JP3299014B2 - Red dye composition, dyeing method using the same and dyed product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye composition for dyeing polyamide fibers, a method for dyeing polyamide fibers using the same, and a dyed product thereof.

[0002]

2. Description of the Related Art In recent years, with the expansion of the sports clothing market, there is a high demand for polyamide fibers having a wet fastness of dyeings of medium and high concentrations. Conventionally, polyamide fiber is yellow,
When performing dyeing with so-called three primary colors dyes of red and blue colors, it is known that uniform dyeing can be easily obtained using a so-called leveling-type acid dye having good transferability. It has a disadvantage of inferior degree.

In order to solve this drawback, use of fast acid dyes having good wet fastness has been recognized in some cases. However, wet fastness type dyes are poor in transferability and generally inferior in levelness because the amount of dyeing increases in a temperature range of 70 to 90 ° C. For this reason, even if the operation is devised such as slowly raising the temperature, the leveling property cannot be easily obtained. Therefore, it takes a very long time to dye and is not practical. In the case of dyeing using only one type of fast-acting acid dye, the characteristics are grasped and the dyeing conditions (PH, temperature, heating rate, etc.) are adjusted, or the dyeing aid is used. It is possible to obtain uniform dyeings.

[0004] However, it is extremely rare to dye using only a single dye in general, and in order to obtain a dyed product over a wide hue range, several kinds of different color dyes are mixed.
It must be toned and correspond to the desired hue. Nevertheless, in the case of the fast acid dyes, the dyed product of the compound dyeing is poor in uniformity, and the preferred three primary colors of fast acid dyes have not yet been obtained.

[0005] The inventors of the present invention can impart wet fastness and levelness by selecting and blending a single dye from each of the three groups in each of the three primary color systems. The dye composition for three primary colors is obtained, and the dyeing speed of each of the three primary colors is uniformed, so that it is possible to dye in a so-called good compatibility state. A possible method has been proposed (JP-A-2-53972). After that, they further developed this and found a red dye composition satisfying the needs and demands of the industry, and filed a patent application (Japanese Patent Application No. 4-345232).

[0006]

However, these have unclear hues and do not satisfy the needs and demands of the industry. The present inventors have conducted intensive studies and found that by using an azo dye having a specific dye structure matrix in combination, the polyamide fiber is finally dyed uniformly, and in a desirable clear red region, good wet fastness is obtained. They have found a dye and a dyeing method that can be imparted, and have found that this is a red dye composition that can also expand the range of hues obtained by combining the three primary colors to a sharper region, and complete the present invention. Reached.

[0007]

SUMMARY OF THE INVENTION The present invention is a red dye composition for dyeing polyamide fibers, wherein the composition has the general formula (1) in the form of a free acid.

[0008]

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Wherein n represents 0 or 1; a disazo dye represented by the following general formula (2):

[0010]

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(Wherein X represents a sulfonic acid ester group, a sulfonic acid amide group or a trifluoromethyl group, Y is a hydrogen atom, a lower alkyl group or a lower alkoxy group which may be further substituted, an acylamino group or a halogen atom. An azo dye represented by the following general formula (3):

[0012]

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Wherein Z represents a hydrogen atom, a phenoxy group or a lower alkoxy group which may be further substituted, an acylamino group or a halogen atom, and a free acid in the form of the following general formula ( 4)

[0014]

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(Wherein P and Q each independently represent a hydrogen atom, a lower alkyl group or a lower alkoxy group which may be further substituted, an acylamino group or a halogen atom, and K may be further substituted. A acetyl group, a phenylsulfonyl group or a phenylcarbonyl group, and m represents an integer of 1 to 2). .

The red dye composition of the present invention has the general formula (1)
The mixing ratio of each dye represented by the general formula (4) is such that the disazo dye represented by the general formula (1) is 30 to 80% by weight, the azo dye represented by the general formula (2) is 5 to 40% by weight, The red color according to any one of claims 1 to 5, wherein the azo dye represented by the formula (3) is in a range of 0 to 10% by weight, and the azo dye represented by the general formula (4) is in a range of 0 to 10% by weight. It is a dye composition.

The most preferred composition of the red dye composition of the present invention is a disazo dye represented by the general formula (1):
Azo dye represented by the general formula (2)
20% by weight of the azo dye represented by the general formula (3)
0% by weight, and 2 to 10 azo dyes represented by the general formula (4)
A red dye composition for dyeing polyamide fibers in the range of weight percent.

Hereinafter, the present invention will be described in more detail. Conventionally, dyes for dyeing polyamide fibers in red are known and have been awarded, but they are insufficient in hue or fastness and the like, and particularly preferred hue (bluish red).
Red dyes which can be dyed with high fastness to a sharp red color and have high compatibility with other two-color dyes, that is, yellow dyes and blue dyes having the same fastness and which are excellent in compatibility with dyeing, are almost known. Not been.

The present inventors have found for the first time that the above-mentioned drawbacks can be eliminated at once by using a specific mixed dye of the general formulas (1) to (4) in the present invention. Was done. Therefore, the dye composition for dyeing the polyamide fiber of the present invention can solve the conventional disadvantages even when used alone, and can obtain a dye having a favorable hue, fastness, and good levelness. Can be. Another object of the present invention is to provide a method for dyeing a polyamide fiber, which dyes the polyamide fiber with a preferable red hue and a clear red color. Still another object of the present invention is to provide a polyamide fiber dyed by using a mixed dye for dyeing the polyamide fiber.

The red dye composition of the present invention is more excellent when it is used as one component of a three primary color dye. That is, the dye composition of the present invention is a dye composition other than the three primary color dyes, specifically as disclosed in Japanese Patent Application Laid-Open No. 2-53972 or Japanese Patent Application No. 4-345232 previously proposed by the present inventors. For example, when used together with a yellow dye composition and a blue color composition as described below and used as a so-called three primary color dye composition, it has a preferable dye compatibility, and the red color among the three primary color dye compositions It can be used as a system dye composition to provide more preferable results.

Here, as the yellow dye composition, dye group (YA): CIAcid Yellow 42, 219 dye group (YB): CIAcid Orange 67, 127 Dye group (YC): CIAcid Orange 95, 127 One or more dyes each selected from
Seed) is a yellow dye composition, and as a blue dye composition, dye group (BA): CIAcid Blue 127, 127: 1 dye group (BB): CIAcid Blue 40 , 260 dye group (BC): one or more dyes each selected from CIAcid Blue 40 and 264 (at least 3 dyes).
Is a blue-based dye composition prepared by mixing

The red dye composition of the present invention has good compatibility in so-called dyeing with these yellow dye composition and blue dye composition, and can dye polyamide fibers uniformly and red. Accordingly, the present invention includes a compound dye composition for three primary colors, a method for dyeing polyamide fibers using these, and a polyamide fiber dyed using these.

As a method for preparing these dyes, each of the selected dyes is added to a dye bath at the time of dyeing, and the dye is prepared in the present invention so that the predetermined dye is mixed with the dye bath. However, when it is complicated, it is preferable to prepare a dye composition in which the selected individual dyes have been prepared before adding to the dye bath.

In the three primary color dyeing using the thus obtained yellow, red and blue mixed dye compositions,
Even if these are blended at an arbitrary ratio, a unique effect that industrially advantageous dyeing can be realized in a short time without impairing the leveling property is exhibited. The dye composition of the present invention may contain, in addition to the above-described dye composition, usual known diluents and additives such as salt, inorganic salts such as sodium sulfate, dextrin, naphthalenesulfonic acid-formalin condensate, and dust. -An anti-scattering agent and the like can be appropriately compounded and used.

The polyamide fiber applied to the present invention is a natural polyamide fiber such as wool, a synthetic polyamide fiber such as nylon, or a fiber blended with natural and synthetic polyamides. Wool, yarn, woven, knitted, carpet, etc. The dye composition according to the present invention is characterized in that the change in the dyeing speed with the change in the dyeing temperature is smaller than that of the conventional fast acid dyes, and that the maximum dyeing speed is small, so that the dyeing composition is excellent in levelness. Have.
In particular, the dye composition of the present invention is excellent in dyeing a synthetic polyamide such as 6-nylon and 66-nylon.

Conventionally, in the case of compound dyeing using a single fast acid dye, a very complicated dyeing operation requiring setting of heating conditions and adjustment of dyeing conditions corresponding to each dyeing speed is required. However, in the dye composition according to the present invention and the compounded dye composition thereof, a dyeing program suitable for the processing form of the polyamide fiber and the type of the dyeing apparatus can be arbitrarily set, that is, the allowable range of the dyeing program. , And a dyed product having a wide, uniform and good wet fastness can be easily obtained with good reproducibility. As a result, the dyeing time which conventionally required a long time can be inevitably shortened, and an industrially advantageous dyeing method can be established.

The azo dyes represented by the general formulas (2) to (4) formulated in the red dye composition of the present invention include:
Specifically, the following azo dyes are exemplified. As the azo dye represented by the general formula (1), the following B-1 to B-1
And dyes represented by -5.

[0028]

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Examples of the azo dye represented by the general formula (3) include the dyes represented by the following C-1 to C-2.

[0030]

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The azo dyes represented by the general formula (4) include the dyes represented by the following C-1 to C-2.

[0032]

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[0033]

According to the present invention, polyamide fibers can be dyed in a preferable red color with good levelness by using a specific compounding dye. Further, by using the red dye composition of the present invention in combination with other yellow and blue dyes for three primary colors, the dyeing compatibility is extremely good at any mixing ratio.

[0034]

Next, the present invention will be described by way of examples. In the examples, parts and% mean parts by weight and% by weight, respectively.

Example 1 As fast acid dyes, each in the form of the free acid

[0036]

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43 parts of a sodium salt of a disazo dye represented by

[0038]

Embedded image 10 parts of sodium salt of azo dye represented by

[0039]

Embedded image 5 parts of sodium salt of azo dye represented by

[0040]

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A synthetic polyamide fiber was dyed using a dye composition comprising 5 parts of sodium salt of azo dye represented by and 37 parts of sodium sulfate and dyeing speed curve was measured at the same time.

The dyeing conditions are as follows. Equipment used: Minicolor 12 type (manufactured by Texam Giken) Dyeing object: nylon jersey (manufactured by Toray Industries) Bath ratio: 1:30 Dyeing concentration: 1.0% o.w.f Auxiliary agent; ammonium sulfate 2.0% o.w.f

This dye composition dyed a polyamide fiber in a desirable blue-red color with good levelness. FIG. 1 shows the dyeing speed curves of the components of the dye composition and the dye mixture. This compounded dye exhibited a good compatibility dyeing speed curve.

Example 2 A compound dye of Example 1 was used as a blue dye of a fast acid dye and a compound dye having the following composition was used as a yellow dye. (1) CIAcid Yellow 42 (dye group YA) (2) CIAcid Orange 67 (Dye group YB) (3) CIAcid Orange 127 (Dye group YC) Same amount of the dye of (1) (2) (3) above

(4) CIAcid Blue 127 (dye group BA) (5) CIAcid Blue 260 (dye group BB) (6) CIAcid Blue 40 (dye group BC) The above (4) (5) Using the same amount of the dye of (6),
Staining was carried out under the same staining conditions. However, the usage fee of each prepared dye was red dye; 0.25% owf yellow dye; 0.86% owf blue dye; 0.5% owf. The dyeing speeds of these three primary colors were similar, and a uniform brown dyed product having good compatibility was obtained.

Example 3 Sodium salt of disazo dye of the formula A-1 as a fast acid dye in the form of a free acid 40 parts Sodium salt of the disazo dye of the formula B-2 12 parts Disazo dye of the formula C-1 The synthetic polyamide fiber was dyed using a red dye composition consisting of 8 parts of a sodium salt of disazo dye of the formula D-4 and 8 parts of sodium sulfate. The staining conditions are as follows.

Dyeing material: Nylon jersey (manufactured by Toray Industries) Bath ratio: 1:30 Dyeing concentration: 1.0% owf acetic acid; Added to make pH = 4 Glauber's salt; 5% owf temperature; Temperature rise in 100 minutes, 100
Hold at ℃ for 30 minutes

The dyeing behavior exhibited good compatibility and a bluish-red dyed product was obtained. This dye composition was used for dyeing three primary colors in the same manner as in Example 2, and the dyeing speeds of the three primary colors were similar, and a dyed product with good compatibility and uniform brown color was obtained.

[0049]

[Brief description of the drawings]

FIG. 1 shows the dyeing speed curves of the components of the dye composition described in Example 1 and the prepared dyes. In the figure,

Reference numeral 1 denotes a dyeing rate curve of the chemical formula (A-1). 2 shows the dyeing speed curve of the chemical formula (B-1).
3 shows the dyeing speed curve of the chemical formula (C-1). 4 shows the dyeing speed curve of the chemical formula (D-1). A shows a dyeing speed curve of these four-component dye compositions.

Continued on the front page (72) Inventor Shuhei Hashizume 3-1-198 Kasuganaka, Konohana-ku, Osaka Examiner, Sumitomo Chemical Co., Ltd. Shoei Hoshino (56) References JP-A-58-120883 (JP, A) JP-A-59-173384 (JP, A) JP-A-59-173385 (JP, A) JP-A-58-197384 (JP, A) JP-B 32-5939 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) C09B 67/22 D06P 3/24

Claims (11)

(57) [Claims] 1. A dye composition for dyeing polyamide fibers, wherein the composition has the following general formula (1) in the form of a free acid: (Wherein n represents 0 or 1) in the form of a disazo dye or free acid represented by the following general formula (2): (In the formula, X represents a sulfonic acid ester group, a sulfonic acid amide group or a trifluoromethyl group, and Y represents a hydrogen atom, a lower alkyl group or a lower alkoxy group which may be further substituted, an acylamino group or a halogen atom. Azo dyes represented by the following general formula (3): (Wherein, Z represents a hydrogen atom, a phenoxy group or a lower alkoxy group which may be further substituted, an acylamino group or a halogen atom) and a free acid in the form of the following general formula (4): Chemical-4 (Wherein P and Q each independently represent a hydrogen atom, a lower alkyl group or a lower alkoxy group which may be further substituted, an acylamino group or a halogen atom, and K represents an acetyl group which may be further substituted. A phenylsulfonyl group or a phenylcarbonyl group, and m represents an integer of 1 to 2.) 2. The disazo dye represented by the general formula (1) is converted into a free acid in the form of the following formula (A): The red dye composition according to claim 1, which is a disazo dye represented by the following formula: 3. An azo dye represented by the general formula (2) is obtained by converting the azo dye represented by the following formula (B) in the form of a free acid. The red dye composition according to claim 1, which is an azo dye represented by the formula: 4. An azo dye represented by the general formula (3) is obtained by converting the azo dye represented by the following formula (C) in the form of a free acid. The red dye composition according to claim 1, which is an azo dye represented by the formula: 5. An azo dye represented by the general formula (4) is obtained by converting the azo dye represented by the following formula (D) in the form of a free acid. The red dye composition according to claim 1, which is an azo dye represented by the formula: 6. The disazo dye represented by the general formula (1) is 30 to 80% by weight, the azo dye represented by the general formula (2) is 5 to 40% by weight, and the azo dye represented by the general formula (3) is 0
10 to 10% by weight, the azo dye represented by the general formula (4)
The red dye composition according to any one of claims 1 to 5, which is in a range of 10% by weight. 7. The disazo dye represented by the general formula (1) is 30 to 60% by weight, the azo dye represented by the general formula (2) is 5 to 20% by weight, and the azo dye represented by the general formula (3) is The red dye composition according to any one of claims 1 to 5, wherein the content of the azo dye represented by the general formula (4) is in the range of 2 to 10% by weight and 2 to 10% by weight. 8. A method for dyeing polyamide fibers, comprising dyeing polyamide fibers with the red dye composition according to claim 1. Description: 9. The general formula (1) according to claim 1
Dyeing a polyamide fiber from a dye bath containing a disazo dye represented by the following formula, an azo dye represented by the general formula (2), an azo dye represented by the general formula (3) and an azo dye represented by the general formula (4). Characteristic method for dyeing polyamide fiber. 10. Dye group (YA), (YB) and (YC) Dye group (YA); CIAcid Yellow 42, 219 Dye group (YB): CIAcid Orange 67, 127 Dye group (YC): CIAcid Orange 95 , 127, respectively (at least 3 dyes)
Species), a yellow dye composition, a dye group (BA) shown below,
(BB) and (BC) Dye group (BA): CIAcid Blue 127, 127: 1 Dye group (BB): CIAcid Blue 40, 260 Dye group (BC): One or more selected from CIAcid Blue 40, 264, respectively Dyes (at least 3
Dyeing a polyamide fiber by using the blue dye composition prepared by blending the above-mentioned (seed) and the red dye composition according to any one of claims 1 to 7 as a three primary color dye. Method. 11. A polyamide fiber dyed by the dyeing method according to claim 8. Description: [0001]