KR0145810B1 - Polyimide type dye composition for fibers and leathers - Google Patents

Abstract

The present invention relates to a polyamide fiber and a dye composition for leather, which is harmless to the human body.

The present invention is a dye composition having a composition in which the following formula (1) dye and the following formulas (1) to (3) dyes are blended in a ratio of 50:50 to 90:10. Dyeing of textiles and leather results in daylight, wash and chlorine fastness equal to CIAcid Red 114.

D-N = N-E

{Where D is Group (wherein m is an integer of 4 to 14, preferably 10 to 12, n is an integer of 1 to 0, and the position of the CH ₃ (CH ₂ ) m group is ortho, meta, para or a mixture thereof) E) Group wherein Y ₁ represents -COCH ₃ , -COC ₂ H ₅ , -CO ₃ CH ₇ or Group and the position of the SO ₃ Na group in the naphthalene nucleus is one of the * mark positions)}

Wherein X ₁ and X ₂ independently represent —SO ₃ Na and hydrogen, respectively, and contain at least one —SO ₃ Na group. W is Q or Q ′ and Q is Q 'is being)

(Where X ₅ represents —NO ₂ , X ₆ represents —SO ₃ Na group, X ₇ represents hydrogen or —CH ₃ , X ₈ represents —OH, —OCH ₃ , —OC ₂ H ₅ or Indicates.

Description

Dye composition for polyamide fiber and leather

The present invention relates to a red dye composition which not only obtains high fastness in dyeing polyamide fibers and leather, but also has high safety for humans.

Fibers based on polyamides are mainly used in sports and leisure products, and have been required to have high fastness for daylight, laundry, and chlorine fastness according to the trend of high quality leather. One of the most commonly used dyes for this purpose is C.I.Acid Red 114, which has been used most often because of its low cost as well as meeting the above requirements.

However, this dye has been controversial over the problem of carcinogenicity since 3,3'-dimethylbenzidine is used as an intermediate. Recently, in Germany, the dye is classified as a MAK IⅠ A2 group, that is, a carcinogenic dye. Processed products that have been dyed and come into contact with human skin have been banned from imports since July 1995, and these measures are gradually spreading around the world, and their replacement dyes are urgently required.

The present inventors have diligently studied to solve these problems, and as a result, the dye of the following formula (1) is excellent in compatibility with the dyes of the following formulas (1) to (3), and thus, the above-mentioned object is mixed. Came to discover that it can be achieved.

D-N = N-E

{Where D is Group (wherein m is an integer of 4 to 14, preferably 10 to 12, n is an integer of 1 to 0, and the position of the CH ₃ (CH ₂ ) m group is ortho, meta, para or a mixture thereof) E) Group (wherein Y ₁ represents -COCH ₃ , -COC ₂ H ₅ , -COC ₃ H ₇ or Group, and the position of the -SO ₃ Na group in the naphthalene nucleus is one of the * marks.)}

Wherein X ₁ and X ₂ independently represent —SO ₃ Na or hydrogen, respectively, and include at least one —SO ₃ Na group. W is Q or Q ′ and Q is Q 'is being)

Wherein X ₅ represents —NO ₂ , X ₆ represents a —SO ₃ Na group, X ₇ represents hydrogen or —CH ₃ , X ₈ represents —OH, —OCH ₃ , —OC ₂ H ₅ , or Indicates.

The combination of these dyes is formula (1): formula (1) = 50: 50 ~ 90:10, formula (1): formula (2) = 60: 40 ~ 90:10, formula (1) by weight ratio When using the ratio of the formula (3) = 60:40 ~ 90:10, excellent results were obtained.

Of course, the dyes of the above formulas (1) and (1), (2) and (3) are in the form of water-soluble salts.

The dye composition of the present invention has satisfactory properties as a substitute for C.I.Acid Red 114, which is the object of the invention. That is, not only in terms of economic efficiency, color and color fastness, but also in terms of safety of the human body could be satisfied.

The dye composition of the present invention exhibits color and color fastness similar to C.I.Acid Red 114 when dyed leather, wool, silk, and polyamide fibers, and is particularly preferably a dyed material such as leather or synthetic polyamide fibers.

Dye composition of the present invention using the dye composition of the present invention is a method of dyeing the synthetic polyamide-based fiber in a salt bath using a primary dyeing machine, Jiger dyeing machine, Hanker dyeing machine, etc. in a bath ratio of 1:10 ~ 1:40 When the temperature is increased with the salts, the dyeing starts from around 40 ℃, the dyeing is done at 70 ~ 85 ℃, and the dyeing method is completed by raising the temperature to 95 ℃ and completing the thiodiethylene glycol, thiourea, ammonium stannate and dyes. There is a printing method that mixes and seals the sachets with steam and then treats them with steam for 30 to 40 minutes.

In addition, the leather dyeing method is pretreated with ammonia water (1%) on tanned leather with chromium compound, and then dye with a suitable amount of dye and softener for 90 minutes at 60 ℃ and then formic acid is fixed for 10 minutes in 1 ~ 2% owf. .

Hereinafter, the present invention will be described in detail with reference to Examples. In addition, the scope of this patent is not limited to an Example. Where parts and% means parts by weight and% by weight.

Example 1

(1) After dispersing 35.8 parts of monosodium H acid salt in 60 parts of water, 10 parts of calcium carbonate powder is added to dissolve it at pH 6.5 to 7.0. Add 30 parts of calcium carbonate powder, add 60 parts of paratoluenesulfonyl chloride over 3 hours while maintaining 55-60 ° C., stir at 70 ° C. for 4 hours, add 29 parts of sodium hydroxide solution (50%), and add 2 parts at 85 ° C. After stirring for 30 hours, neutralized with 26 parts of concentrated hydrochloric acid, 168 parts of sodium carbonate powder and 400 parts of water were added thereto, and the resultant was stirred at 80-90 ° C. for about 1 hour, filtered to remove insoluble content, and cooled to prepare a coupler solution.

(2) On the other hand, add 26.2 parts of 4-dodecylaniline to 100 parts of hot water (60 ° C), add 33 parts of hydrochloric acid (35%) and 1 part of a dispersant, and disperse it. The solution is dropped into diazotized by dropping, and then 0.5 parts of sulfamic acid is used to remove excess nitrite. Subsequently, crushed ice was added to the Coppler solution prepared in (1), 4-dodecyl aniline diazotized solution was added at 5 ° C. or less, and the mixture was stirred overnight to complete the coupling reaction. 84.6 parts of red dye were obtained.

To the red dye of formula (4) to prepare a yellow dye of the formula (5) by a known method

After dissolving 0.2 part of the red dye composition prepared by mixing in a weight ratio of Formula (4): Formula (5) = 75:25 in 100 parts of hot distilled water, diluting it with 400 parts by adding distilled water, and adding 2 parts of glacial acetic acid (10%) 10 parts of nylon cloth is added to the salt bath, and the temperature is gradually raised for about 30 minutes, dyed for about 1 hour near the boiling point, the nylon cloth is taken out, washed well, and dried at about 70 to 80 ° C to give a uniform red dye solution. Got it. This was similar to staining with C.I.Acid Red 114.

In addition, 5 parts of the mixed dye, 3 parts of thiodiethylene glycol, 3 parts of thiourea, 3 parts of ammonium stannate (50%), and 60 parts of arc and 26 parts of water are mixed well without foaming, and then dried by drying with nylon fabric Fixing with steam for 30-40 minutes, washing with hot water and drying showed similar results with staining with CIAcid Red 114. In the leather dyeing method, 0.5 part of the mixed dye is dissolved in 50 parts of distilled water, 10 parts of ammonia water (1%) is added, 10 parts of grain leather is added to the dye bath, and the temperature is gradually raised to 60 ° C. over 10 minutes. After dyeing and softening for 90 minutes, add 2 parts of formic acid (10%), fix it for 10 minutes, take out the leather, wash it well with hot water (40 ℃), wash it again with cold water, and dry it, and dye it vividly. Salt was obtained. This showed similar results with staining with C.I.Acid Red 114.

Example 2

A dye composition prepared by mixing a yellow dye of formula (6) with a red dye of formula (4), described in Example 1, by a known method, and then mixing it in a weight ratio of formula (4) :( 6) = 67:33. The staining as in Example 1 using the results showed similar results to the staining using CIAcid Red 114.

Example 3

A dye composition prepared by mixing the red dye of formula (4) described in Example 1 with an orange dye of formula (7) by a known method and mixing in a weight ratio of formula (4): formula (7) = 65:35 Using the same staining as in Example 1 showed similar results with staining using CIAcid Red 114.

Example 4

75 parts of red dyes of the following Chemical Formula (8) were obtained using K acid instead of H acid of Example 1.

Dyeing was carried out as in Example 1 using a red dye composition prepared by mixing the yellow dye of formula (5) of Example 1 in the formula (8) in a weight ratio of formula (8): formula (5) = 85:15. Results Similar results were obtained with staining with CIAcid Red 114.

Example 5

(1) After dispersing 35 parts of monosodium H acid salt in 160 parts of water, 11 parts of sodium carbonate powder is gradually added to pH 8.0 to 8.5 and completely dissolved. 20.4 parts of anhydrous acetic acid was added dropwise over about 1 hour while maintaining the temperature at 35 ° C. to 40 ° C., and stirred for about 1 hour, and then 9 parts of sodium carbonate was added to adjust the pH to 8.0 to 8.5, followed by stirring at 98-100 ° C. for 1 hour. A coupler solution was prepared.

(2) 34.2 parts of dodecylaniline sulfonic acid mixture is added to 100 parts of hot water (60 ° C), and sodium carbonate powder is gradually added to pH 7-8 to dissolve. Subsequently, 8.4 parts of sodium nitrite is added to dissolve and cooled to room temperature. 50 parts of water, 300 parts of crushed ice and 28 parts of concentrated hydrochloric acid were slowly added to the solution while maintaining 0 ° C., and stirred for about 1 to 2 hours to diazotize. Crushed ice was added to the Coppler solution prepared in the above), and the diazotized solution of the dodecyl aniline sulfoic acid mixture was added at 5 ° C. or lower, and the mixture was stirred overnight to complete the coupling reaction. 120 parts were obtained.

CIAcid Red was stained as in Example 1 using a red dye composition prepared by mixing the yellow dye of Formula (6) with the weight ratio of Formula (9): Formula (6) = 76:24 in Formula (9). Similar results were obtained with staining using 114.

[Examples 6-17]

As shown in Table 1, the dye composition was prepared and dyed as in Example 1, and the results similar to those obtained using C.I.Acid Red 114 were obtained.

[Examples 18-21]

As shown in Table 2, a dye composition was prepared and dyed as in Example 1, whereby a result similar to that obtained using C.I.Acid Red 114 was obtained.

[Examples 22-38]

As shown in Table 3, the dye composition was prepared and dyed as in Example 1, and the results similar to those obtained using C.I.Acid Red 114 were obtained.

(Z in Table 3 Is displayed.)

Comparative Example 1

The color fastness of C.I.Acid Red 114 and the dye compositions of Examples 3, 4, 10, 17, and 18 of the present invention were compared by the same method, and the results were as shown in Table 4.

*Test Methods:

1) Daylight: ISO 105-B02 (Xenon Arc)

2) Laundry: ISO 105-C03-1978

3) Wear: ISO 105-X12-1978

4) Chlorine: ISO 105-E02-1978

Claims (3)

A dye composition for polyamide fibers and leather blended with a red dye of the following formula (1) and a dye of the following formula (1) in a weight ratio of formula (1): formula (1) = 50:50 ~ 90:10 D-N = N-E {Where D is Group (wherein m is an integer from 4 to 14, n is an integer from 1 to 0, and the position of the CH ₃ (CH ₂ ) m group is ortho, meta, para or a mixture thereof), E is Group (wherein Y ₁ represents -COCH ₃ , -COC ₂ H ₅ , -COC ₃ H ₇ or Group, and the position of -SO ₃ Na group in the naphthalene nucleus is one of the * mark positions)} Where X ₁ and X ₂ independently represent -SO ₃ Na and a hydrogen group, each of which must contain at least one -SO ₃ Na group. W is Q or Q 'and Q is Q 'is being) A dye composition for polyamide fibers and leather, wherein a red dye of the following formula (1) and a dye of the following formula (2) are formulated in a weight ratio of formula (1): formula (2) = 60:40 to 90:10 D-N = N-E Where D is Group (wherein m is an integer from 4 to 14, n is an integer from 1 to 0, and the position of the CH ₃ (CH ₂ ) _m group is ortho, meta, para or a mixture thereof), E is Group wherein Y ₁ represents -COCH ₃ , -COC ₂ H ₅ , -COC ₃ H ₇ or Group, the position of the SO ₃ Na group in the naphthalene nucleus is one of the * position A dye composition for polyamide fiber and leather blended with the red dye of the following formula (1) and the dye of the following formula (3) in a weight ratio of formula (1): formula (3) = 60:40 ~ 90:10 D-N = N-E {Where D is Group (wherein m is an integer from 4 to 14, n is an integer from 1 to 0, and the position of the CH ₃ (CH ₂ ) m group is ortho, meta, para or a mixture thereof), E is Group (wherein Y ₁ represents -COCH ₃ , -COC ₂ H ₅ , -COC ₃ H ₇ or Group and the position of the SO ₃ Na group in the naphthalene nucleus is one of the * mark positions)} Wherein X ₅ represents -NO ₂ , X ₆ represents -SO ₃ Na group, X ₇ represents hydrogen group or -CH ₃ , X ₈ represents -OH, -OCH ₃ , -OC ₂ H ₅ or Indicates.