2))
(C) C.I. I. Basic Blue 54 (corresponding to the basic dye of formula (2))
(D) C.I. I. Basic Blue 3 (corresponds to the basic dye of formula (3))
(E) C.I. I. Basic Yellow 51 (corresponding to the basic dye of formula (4))
(F) C.I. I. Basic Yellow 29 (corresponding to the basic dye of formula (4))
(G) C.I. I. Basic Yellow 28 (corresponding to the basic dye of formula (4))
(H) C.I. I. Basic Red 46 (corresponding to the basic dye of formula (5))
(I) C.I. I. Basic Red 29 (corresponding to the basic dye of formula (6))

[Example of formulation of basic dye composition]
The basic dye compositions of Formulation Examples 1 to 18 and Comparative Formulation Examples 1 to 9 were prepared according to the combinations of the basic dyes shown in Table 1 below and the amounts used thereof. The numerical values in Table 1 represent the amount (unit: part) of each basic dye used.

[Evaluation]
Each of the obtained basic dye compositions was evaluated by a dyeing distributability test and a fastness test.

(Dyeing distributability test)
(1) Procedure Water was added to each of the basic dye compositions of Formulation Examples 1 to 18 and Comparative Formulation Examples 1 to 9 shown in Table 1 and 1 part of acetic acid to prepare a dyeing bath having a total amount of 600 parts. 25 parts of acrylic muslin (manufactured by Mitsubishi Chemical Co., Ltd., obtained from Color Dyeing Co., Ltd.) and CDP knit ("cation dyeable polyester knit smooth (processing system)", manufactured by Teijin Limited, etc. (Obtained from Color Dyeing Co., Ltd.) 25 parts of two types of fiber materials were added, treated at 40 ° C for 10 minutes, and then heated to a top temperature of 100 ° C or 105 ° C at a heating speed of 1 ° C / min. .. The fibrous material was dyed at each top temperature for 60 minutes and then washed with water. Next, soaping was performed at 70 ° C. for 15 minutes in 1000 parts of an aqueous solution containing 2 g / L of a commercially available soaping agent (Kayatector E, manufactured by Nippon Kayaku Co., Ltd.), 2 g / L of hydrosulfite, and 1 g / L of caustic soda. Then, it was washed with water and dried to obtain a dyed product.

(2) Judgment method C.I. of the obtained acrylic muslin and CDP knit dyed products. I. E. The density (brightness L *) and hue (a *, b *) in the LAB color space were measured under a D65 light source using a colorimeter Color Eye CE7100 (manufactured by Macbeth). The color difference ΔE is C.I. I. It was calculated using the E color difference formula. Table 2 below shows the relative concentration of the CDP knit dyed product (concentration of the acrylic muslin dyed product: 100) and the color difference ΔE based on the acrylic muslin dyed product. The closer the relative density is to 100, the better, and the closer the color difference ΔE is to 0, the better.

(3) Test Results As shown in Table 2, even when any of the basic dye compositions of Formulation Examples 1 to 18 was used, the difference in concentration and the change in hue were extremely small, and acrylic muslin and CDP knit were used. The difference in dyeing distribution was small. From this result, it was shown that the basic dye compositions of Formulation Examples 1 to 18 can uniformly dye a fiber material containing a blended fabric of acrylic fiber and CDP fiber, a mixed fabric, or a mixed knitted fabric. On the other hand, the basic dye compositions of Comparative Formulation Examples 1 to 9 had a large difference in concentration of acrylic muslin and CDP knit and a large color difference ΔE as compared with the basic dye compositions of Formulation Examples 1 to 18.

Even if the mixing ratio of acrylic muslin and CDP knit was changed, the dyeing and distributability when the basic dye compositions of Formulation Examples 1 to 18 were used gave the same results (data not shown). From this result, it was shown that the basic dye compositions of Formulation Examples 1 to 18 can uniformly dye the fiber material including the blended products of the acrylic fibers and the CDP fibers regardless of the mixing ratio of the acrylic fibers and the CDP fibers.

(Robustness test)
(1) Test Preparation Water was added to each of the basic dye compositions of Formulation Examples 1, 4, 5, 8 and 10 to 17 shown in Table 1 and 1 part of acetic acid to prepare a dyeing bath having a total amount of 600 parts. 50 parts of a mixed knitted fabric of acrylic fiber and CDP fiber was put into this dyeing bath, treated at 40 ° C. for 10 minutes, and then heated to a top temperature of 105 ° C. at a heating speed of 1 ° C./min. The mixed knitted fabric was dyed at the top temperature for 60 minutes and then washed with water. Next, soaping was performed at 70 ° C. for 15 minutes in 1000 parts of an aqueous solution containing 2 g / L of a commercially available soaping agent (Kayatector E, manufactured by Nippon Kayaku Co., Ltd.), 2 g / L of hydrosulfite, and 1 g / L of caustic soda. Then, it was washed with water and dried to obtain a dyed product.

(2) Light resistance (JIS L 0843)
Dyeing fastness to xenon arc lamp was performed according to JIS L 0843. The irradiation was performed under the conditions of an irradiance of 50 W / m2 (wavelength 300 to 400 nm), a BPT (black panel temperature) of 63 ° C., a relative humidity of 50%, and an irradiation exposure of 7100 kJ / m2. The evaluation judgment was displayed with a grade showing a discoloration similar to that of the blue scale irradiated at the same time. Grade 5 is the strongest against light, and grade 1 is the weakest against light. The results are shown in Table 3 below.

(3) Laundry (JIS L 0844)
The fastness to washing was carried out according to JIS L 0844. Acrylic and cotton were attached to the dyed product as attached white cloth, and treated by the A-2 method (Marcel soap 5 g / L, liquid volume 100 mL, 50 ° C., 30 minutes). In the evaluation judgment, the degree of contamination of the attached white cloth was indicated by a grade based on the gray scale JIS L 0805 for contamination. Grade 5 shows the best result, and grade 1 shows the worst result. The results are shown in Table 3 below.

(4) Results As shown in Table 3, the dyed products obtained by using the basic dye compositions of Formulation Examples 1, 4, 5, 8 and 10 to 17 were all tested for fastness to light. The grade was "5", indicating excellent light resistance. In addition, in the fastness test for washing, all dyed products show a high grade of "5" or "4-5", and it is difficult for color fading and color transfer due to washing, and it is also excellent in washing fastness. Shown.

Claims (9)

The basic dye represented by the following formula (1) and
A blue basic dye composition containing at least one basic dye represented by the following formulas (2) to (3).

[In formula (2), R ¹ represents an (C1 to C3) alkyl group or a cyano (C1 to C3) alkyl group. In formula (3), R ² represents a hydrogen atom or an alkoxy group (C1 to C3). In formulas (1) to (3), X ⁻ represents OH ⁻ , CH ₃ SO ₄ ⁻ , or a halide ion. ] The content of the basic dye represented by the formula (1) is 50 to 95% by mass.
The blue basic dye composition according to claim 1, wherein the total content of the basic dyes represented by the formulas (2) to (3) is 5 to 50% by mass. The blue basic dye composition according to claim 1 or 2, wherein X ⁻ is Br ⁻ or Cl ⁻ in the formulas (1) to (3). The blue basic dye composition according to any one of claims 1 to 3 and
A yellow basic dye composition containing a basic dye represented by the following formula (4), and a red basic dye composition containing at least one basic dye represented by the following formulas (5) to (6). A basic dye composition containing at least one of the above compositions.

[In formula (4), R ³ represents a hydrogen atom, (C1 to C3) alkyl group, or (C1 to C3) alkoxy group. In formulas (4) to (6), X ⁻ represents OH ⁻ , CH ₃ SO ₄ ⁻ , or a halide ion. ] The content of the blue basic dye composition is 30 to 60% by mass.
The content of the yellow basic dye composition is 35 to 60% by mass.
The content of the red basic dye composition is 5 to 20% by mass.
The content of the basic dye represented by the formula (1) in the blue basic dye composition is 60 to 80% by mass.
The basic dye composition according to claim 4, wherein the total content of the basic dyes represented by the formulas (2) to (3) in the blue basic dye composition is 20 to 40% by mass. The basic dye composition according to claim 4 or 5, wherein X ⁻ is Br ⁻ or Cl ⁻ in the formulas (4) to (6). The step of dyeing a fiber material with the blue basic dye composition according to any one of claims 1 to 3 or the basic dye composition according to any one of claims 4 to 6 is included. Dyeing method. The dyeing method according to claim 7, wherein the fiber material includes acrylic fiber, a basic dye dyeable synthetic fiber (CDP), or a blended fabric, a mixed fabric, or a mixed knitted fabric thereof. Acrylic fiber, basic dye dyed with the blue basic dye composition according to any one of claims 1 to 3 or the basic dye composition according to any one of claims 4 to 6. Dyeable synthetic fibers (CDPs), or dyes containing blends, mixed fabrics, or mixed knits thereof.