TW201940600A - Basic dye composition, and dyeing method using the same and dyeing product - Google Patents

Abstract

The present invention provides a basic dye composition, and a dyeing method using the same and a dyeing product; the basic dye composition containing a basic dye represented by the following formula (1) and at least one type of basic dye represented by the following formulas (2) to (3). In the formula (2), R1 represents a (C1-C3) alkyl group or a cyano (C1-C3) alkyl group. In the formula (3), R2 represents a hydrogen atom or a (C1-C3) alkoxy group. In the formulas (1) to (3), X- represents OH-, CH3SO4- or a halide ion.

Description

Basic dye composition, dyeing method and dyed matter using same

The present invention relates to a basic dye composition suitable for dyeing acrylic fibers or basic dye dyeable synthetic fibers (Cation Dyeable Polyester; CDP) (hereinafter also referred to as "CDP fibers"), and to use the basic dye Dyeing method and composition of composition.

It is known that the dyeing of the three primary colors of yellow, red, and blue is used in the dyeing of acrylic fibers or CDP fibers using basic dyes, and these are dyed in various proportions (for example, refer to Patent Documents 1 to 5).

The basic dyes used in the three primary colors must be excellent in build-up of each dye, the dyeing speed of the three primary colors is about equal, the temperature dependence is consistent, and the color development of the three primary colors and the fastness are excellent.

However, in recent years, attention has been paid to fashionable or functional hygroscopic heat, and the blending and interweaving of acrylic fibers and CDP fibers has continued to expand.

In the past, the basic dyes used in the three primary colors did not cause problems when acrylic fibers or CDP fibers were used alone, but in the blending and interweaving of acrylic fibers and CDP fibers, the dyeing behaviors were different due to different affinity. , The problem that the uniform dyeing cannot be produced, and the reproducibility is poor. Therefore, the three primary colors that can be uniformly dyed and excellent in reproducibility are strongly expected.

Various studies have been made to solve such problems, but satisfactory results have not yet been obtained (for example, refer to Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 51-012754
[Patent Document 2] US Patent No. 4638053
[Patent Document 3] Japanese Patent Publication No. 03-074707
[Patent Document 4] Japanese Patent Publication No. 57-054594
[Patent Document 5] Japanese Patent Publication No. 55-043022

[Questions to be Solved by the Invention]

An object of the present invention is to provide a basic dye composition that enables acrylic fibers, CDP fibers, or blends, interwoven fabrics, or knitted fabrics to be uniformly reproducible and can be dyed to high fastness, and to use the basic dye composition. Method of dyeing and dyeing.
[Means to solve the problem]

In order to solve the above-mentioned problems, the present inventors have made intensive research and found that a basic dye composition containing a specific blue basic dye and any specific red basic dye and / or a specific yellow basic dye And a dyeing method using the basic dye composition, the present invention is finally completed.

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

In formula (2), R ¹ represents (C1 to C3) alkyl or cyano (C1 to C3) alkyl; in formula (3), R ² represents hydrogen atom or (C1 to C3) alkoxy; (1) to (3), X ^- line represents _{^{OH -, CH 3 SO 4 -}} , or halide ion.

2) The blue basic dye composition according to item 1), wherein the content of the basic dye represented by the formula (1) is 50 to 95% by mass, and the formula (2) to (3) The total content of the basic dyes shown is 5 to 50% by mass.

Blue basic dye composition according to the item 3), such as 1) or 2), wherein, in the formula (1) to (3), X ^- is Br ^- or Cl ^-.

4) A basic dye composition comprising: the blue basic dye composition according to any one of items 1) to 3); and a yellow base containing a basic dye represented by the following formula (4) A composition of at least one of a basic dye composition and a red basic dye composition containing at least one basic dye represented by the following formulae (5) to (6);

Formula (4), R ³ represents a hydrogen atom Department, (C1 to C3) alkyl group, or a (C1 to C3) alkoxy; of formula (4) to (6), X ^- line represents OH ^-, CH ₃ SO ₄ ^-, or halide ion.

5) The basic dye composition according to item 4), wherein
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 total content of the basic dyes represented by the formulae (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 6)), where, in the formulas to (4) (6), X - is Br ^- or Cl ^-.

7) A dyeing method comprising 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) The step of dyeing fiber materials.

8) The dyeing method according to item 7), wherein the fiber material comprises: acrylic fiber, basic dye-dyeable synthetic fiber (CDP), or a blended fabric, interwoven fabric, or interwoven fabric.

9) A dyestuff comprising: the blue basic dye composition according to any one of items 1) to 3), or the basic dye composition according to any one of 4) to 6) Acrylic fibers to be dyed, basic dyeable synthetic fibers (CDP), or blends, interwoven fabrics or knitted fabrics of these.
[Effect of the invention]

According to the present invention, it is possible to provide an alkaline dye composition which enables acrylic fibers, CDP fibers, or blends, interwoven fabrics, or interwoven fabrics thereof to be uniformly reproducible and can be dyed into high fastness, and to use the basic dye composition. Dyeing method and dyed matter of dye composition.

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

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

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

In the above formula to (1) (3), X - line represents _{^{OH -, CH 3 SO 4 -}} , or halide ion, preferably line represents Br ^- or Cl ^-.

The basic dye system represented by the above formula (1) is described in Patent Document 1 and the like. Basic dye-based formulas of the above formula (2) described in Patent Document 2 includes, for example CIBasic Blue 162 (formula (R 2) in the ^{1-cyanoethyl,} X ^- is CH ₃ SO ₄ ^-) and CIBasic Blue 54 (wherein R ¹ in formula (2) is a methyl group, and X ⁻ is CH ₃ SO ₄ ⁻ ). The basic dyes represented by the formula (3) are described in Japanese Patent Application Laid-Open No. 10-3183 and the like. The above formula (3) can be exemplified as basic dyes CIBasic Blue 3 (formula (R 3) ² in the hydrogen atom, X ^- is Cl ^-). The basic dyes represented by the above formulae (1) to (3) are commercially available.

The blue basic dye composition (B) according to this 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). Therefore, the dyeing rate of acrylic fibers and CDP fibers can be approximated, and the dyeing properties of dyed fabrics of blended fabrics, interwoven fabrics, or knitted fabrics containing these fibers can be made visually uniform.

The blue basic dye composition (B) according to this embodiment has a content of the basic dye represented by the formula (1) of 50 to 95% by mass, and is represented by the formulas (2) to (3). The total content of the basic dye is preferably 5 to 50% by mass. The content of the basic dye represented by the formula (1) is 50 to 80% by mass, and the formulas (2) to (3) are preferable. The total content of the basic dyes shown is more preferably 20 to 50% by mass. By setting the content ratio of the basic dye to the above range, the dyeing ratio to acrylic fibers and CDP fibers can be more similar.

The blue basic dye composition (B) according to this embodiment may contain C.I. Basic Blue 35. The content of C.I. Basic Blue 35 can be adjusted appropriately according to the desired hue.

[Basic Dye Composition]
The basic dye composition according to this embodiment contains the above-mentioned blue basic dye composition (B) and a yellow basic dye composition (Y) containing a basic dye represented by the following formula (4). A composition with at least one of a red basic dye composition (R) containing at least one basic dye represented by the following formulae (5) to (6). In addition to the blue basic dye, a yellow basic dye and / or a red basic dye are further contained, whereby a basic dye composition having a desired hue can be obtained. The respective content ratios 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, (C1 to C3) alkyl, or (C1 to C3) alkoxy. Examples of the (C1 to C3) alkyl group include methyl, ethyl, n-propyl, 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. R ³ is preferably a hydrogen atom or a methoxy group.

In the above formula to (4) (6), X - line represents _{^{OH -, CH 3 SO 4 -}} , or halide ion, preferably line represents Br ^- or Cl ^-.

Basic dye-based formulas of the above formula (4) described in Patent Document 5 and the like, can be exemplified as CI Basic Yellow 51 (the formula (R 4) is a hydrogen atom in the ^3, X ^- is CH ₃ SO ₄ ^-), CI Basic Yellow 29 (the formula (R 4) ³ in the methyl group, X ^- is Cl ^-), and CI Basic Yellow 28 (the formula (R 4) ³ in the methoxy group, X ^- is CH ₃ SO ₄ ^- ). Basic dye-based formulas of the above formula (5) described in Patent Document 4 and the like, can be exemplified as CI Basic Red 46 (formula (5) in the X ^- is Br ^-). Basic dye is the above formula (6) described in the Patent Document 5 and the like, can be exemplified as CI Basic Red 29 (formula (6) in the X ^- is Cl ^-). The basic dyes represented by the above formulae (4) to (6) are commercially available.

The basic dye composition according to this embodiment may be a basic dye composition for black. The basic dye composition for black is preferably a blue basic dye composition (B) with a content of 30 to 60% by mass, a yellow basic dye composition (Y) with a content of 35 to 60% by mass, and red. The content of the basic dye composition (R) is 5 to 20% by mass. The blue basic dye composition (B) is preferably 60 to 80% by mass of the basic dye represented by the formula (1), and the basicity represented by the formulas (2) to (3). The total content of the dye is 20 to 40% by mass, more preferably the content of the basic dye represented by the formula (1) is 70 to 80% by mass, and the basic content of the dye represented by the formulas (2) to (3) is basic. The total content of the dye is 20 to 30% by mass. By setting the content ratio of the basic dye composition of each color to the above range, the dyeing ratio to acrylic fibers and CDP fibers tends to be closer.

As described above, the blue basic dye composition (B) may contain C. I. Basic Blue 35. The content of C. I. Basic Blue35 can be adjusted appropriately according to the desired hue.

[Blue basic dye composition and method for preparing basic dye composition]
In the preparation of the blue basic dye composition and the basic dye composition, the method for preparing each basic dye is not particularly limited. For example, the following methods can be used: a method of synthesizing each basic dye separately and then preparing it; a method of mixing a dye solution containing each basic dye generated during the synthesis and then drying to form a composition; A method of dissolving individual dyes in a dye bath and making each composition the same composition in a dye bath; etc. At this time, the mixing ratio of each basic dye is appropriately determined according to the desired hue.

The blue basic dye composition and the basic dye composition may also contain known additives, such as a concentration adjuster, a dispersant, a leveling agent, a precipitation inhibitor, a metal ion chain-linking agent, and a reduction inhibitor, as needed.
The morphology of the blue basic dye composition and the basic dye composition is not particularly limited, and may be, for example, powdery, granular, or liquid.

Each basic dye constituting the blue basic dye composition or the basic dye composition, and the above-mentioned additives, etc., as necessary, are added to a dyeing bath, a padding bath, or a dyeing paste, and prepared into dyes. When dyeing in a bath or the like, the order of dissolving each basic dye, additive, etc. may be any order. The amount of each component to be used may be determined by referring to a known method.

The blue basic dye composition and basic dye composition according to this embodiment can be used for dyeing fiber materials containing acrylic fibers or CDP fibers, and are particularly suitable for blends of acrylic fibers and CDP fibers, cross fabrics, or Dyeing of cross-woven fabric materials. The respective proportions of the acrylic fibers and CDP fibers in the blend, cross fabric, and cross knit can be arbitrarily adjusted according to the desired properties. Furthermore, the dyeable fiber material can be exemplified by such fibers or mixed fibers and other fibers (for example, cotton, rayon, polyester fiber, acetate fiber, wool, silk, nylon and other polyamide fibers, etc.) Blends, interwoven fabrics, interwoven fabrics, etc.

The CDP fiber may be, for example, an acid-modified polyester fiber. The acid-modified polyester fiber is, for example, using sulfonic acid isophthalic acid as a part of the phthalic acid component between the polyester fibers, and the sulfonic acid group is introduced into the fiber molecule to be modified into a fiber capable of being dyed with a basic dye. .

If the blue basic dye composition and the basic dye composition of this embodiment are used, a dyed material that is uniformly dyed can be manufactured, for example, containing acrylic fiber, CDP fiber, or a blended fabric, cross fabric, or knitted fabric. Dyed material and excellent reproducibility. Furthermore, the blue basic dye composition and the basic dye composition system according to this embodiment can dye acrylic fibers, CDP fibers, or blended fabrics, cross fabrics, or knits of these fibers with high fastness, It also has excellent color properties.

[Dyeing method using blue basic dye composition or basic dye composition]
The dyeing method according to this 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 capable of being dyed with a blue basic dye composition or a basic dye composition can be used.

The step of dyeing the fiber material using the blue basic dye composition or the basic dye composition can be performed, for example, according to a known method described below, but is not limited thereto.
In the dyeing step, for example, a blue basic dye composition or a basic dye composition corresponding to a desired hue and concentration is added to a dyeing bath, and an acid liquid conditioner is added. Examples of the acid liquid 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; and the like. These acid liquid conditioners can be used alone or in combination of two or more. The amount of the acid liquid preparation to be used may be appropriately adjusted and is not particularly limited.
After the dyeing step is completed, washing with water or hot water is followed by washing with a soap bath containing a commercially available soap lotion, or reducing washing with bisulfite, sulfur dioxide, or the like, and the dyeing is completed.

The usage amount of the blue basic dye composition or the basic dye composition is generally preferably set to about 0.0005 to 15% by mass based on the mass of the fiber material.
(Example)

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

The basic dyes represented by the above formulae (1) to (7) are those using the following (a) to (i). C. I. Basic Dye Index Common Name. The blending ratio of the basic dye is shown in Table 1. In addition, as long as there is no special description in this text, "part" means a mass part.

(a) Dye in which X ^- is Cl ^- in formula (1)
(b) CI Basic Blue 162 (equivalent to the basic dye of formula (2))
(c) CI Basic Blue 54 (equivalent to the basic dye of formula (2))
(d) CI Basic Blue 3 (equivalent to the basic dye of formula (3))
(e) CI Basic Yellow 51 (equivalent to the basic dye of formula (4))
(f) CI Basic Yellow 29 (equivalent to the basic dye of formula (4))
(g) CI Basic Yellow 28 (equivalent to the basic dye of formula (4))
(h) CI Basic Red 46 (equivalent to the basic dye of formula (5))
(i) CI Basic Red 29 (equivalent to the basic dye of formula (6))

[Example of Blending 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 thereof used. The numerical values in Table 1 indicate the amount (unit: part) of each basic dye used.

[Table 1]

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

(Dye distribution test)
(1) Water was added to each of the basic dye compositions 1 to 18 shown in Table 1 and Comparative Preparation Examples 1 to 9 and acetic acid in order to prepare a dye bath of 600 parts in total. 25 parts of Acrylic Muslin (Muslim thin cloth made of acrylic acid) (made by Mitsubishi Chemical Co., Ltd., obtained from Dyeing Co., Ltd.) and CDP knitting (`` Cationic dyeable polyester Knit Smooth (Processing) System) ", manufactured by Teijin Co., Ltd. and obtained from Co., Ltd.) 25 parts of two types of fiber materials, after being treated at 40 ° C for 10 minutes, and heated to a tip temperature of 100 ° C at a heating rate of 1 ° C / minute. ℃ or 105 ℃. The fiber material was dyed at each tip temperature for 60 minutes, and then washed with water. Then, soaping was performed at 70 ° C 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 hydrogen sulfite, and 1 g / L of caustic soda. After 15 minutes, washing and drying were performed to obtain a dyed substance.

(2) Method of evaluation using a colorimeter color eye CE7100 (Macbeth Corporation), obtained from Acrylic Muslin and CDP Knit of staining was measured under a D65 light source at a concentration of CIELAB color space of the (brightness L ^*) and hue (a ^*, b ^* ). The color difference ΔE is obtained using a CIE color difference formula. The relative concentration of the CDP knit stain (Acrylic Muslin stain: 100) and the color difference ΔE based on the Acrylic Muslin stain are shown in Table 2 below. The closer the relative density system is to 100, the better, and the closer the color difference ΔE system to 0, the more excellent.

[Table 2]

(3) The test results are shown in Table 2. Even when using any of the basic dye compositions of Formulation Examples 1 to 18, the difference in concentration and hue change are still very small. small. The results show that the basic dye compositions of Formulation Examples 1 to 18 can uniformly dye fiber materials including blends of acrylic fibers and CDP fibers, interwoven fabrics, or interwoven fabrics. On the other hand, the basic dye compositions of Comparative Formulations 1 to 9 have a larger difference in the concentrations of Acrylic Muslin and CDP Knit than the basic dye compositions of Formulations 1 to 18, and the color difference ΔE is also large.

In addition, even when the mixing ratio of Acrylic Muslin and CDP Knit was changed, the same dyeing distribution properties were obtained when the basic dye compositions of Formulation Examples 1 to 18 were used (data not shown). The results show that the basic dye compositions of Formulation Examples 1 to 18 can uniformly dye fiber materials such as blends containing these fibers regardless of the mixing ratio of acrylic fibers and CDP fibers.

(Fastness test)
(1) Test preparation A water bath was prepared by adding water to 1 part of each of the basic dye compositions and acetic acid of the formulation examples 1, 4, 5, 8, 10 to 17 shown in Table 1 to prepare a total amount of 600 parts. Into this dyeing bath, 50 parts of an interwoven fabric of acrylic fibers and CDP fibers were charged, and after being treated at 40 ° C for 10 minutes, the temperature was raised to a tip temperature of 105 ° C at a heating rate of 1 ° C / minute. After knitting the cross stitch at the tip temperature for 60 minutes, it was washed with water. Then, soaping was performed at 70 ° C 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 bisulfite, and 1 g / L of caustic soda. After 15 minutes, washing and drying were performed to obtain a dyed substance.

(2) Light resistance (JIS L 0843)
Dyeing fastness to xenon arc light is implemented in accordance with JIS L 0843. The irradiation was performed under the conditions of an irradiation illuminance of 50 W / m ² (wavelength of 300 to 400 nm), a BPT (black panel temperature) of 63 ° C., a relative humidity of 50%, and an irradiation exposure of 7100 kJ / m ² . The evaluation is expressed by a grade, which shows the same degree of discoloration as the blue scale (Blue Scale) irradiated at the same time. Level 5 indicates the strongest light resistance, and level 1 indicates the weakest light resistance. The results are shown in Table 3 below.

(3) Washing (JIS L 0844)
The fastness to washing was implemented in accordance with JIS L 0844. Acrylic acid and cotton were added to the dyed matter as an additional white cloth, and treated by A-2 method (Marseile soap 5g / L, liquid volume 100mL, 50 ° C, 30 minutes). The evaluation is based on the gray standard for pollution JIS L 0805 to indicate the degree of pollution of the additional white cloth. A level 5 indicates the best result, and a level 1 indicates the worst result. The results are shown in Table 3 below.

[table 3]

(4) The results are shown in Table 3. The grades of the light fastness test for each of the dyed materials obtained by using the basic dye compositions of Preparation Examples 1, 4, 5, 8, 10 to 17 were all "5" indicates excellent light resistance. In addition, in the washing fastness test, any of the dyed materials also showed a high grade of "5" or "4-5", which was unlikely to cause discoloration or color transfer due to washing, and showed excellent washing fastness.

Claims (9)

A blue basic dye composition comprising: a basic dye represented by the following formula (1) and at least one basic dye represented by the following formulas (2) to (3); In formula (2), R ¹ represents (C1 to C3) alkyl or cyano (C1 to C3) alkyl; in formula (3), R ² represents hydrogen atom or (C1 to C3) alkoxy; (1) to (3), X ^- line represents _{^{OH -, CH 3 SO 4 -}} , or halide ion. The blue basic dye composition according to item 1 of the scope of patent application, wherein the content of the basic dye represented by the aforementioned formula (1) is 50 to 95% by mass, and the aforementioned formulas (2) to (3) The total content of the basic dyes shown is 5 to 50% by mass. As defined in claim 2 or 1 range of blue basic dye composition, wherein, in the formula (1) to (3), X ^- is Br ^- or Cl ^-. A basic dye composition comprising: the blue basic dye composition described in any one of claims 1 to 3 of the scope of patent application; and a yellow base containing a basic dye represented by the following formula (4) A composition of at least one of a basic dye composition and a red basic dye composition containing at least one basic dye represented by the following formulae (4) to (6); Formula (4), R ³ represents a hydrogen atom Department, (C1 to C3) alkyl group, or a (C1 to C3) alkoxy; of formula (4) to (6), X ^- line represents OH ^-, CH ₃ SO ₄ ^-, or halogen compound ions. The basic dye composition according to item 4 of the scope of patent application, wherein: 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 total content of the basic dyes represented by the formulae (2) to (3) in the blue basic dye composition is 20 to 40% by mass. The application of the basic patents in item 4 dye composition range, wherein, in the formulas to (4) (6), X - is Br ^- or Cl ^-. A dyeing method comprising using the blue basic dye composition described in any one of claims 1 to 3 in the patent application scope or the basic dye described in any one of claims 4 to 6 in the patent application scope The composition is a step of dyeing a fibrous material. The dyeing method according to item 7 of the scope of the patent application, wherein the aforementioned fiber material includes: acrylic fiber, basic dye-dyeable synthetic fiber (CDP), or a blended fabric, cross-woven fabric, or cross-knitted fabric. A dyeing material, comprising: the blue basic dye composition described in any one of claims 1 to 3 in the scope of patent application, or the basic dye described in any one of claims 4 to 6 in the scope of patent application Acrylic fibers, basic dye-dyeable synthetic fibers (CDP), or blends, interwoven fabrics, or knitted fabrics of which the composition is dyed.