JPH1129714A - Dyeing of polyamide based fiber characterized by using anthrapyridone compound, and piece dyed thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which a dyed piece having a sharp hue and high light color fastness can be obtained, and formalin discoloration in wool dyeing does not occur and which comprises using an anthrapyridone compound having a specified structure or a salt thereof in dyeing a polyamide fiber. SOLUTION: The anthrapyridone compound is represented by the formula (wherein R1 is an alkoxycarbonyl, carboxyl, benzoyl or 3-sulfobenzoyl; R2 is H or an alkyl; R3 and R4 are each H, a halogen, an alkyl or an alkoxyl; and (n) is 1-3), and the salt is exemplified by an alkali metal salt, an ammonium salt or a salt with an amine. It has a sharp bluish red. Its amount of use is 0.01-10 o.w.f., based on the weight of the fiber. The dyeing is performed by general dip dyeing, printing or the like. In a typical method for dyeing wool or nylon, it is performed under conditions including an acid to neutral pH range (2-7), a temperature of 90-100 deg.C and a time of 20-60 min. In textile printing, the fiber is first printed with a color paste and then treated with saturated steam at 100-105 deg.C and superheated steam at 120-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dyeing method and a dyed product. More specifically, the present invention relates to a method for dyeing polyamide fibers using a specific anthrapyridone compound, and a dyed product thereof.

[0002]

2. Description of the Related Art Polyamide fibers include natural polyamide fibers typified by wool and silk and 6-nylon and 6,6-
There is a synthetic polyamide fiber represented by nylon. To dye these fibers, an acid dye is generally used. Almost all red acid dyes are H acid azo dyes having a clear hue, but have the problem of poor light fastness. Therefore, in such a request, γ-
Although an acid-based azo dye is used, the hue of such a dye is dark, and the desired color may not be obtained in some cases. Wool, which is a representative of natural polyamide fibers, is heated to 90 ° C or more (125 ° C
In the case of dyeing in the following), protein bonds constituting the fiber may be cleaved, and the fiber may be embrittled or wrinkled at the time of reconnection. In order to suppress this, a functional agent such as formalin is added, but there is a problem that formalin also reacts with a dye to cause discoloration of a dyed product. or,
In recent years, demand for nylon, which is one of synthetic polyamide fibers, has been increasing with the expansion of applications for sports clothing.
In such a market, fashionability is strongly demanded, and a product having a clear hue and strong light fastness is demanded. However, at present, there is still no product capable of meeting these demands.

[0003]

The improvement of azo dyes used in conventional polyamide fibers cannot completely meet the needs of the market. To find a new dyeing method in which the color of polyamide-based fibers such as wool and nylon is sharp, has a strong light fastness, and does not cause formalin discoloration during wool dyeing.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have accomplished the present invention.

That is, the present invention provides:

(1) Equation (1)

[0007]

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Wherein R ₁ is an alkoxycarbonyl group,
A carboxy group, a benzoyl group or a 3-sulfobenzoyl group, R ₂ is a hydrogen atom or an alkyl group, R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and n is 1 to 3 Represents an integer. (2) A method for dyeing polyamide fibers, characterized by using an anthrapyridone compound represented by the formula (1) or a salt thereof: (2) dyeing using an anthrapyridone compound represented by the formula (1) or a salt thereof represented by the above-mentioned (1). To dyed polyamide fibers.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the above formula (1), R ₁ is an alkoxycarbonyl group,
It is a carboxy group, a benzoyl group or a 3-sulfobenzoyl group. Examples of the alkoxycarbonyl group for R ₁ include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, n
-C ₁ -C ₆ alkoxycarbonyl groups such as -propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group and t-butoxycarbonyl group. In the above formula (1), R ₂ is a hydrogen atom or an alkyl group. Examples of the alkyl group for R ₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and t.
- butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, an alkyl group of decyl group C ₁ -C ₁₀ and the like.

In the above formula (1), R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include a methyl group, an ethyl group, and n-
C ₁ -C ₄ alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, isobutoxy group, t-butoxy group C ₁ -C
_{And 6} alkoxy groups. As for the bonding position of R ₃ and R ₄ , assuming that the bonding position of the imino group is the first position, it is preferable that R ₃ is the second or third position and R _{4 is the} third or fourth position. In the above formula (1), n is an integer of 1 to 3, and the sulfonic acid group is 2 when the bonding position of the imino group is 1-position.
Those bonded to any of the 4-, 4- or 6-positions are preferred.

In the above formula (1), R ₁ , R ₂ ,
As a preferable combination of R ₃ , R ₄ and n, for example, R ₁ is an alkoxycarbonyl group, a carboxy group, a benzoyl group or a 3-sulfobenzoyl group, R ₂ is a hydrogen atom or a methyl group, and R ₃ is bonded to the 3-position. This is the case where a hydrogen atom, a methyl group or a chloro group, R ₄ is a hydrogen atom, n is an integer of 1 to 2, and the sulfonic acid group is bonded to the 4-position or the 4- and 6-positions. More preferably, R ₁ is an alkoxycarbonyl group or a carboxy group, R ₂ is a hydrogen atom or a methyl group, R ₃ is a hydrogen atom or a methyl group bonded to the 3-position, R ₄
Is a hydrogen atom, n is 2 and a sulfonic acid group is bonded to the 4- and 6-positions. More preferably, R ₁ is an ethoxycarbonyl group or a carboxy group, R ₂ is a methyl group,
R ₃ is a hydrogen atom or a methyl group bonded to the 3-position, R ₄ is a hydrogen atom, n is 2, and a sulfonic acid group is bonded to the 4- and 6-positions.

In the present invention, the anthrapyridone compound represented by the formula (1) may be a free sulfonic acid or a salt thereof. Salts are salts at the sulfonic acid group. Examples of the salt of the compound represented by the formula (1) include an alkali metal salt such as a sodium salt, a potassium salt, and a lithium salt, an ammonium salt, and a salt with various amines. The various amines, for example mono- methanol amine, dimethanol amine, triethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono propanolamine, di-propanolamine, alkanolamines, etc. tripropanolamine, etc. C ₁ -C ₄ is can give. In order to obtain each of the above-mentioned salts of the formula (1), for example, the obtained sodium salt crystals are dissolved in water, acidified by adding an acid, and optionally a cake obtained by filtration is again obtained. By dissolving in water and adding an amine such as potassium hydroxide, lithium hydroxide, aqueous ammonia, diethanolamine or triethanolamine, an amine such as a potassium salt, a lithium salt, an ammonium salt, a diethanolamine salt or a triethanolamine salt is added, respectively. It can be a salt.

The compound represented by the above formula (1) and used in the present invention is produced, for example, as follows. The following general formula (2)

[0014]

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Wherein R ₂ , R ₃ and R ₄ have the same meanings as described above, and a compound of the general formula (3)

[0016]

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(Wherein, R ₁ has the same meaning as described above;
₅ represents an alkyl group. ), And the resulting compound is sulfonated to obtain a sulfonic acid derivative of the formula (1) (specifically, for example, in the formula (1), n is 1 to 3). Compound) is obtained.

The reaction between the compound of the general formula (2) and the compound of the general formula (3) is carried out, for example, in the presence of a base such as sodium carbonate or potassium carbonate as a catalyst in the presence of orthodichlorobenzene, monochlorobenzene, nitrobenzene, xylene or the like. What is necessary is just to carry out at 100-200 degreeC in a solvent. After completion of the reaction, the reaction mixture was cooled, diluted with a solvent such as methanol, ethanol, or propanol and filtered, and then, if necessary, methanol,
After washing with alcohols such as ethanol and propanol,
Obtained by drying.

The sulfonation reaction is carried out in a sulfuric acid containing fuming sulfuric acid according to a usual sulfonation method. The concentration of fuming sulfuric acid in sulfuric acid is preferably about 2 to 20% by weight, more preferably about 5 to 15% by weight, and still more preferably about 7 to 12% by weight. The reaction temperature is generally 0-100 ° C, preferably 10-50 ° C. The reaction time varies depending on the reaction temperature, but is usually 5 minutes to 20 hours, preferably 15 minutes to 5 hours.
About an hour. After the reaction is completed, pour the reaction solution into ice water,
Salting out, filtration, and drying yield a sulfonic acid derivative of the general formula (1) (specifically, a compound in which n is 1 to 3).

Examples of the polyamide fibers applicable to the present invention include natural polyamide fibers such as wool, silk, and leather; synthetic polyamide fibers such as 6-nylon and 6,6-nylon; There is a form of processing such as rose hair, thread, woven fabric, knitted fabric and the like.

As a dyeing method, dyeing is performed by a dip dyeing method, a printing method, or the like which is common in the art. A typical dyeing method for wool and nylon is 90 ° C. under acidic to neutral conditions (pH 2 to 7).
Stained at １００100 ° C. for 20 to 60 minutes. In the printing method, printing is performed using a color paste, followed by treatment using saturated steam at 100 to 105 ° C and superheated steam at 120 to 200 ° C for 5 to 30 minutes to fix the ink. The dye of the general formula (1) is used in an amount of 0.01 to 10 o. w. f. It is preferably used. In recent years, along with the development of new technologies, ink-jet printing of fibers is being carried out by utilizing the ink-jet printing technology generally used for paper. In this case, mainly Yellow, Magenta, C
This is performed in four colors, yan and Black. Equation (1)
Is a bright bluish red, and
It is suitable as a and has high utility value.

Heretofore, many dyes have been known and awarded as acid dyes for dyeing polyamide fibers in red color. However, there is no dye having both hue and fastness, which is unsatisfactory. In the dyeing method of the present invention, by using the compound of the formula (1), (1) clear color can be obtained, and (2) a high sunlight fastness which cannot be obtained conventionally can be obtained. 3) Uneven dyeing such as skittle and chipping peculiar to wool is eliminated, and a dyed material having good levelness can be obtained. The reason is that the compound of the formula (1) is an anthrapyridone compound and exhibits a sharp red color peculiar to the bone nucleus. It seems to be stronger than the azo dyes.
Because wool is a natural fiber obtained from living organisms, its dyeing properties vary greatly depending on the site where the wool is obtained (for example, the back and the abdomen not exposed to sunlight). It is well known that the dyeing properties are different, and when dyeing with an acid dye, uneven dyeing called skittle or chipping is likely to occur. The compound of the formula (1) has a smaller molecular volume than the azo dye, and uniformly diffuses and dyes the crystal part and the non-crystal part of the fiber, so that a uniformly dyed wool can be obtained. Furthermore, wool is characterized by having one amino acid cysteine as a constituent and having a cysteine bond in the polymer. The cysteine bond is cleaved by heating (90 to 130 ° C.) at the time of dyeing, resulting in embrittlement of the fiber and recombination with a site different from the initial state, causing phenomena such as wrinkles and shrinkage. In order to prevent this, a highly reactive functional agent is added for improvement. A representative of this functional agent is formalin, and various functional agents such as those that generate formalin by heating are used. But,
Formalin reacts not only with fibers but also with dyes, and has a problem with discoloration of dyed products. The compound of the formula (1) or the dyed product obtained by using the compound has no discoloration due to formalin, and the dyeing method of the present invention is also excellent in this respect.

Specific examples of the anthrapyridone compound (1) of the present invention include the compounds shown in Table 1 below.

[0024]

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Next, specific examples of the compound represented by the above formula (1) will be shown.

[0026]

TABLE 1 Compound No. R ₁ R ₂ R ₃ R ₄ n Salt 001 -COOC2H5 -CH3 HH 2 (4,6 position) Na 002 -COOC2H5 -CH3 H -CH3 (3 position) 2 (4,6 position ) Na 003 -COOC2H5 HH -CH3 (3rd position) 2 (4,6 position) Na 004 -COOC2H5 HHH 2 (4,6 position) Na 005 -COOH HHH 2 (4,6 position) Na 006 -COPh HH -CH3 (3rd) 2 (4,6th) K 007 -3S-BENZOYL HH -CH3 (3rd) 2 (4,6th) Na 008 -COPh -CH3 HH 2 (2,4th) Na 009 -3S- BENZOYL -CH3 HH 2 (2,4) Na 010 -COPh HHH 2 (2,4) Na 011 -3S-BENZOYL HHH 2 (2,4) Na 012 -COPh -CH3 H -CH3 (3) 2 (position 4,6) Na 013 -COOH -CH3 HH 2 (position 4,6) Na 014 -COOC2H5 -CH3 H -CH3 (position 4) 1 (position 2) Na 015 -COOC2H5 -CH3 H -CH3 (2 1) (4) NH ₄ 016 -COOC2H5 -CH3 H -Cl (3) 2 (4,6) Na 017 -COOC2H5 -CH3 H -Cl (4) 1 (2) Na 018 -COOC2H5 -CH3 H -OCH3 (4th position) 1 (2nd position) K 019 -COOC2H5 -CH3 H -OCH3 (2nd position) 1 (4th position) Na 020 -COOC2H5 -CH3 -CH3 (2nd position) -CH3 (6th position) 1 (4th) Na 021 -COOC2H5 -CH3 H -C4H9 (4th) 1 (2nd) Na 22 -COOC2H5 -C2H5 HH 2 (2,4-position) Na 023 -COOC2H5 -C4H9 HH 2 ( 2,4 -position) Na 024 -COOC2H5 HH -CH3 (4-position) 1 (# 2) NH ₄ 025 -COOC2H5 HH - CH3 (position 4) 2 (position 2,6) Na 026 -COOC2H5 HH -CH3 (position 2) 1 (position 4) Na 027 -COOC2H5 HH -Cl (position 3) 2 (position 4,6) Na 028 -COOC2H5 HH -Cl (4th position) 1 (2nd position) Na 029 -COOC2H5 HH -OCH3 (4th position) 1 (2nd position) Na 030 -COOC2H5 HH -CH3 (2nd position) 1 (4th position) Na 031 -COOC2H5 HH- C4H9-n (4th position) 1 (2nd position) Na 032 -COOCH3 HHH 2 (2,4 position) Na 033 -COOC4H9 HHH 2 (2,4 position) Na 034 -COPh -CH3 H -CH3 (4th position) 1 (2nd) NH ₄ 035 -COPh -CH3 H -CH3 (2nd) 2 (4,6) Na 036 -COPh -CH3 H -Cl (3rd) 2 (4,6) Na 037 -COPh- CH3 H -Cl (4th) 1 (2nd) Na 038 -COPh -CH3 H -OCH3 (4th) 1 (2nd) Na 039 -COPh -CH3 H -OCH3 (2nd) 1 (4th) Na 040 -COPh -CH3 -CH3 (2nd position) -CH3 (6th position) 1 (4th position) Na 041 -COPh -CH3 H -C4H9-n (4th position) 1 (2nd position) Na 042 -COPh -C2H5 HH 2 (2,4 position) Na 043 -COPh -C4H9 HH 2 (2,4 position) Na 044 -COPh HH -CH3 (4 ) 1 (2nd position) Na 045 -COPh HH -CH3 (2nd position) 2 (2,4 position) Na 046 -COPh HH -Cl (3rd position) 2 (4,6 position) Na 047 -COPh HH -Cl ( 4th) 1 (2nd) K 048 -COPh HH -OCH3 (4th) 1 (2nd) Na 049 -COPh HH -OCH3 (2nd) 1 (4th) Na 050 -COPh H -CH3 (2nd) ) -CH3 (6th) 1 (4th) Na 051 -COPh HH -C4H9-n (4th) 1 (2nd) Na 052 -COOC2H5 -C2H5 HH 2 (4,6th) Na 053 -COOC2H5 -C3H7 -n HH 2 (position 4,6) Na 054-COOC2H5 -C4H9-n HH 2 (position 4,6) K 055 -COOC2H5 -CH (CH3) C2H5 HH 2 (position 4,6) Na 056 -COOC2H5 -C (CH3) 3 HH 2 (position 4,6) Na 057 -COOC2H5 -C6H13-n HH 2 (position 4,6) Na 058 -COOC2H5 -C8H17-n HH 2 (position 4,6) Na 059 -COOC2H5 -2EH HH 2 (position 4,6) Na 060 -COOC2H5 -2EH H -CH3 (position 3) 2 (position 4,6) Na 061 -COOC2H5 -C1OH21-n HH 2 (position 4,6) Na

(Note) In the table, "Ph" indicates a phenyl group.
"2EH" is a 2-ethylhexyl group (-CH2CH (C2H5) C4H9-
n), “3S-BENZOYL” represents a 3-sulfobenzoyl group,
"-N" indicates that the compound is linear.

[0028]

Next, the present invention will be described more specifically with reference to examples. In the examples, parts and% indicate parts by weight and weight%, respectively. It should be noted that the present invention is not limited only to the present embodiment.

Example 1 5 parts of a wool cloth (wool muslin) were put into 150 parts of a dye bath containing the dyes shown in Table 2 (compound No. 1 in Table 1) and 0.2 part of ammonium acetate, and it took 40 minutes. The temperature was raised to 98 ° C., and dyeing was performed at the same temperature for 30 minutes. After dyeing, gradually cool to 60 ° C,
Washed and dried. The evaluation results of the dyed products are shown in Table 2.
As well-known dyes, Kayanol Rubinol 3GS and Kayano
l Milling Red BW was similarly stained and compared.

[0030]

[Table 2]

Example 2 As the three primary colors for anti-dyeing of wool fabric, Y (yellow component): CI Acid Yellow 17, R (red component): CI Acid Re
d 37, B (blue component): CI Acid Blue 182 is known as a dye having good levelness. So, CI Acid Red
37 in place of Compound No. Using the compound No. 1, the dyeing speed and levelness of the three primary colors were evaluated with the following dye composition. (Dye composition) CI Acid Yellow 17 0.5% o. w. f. Compound No. of Table 1 1 0.5% o. w. f. CI Acid Blue 182 0.5% o. w. f. ──────────────────────────── Total) 1.5% o. w. f.

[0032]

[Table 3]

(Note) Residual dyeing is performed to check the dye remaining in the liquor after the initial dyeing. The wool white cloth is re-charged into the dyeing bath after the initial dyeing, and re-dyed (100 ° C., 20 ° C.). And fixing the remaining dye completely.

The compound of the formula (1) has a typical Y component, B
Ingredients CI Acid Yellow 17 and CI Acid Blue 18
2 and the dyeing speed are the same, and "color separation" does not occur in the initial dyeing and residual dyeing, and the color changes from achromatic gray to black from the start to the end of dyeing. This indicates that the dye reproducibility due to the change in the dyeing conditions is excellent, and is of high practical value.

Example 3 5 parts of nylon jersey were treated with the dye and acetic acid 0.2 of Table 4 below.
Into 150 parts of the dyeing bath containing 100 parts
And dyed at the same temperature for 30 minutes. After dyeing, it was gradually cooled to 60 ° C., washed with water and dried. Table 4 shows the evaluation results after dyeing.

[0036]

[Table 4]

(Note-1) The dyed cloth contains 0.1 part of acetic acid and 0.15 part of Sunlife TN (Nichika Chemical's Fix agent).
A cloth treated in a 0 part bath at 85 ° C. for 30 minutes was used. As a clear Red for nylon dyeing, it has better light fastness than existing products and has high practical value.

[0038]

According to the dyeing method of the present invention, a clear red polyamide fiber dyeing material having excellent levelness and various fastnesses can be obtained. In particular, according to the method of the present invention, discoloration due to formalin does not occur even in wool dyeing performed in the presence of formalin.

Claims (2)

[Claims] (1) Formula (1) (In the formula, R ₁ is an alkoxycarbonyl group, a carboxy group, a benzoyl group or 3-sulfobenzoyl group, R ₂
Represents a hydrogen atom or an alkyl group, R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and n represents an integer of 1 to 3, respectively. A method for dyeing polyamide fibers, comprising using the anthrapyridone compound represented by the formula (1) or a salt thereof. 2. A dyed polyamide fiber dyed with the anthrapyridone compound represented by the formula (1) or a salt thereof according to claim 1.