KR101902752B1 - Method of dyeing polyester - Google Patents

Abstract

상기 화학식 1에서,
G₁ 및 G₂는, 서로 독립적으로 C₁-C₄ 알킬이거나, 함께 펜타메틸렌이고,
Z₁ 및 Z₂는 메틸이거나, Z1 및 Z₂는 함께 브릿징 멤버(bridging member)를 형성하고, 상기 브릿징 멤버는 에스테르, 에테르, 하이드록실, 옥소, 시아노하이드린, 아미도, 아미노, 카복실 또는 우레탄 라디칼에 의해 치환되지 않거나 치환되고,
E는 옥실 또는 하이드록실이다.The present invention relates to a method for dyeing a polyester-containing textile material,
Wherein the textile material comprises,
(a) at least one disperse dye and
(b) at least one compound of formula
≪ / RTI > to a process for dyeing a polyester-containing textile material.
Formula 1

In Formula 1,
G ₁ and G ₂ are independently of each other C ₁ -C ₄ alkyl or together are pentamethylene,
Z ₁ and Z ₂ may be a methyl, Z1 and Z ₂ are together a bridging member (bridging member) for forming, and wherein the bridging member is an ester, ether, hydroxyl, oxo, cyano nohayi gave, amido, amino, carboxyl Or is unsubstituted or substituted by a urethane radical,
E is oxyl or hydroxyl.

Description

[0001] METHOD OF DYEING POLYESTER [0002]

The present invention relates to a method of dyeing a polyester-containing textile material.

Reduction sensitivity of azo disperse dyes is a problem in the polyester dyeing process. The degree of dye breakdown in the dye liquor depends on the chemical structure of the dye, the processing conditions and the type of dye aid. This reduction sensitivity significantly affects the reproducibility of the shade, especially in combination dyeing. Important dyeing conditions are filled bulk dyes, with air and oxygen removed completely. Although lignin sulfonate dispersants are widely used due to their low cost and, in particular, their reliability at high dyeing temperatures (130 DEG C to 135 DEG C), due to their reducing power, these dispersants can be used as reducing- And the like.

It has now surprisingly been found that when the oxide or hydroxide of a sterically hindered amine is added to the salt solution, the reducing decomposition of the sensitive disperse dye under bulk dyeing conditions can be significantly reduced.

The present invention relates to a method of dyeing a polyester-containing textile material,

(a) at least one disperse dye and

(b) at least one compound of formula

≪ / RTI > to a process for dyeing a polyester-containing textile material.

In Formula 1,

G ₁ and G ₂ are independently of each other C ₁ -C ₄ alkyl or together are pentamethylene,

Z ₁ and Z ₂ may be a methyl, Z1 and Z ₂ are together a bridging member (bridging member) for forming, and wherein the bridging member is an ester, ether, hydroxyl, oxo, cyano nohayi gave, amido, amino, carboxyl Or is unsubstituted or substituted by a urethane radical,

E is oxyl or hydroxyl.

In principle, any disperse dyes known for dyeing polyester can be used in the process according to the invention.

Preferably, component (a) is a compound of formula (2), (3) or (4).

In the above Chemical Formulas 2 to 4,

R ₁ is C ₁ -C ₄ alkyl,

R < ₂ > is hydrogen, bromo, chloro, cyano or nitro,

R < ₃ > is bromo, chloro, cyano or nitro,

R < ₄ > is hydrogen, methyl or methoxy,

R ₅ and R ₆ are independently of each other selected from the group consisting of ethyl, benzyl, 2-cyanoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2- (2-methoxyethoxy) Ethyl, 2- (2-ethoxyethoxy) -ethyl, 2-acetyloxyethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 1- methoxycarbonylethyl or 1- ethoxycarbonylethyl,

R < ₇ > is hydrogen, bromo, chloro, cyano or nitro,

R < ₈ > is bromo, chloro, cyano or nitro,

R < ₉ > is methyl or ethyl,

R ₁₀ is hydrogen, methyl, methoxy, acetylamino or propionylamino.

The disperse dyes of formulas (2), (3) and (4) are known or can be prepared according to known methods.

The following disperse dyes are preferred: C.I. Disperse Yellow 114, C.I. Disperse Yellow 211, C.I. Disperse Yellow 54, C.I. Disperse Orange 25, C.I. Disperse Orange 30, C.I. Disperse Orange 31, C.I. Disperse Orange 44, C.I. Disperse Orange 61, C.I. Disperse Red 50, C.I. Disperse Red 73, C.I. Disperse Red 82, C.I. Disperse Red 167, Disperse Red 167: 1, C.I. Disperse Red 324, C.I. Disperse Red 356, C.I. Disperse Red 376, C.I. Disperse Red 382, C.I. Disperse Red 383, C.I. Disperse Violet 93: 1, C.I. Disperse violet 107, C.I. Disperse Blue 56, C.I. Disperse Blue 60, C.I. Disperse Blue 79: 1, C.I. Disperse Blue 93: 1, C.I. Disperse Blue 165, C.I. Disperse Blue 165: 1, C.I. Disperse Blue 183, C.I. Disperse Blue 284, C.I. Disperse Blue 291, C.I. Disperse Blue 337, C.I. Disperse Blue 354 and C.I. Disperse Blue 378.

As the component (a), the compounds of the formulas (201), (202), (301) and (302)

및

And

Compounds of formula 1 are likewise known and are described, for example, in WO 01/85857.

Component (b) for use in the process according to the invention also comprises an ammonium salt obtainable by reaction of the compound of formula (1) with an acid.

The compound of formula (I) is preferred as component (b).

[ Formula 1a ]

In formula (1a)

E is oxyl or hydroxyl,

R < ₁₁ > is hydrogen or methyl,

n = 1 or 2,

  When n = 1,

Y is hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl, propargyl, glycidyl, or is from 1 to 10 hydroxyl groups being unsubstituted or substituted by intervening from 1 to 20 oxygen atoms C ₂ -C ₅₀ alkyl which may be substituted, or

Y is C ₁ -C ₄ alkyl substituted by -COOR ₁₂ , wherein R ₁₂ is hydrogen, C ₁ -C ₄ alkyl or phenyl,

  When n = 2,

Y is capable of intervening C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, or is optionally substituted by 1 to 10 hydroxyl groups, or substituted with from 1 to 20 oxygen atoms are C ₁ - Lt; _/ RTI >

Suitable compounds of formula (I) are, for example,

Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

Bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium citrate,

1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium bisulfate,

1-oxyl-2,2,6,6-tetramethyl-4-oxopiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium acetate,

1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-methoxypiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-methoxypiperidinium acetate,

1-oxyl-2,2,6,6-tetramethyl-4-acetoxypiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium acetate,

1-oxyl-2,2,6,6-tetramethyl-4-propoxypiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-propoxypiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-propoxypiperidinium acetate,

1-hydroxy-2,2,6,6-tetramethyl-4- (2-hydroxy-oxapentoxy) piperidinium acetate,

1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine,

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride,

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate,

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate,

1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate and

Bis (1-hydroxy-2,2,6,6-tetramethylpiperidine-4-hydroxypiperidinium) citrate.

Preferably, the textile material comprises as component (b)

Of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine.

In the process according to the invention, the dyes according to component (a) may be applied individually or as a mixture. Advantageously, a mixture of two or three dyes (di- or tri-chromicity) can be used. However, more than four dye mixtures can also be used, especially for composite hue generation.

The amount of said individual dyes used in the saline solution can vary within a wide range depending on the desired depth of the hue. Generally, amounts of from 0.01% to 35% by weight, in particular from 0.1% to 15% by weight, based on the fiber material to be dyed have proved advantageous. The liquid ratio can be selected within a wide range, for example, in the range of 1: 2 to 1:50, preferably 1: 3 to 1:15.

In addition to the components (a) and (b) defined above, the liquid may further comprise conventional additives such as dispersants, leveling and wetting agents, penetration enhancers, pH-adjusting agents and defoamers.

Suitable dispersing agents may be nonionic or anionic. Nonionic dispersants are, for example, the reaction products of alkylene oxides such as ethylene oxide or propylene oxide with fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides. Anionic dispersants are, for example, lignin sulfonates and their salts, alkyl-sulfonates or alkylaryl-sulfonates, alkylaryl polyglycol ether sulfonates, alkali metal salts of condensation products of naphthalenesulfonic acid and formaldehyde, Nate and ethoxylated novolak.

In a preferred embodiment, the textile material is treated with a liquid that further contains lignin sulfonate as a dispersant.

The textile material may be used in any form, for example, in the form of fibers, yarns, wovens, knits or nonwovens.

In the context of the present invention, the polyester-containing textile material may be a synthetic polyester, a polyester, a polyester / wool or a polyester / elastane blend, as well as pure polyester, Containing blends.

Preferably, the textile material is a polyester or a polyester / cotton blend.

Typically, the polyester fiber material is applied in the temperature range of 80 DEG C to 150 DEG C, preferably 90 DEG C to 140 DEG C, in the range of pH 3.5 to 5.5, especially pH 4.0 to 5.0, in the presence of conventional anionic or nonionic dispersants And are dyed with an aqueous dispersion by a depressurization process in the presence or absence of a conventional swelling agent (carrier).

No special equipment is required. For example, conventional dyeing devices such as open baths, winch becks, jigs, or paddles, jets or circulating devices may be used.

In order to improve the wet-fastness properties of the dyed synthetic polyester fibers, it is preferred that the post-treatment for removing all the unfixed dyes is carried out at a pH value of, for example, 7 to 12, pH value, and at a temperature of, for example, 30 ° C to 100 ° C, particularly 50 ° C to 80 ° C. In the case of intense hues, especially on textile blends, the unfixed dyes are advantageously reduced by the addition of a reducing agent, for example, a hydrosulfite, such as sodium hydrosulfite, to the alkaline post- Can be eliminated. The dye immobilized on the fibrous material is not attacked by the treatment. Advantageously, the amount of reducing agent added is, for example, from 0.1% to 8.0% by weight, especially from 0.5% to 5.0% by weight, based on the weight of the post treatment bath.

According to the method according to the invention, a dyeing on the polyester fiber material is obtained, which shows a considerable improvement in terms of depth of color tone, without the washing fastness or light fastness properties being adversely affected.

The following examples are provided to illustrate the invention. Unless otherwise specified, temperatures are given in degrees centigrade, parts are parts by weight, and percentages are referred to in weight percent. The weight portion is correlated with the volume portion in the same ratio as the kilogram to the liter.

Example  One

5㎖/ℓ, 나트륨 하이드록설파이트 농축액 2g/ℓ 및 시판 비이온성 세척제(에리오폰^? OL(ERIOPON^? OL), 훈츠만에서 공급) 1g/ℓ를 함유하는 액체에서 20분/70℃. 상기 염색물을 헹구고, 중화시키고 건조시킨다.10 g of a 100% polyester knitted fabric was weighed in the same manner as in Example 1 except that 10 g of a commercially available formulation CI Disperse Blue 165: 1 45 mg, 50 mg of the compound of the formula (101), 200 mg of a commercial dispersant (REAX 85A, lignin sulfonate, supplied by BASF) and anti-foaming agents (alba ^flow? UNI ^(ALBAFLOW? UNI), supplied by huncheu only) 50mg, ammonium sulfate to prepare a salt solution of a total volume 100㎖ containing 80% acetic acid for about 0.1㎖ so that the 100mg and pH 4.5 auto Klee And stained in an autoclave. To simulate a filled bulk dyeing machine, the fabric is placed in a saline solution and thoroughly flushed with nitrogen immediately before closing the autoclave, thereby completely removing all air and oxygen. The liquid is heated at 2 [deg.] C per minute, heated to 135 [deg.] C and held at 135 [deg.] C for 60 minutes. After a cold rinse, the dyeing is treated with reducing clearing: caustic soda 36 °

5㎖ / ℓ, sodium hydro sulfite rokseol concentrate 2g / ℓ and a commercially available non-ionic detergents (Erie ^ohpon? OL ^(ERIOPON? OL), supplied by huncheu only) and 20 minutes from the liquid containing 1g / ℓ / 70 ℃. The dyeings are rinsed, neutralized and dried.

Depth of color tone, is determined by reflectance measurement, using the same fabrics, dyes and adjuvants and badin Uni in place of the set to 100%, the compound of formula ^(101)? Expressed as a percentage relative to the depth of the hue obtained by the benchmark process performed using DP (UNIVADINE ^? DP (supplied by Dispersant, Huntsman)).

compare Example  2

The dyeing step described in Example 1 is repeated except for the compound of formula (101).

Example 1 and Comparative Example 2 are repeated with different dyes. The depth values of the resulting shades are summarized in Table 1. [

Example 1 and Comparative Example 2 of the same series of benchmarking processes were carried out using a fabric blend of 65% gray face and 35% polyester instead of a 100% polyester fabric, And 200 g of a commercially available lignin sulfonate dispersant (REAX 85A) in Example 2 of the present invention. The depth values of the resulting hues are summarized in Table 2.

The same series of benchmarking processes, Comparative Example 2 and Example 1, were carried out using a fabric blend of 65% cotton and 35% polyester instead of a 100% polyester fabric and a commercial lignin sulfonate dispersant (REAX) 85A) without washing with nitrogen. The depth values of the resulting hue are summarized in Table 3.

Example  3

5㎖/ℓ, 나트륨 하이드록설파이트 농축액 2g/ℓ 및 시판 비이온성 세척제(에리오폰^? OL, 훈츠만에서 공급) 1g/ℓ를 함유하는 액체에서 20분/70℃. 상기 염색물을 헹구고, 중화시키고 건조시킨다.5 g of a 100% polyester knit fabric was mixed with 75 mg of a commercially available formulation CI Disperse Red 277 (Solvent Red 197), 20 mg of a compound of the formula (101), a commercial wetting agent and defoamer (supplied by Alvaflow ^? UNI, Huntsman) 100 mg, ammonium sulfate 50 mg and a total volume of 50 ml of a saline solution containing about 0.05 ml of 80% acetic acid to make it pH 4.5. The liquid is heated at 2 [deg.] C per minute, heated to 135 [deg.] C and held at 135 [deg.] C for 60 minutes. After a cold rinse, the dye is subjected to a reductive post treatment: caustic soda 36 °

5㎖ / ℓ, sodium hydro sulfite rokseol concentrate 2g / ℓ and a commercially available non-ionic detergents and 20 minutes from a liquid containing the (Erie ^ohpon? OL, supplied by huncheu only) 1g / ℓ / 70 ℃. The dyeings are rinsed, neutralized and dried.

compare Example  4

The dyeing step described in Example 3 is repeated except for the compound of formula (101).

Results: The dyestuff of Example 3 of the present invention provided a significantly brighter hue and significantly stronger fluorescence compared to the dye of Comparative Example 4. [

Example  5 and compare Example  6

Examples 3 and 4 were prepared by dissolving 75 mg of Disperse Red 277 in Disperse Red 362 which gives the same positive effect on hue and fluorescence in the case of Example 5 (using the compound of formula (101)) as compared to Example 6 (Solvent Red 196).

Claims (9)

As a method for dyeing a polyester-containing textile material,
Wherein the textile material comprises,
(a) at least one disperse dye and
(b) at least one compound of formula
≪ / RTI > characterized in that the polyester-containing textile material is treated with a liquid containing a polyester-containing textile material.
Formula 1

In Formula 1,
G ₁ and G ₂ are independently of each other C ₁ -C ₄ alkyl or together are pentamethylene,
Z ₁ and Z ₂ are methyl or, Z1 and Z ₂ wherein the bridging member, and together form a bridging member (bridging member) is unsubstituted or substituted with ester, ether, hydroxyl, oxo, cyano nohayi gave, amido , Amino, carboxyl or urethane radical,
E is oxyl or hydroxyl. The method according to claim 1, wherein the textile material is treated with a liquid containing a compound of formula (2), (3) or (4) as component (a).
(2)

(3)

Formula 4

In the above Chemical Formulas 2 to 4,
R ₁ is C ₁ -C ₄ alkyl,
R < ₂ > is hydrogen, bromo, chloro, cyano or nitro,
R < ₃ > is bromo, chloro, cyano or nitro,
R < ₄ > is hydrogen, methyl or methoxy,
R ₅ and R ₆ are independently of each other selected from the group consisting of ethyl, benzyl, 2-cyanoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2- (2-methoxyethoxy) Ethyl, 2- (2-ethoxyethoxy) -ethyl, 2-acetyloxyethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 1- methoxycarbonylethyl or 1- ethoxycarbonylethyl,
R < ₇ > is hydrogen, bromo, chloro, cyano or nitro,
R < ₈ > is bromo, chloro, cyano or nitro,
R < ₉ > is methyl or ethyl,
R ₁₀ is hydrogen, methyl, methoxy, acetylamino or propionylamino. The method of claim 1, wherein the textile material comprises as component (a)

or

Lt; RTI ID = 0.0 > of: < / RTI > 4. The process according to any one of claims 1 to 3, wherein the textile material is treated with a liquid containing a compound of formula (I) as component (b).
Formula 1a

In formula (1a)
E is oxyl or hydroxyl,
R < ₁₁ > is hydrogen or methyl,
n = 1 or 2,
When n = 1,
Y is hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl, propargyl, glycidyl, or is unsubstituted or substituted, is substituted by one to ten hydroxyl groups, from 1 to 20 oxygen atoms C ₂ -C ₅₀ alkyl which may be interrupted, or
Y is C ₁ -C ₄ alkyl substituted by -COOR ₁₂ , wherein R ₁₂ is hydrogen, C ₁ -C ₄ alkyl or phenyl,
When n = 2,
Y is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, or is unsubstituted or substituted, C ₁ to intervening substituted and 1 to 20 oxygen atoms by one to ten hydroxyl groups Lt; _/ RTI > 4. The process according to any one of claims 1 to 3, wherein the textile material comprises as component (b)

Of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine. 4. The method according to any one of claims 1 to 3, wherein the textile material is treated with a liquid further comprising lignin sulfonate. The method of any one of claims 1 to 3, wherein the textile material is a polyester or a polyester / cotton blend. The method according to any one of claims 1 to 3, wherein after the treatment with the dyeing liquor, the reducing after treatment is performed. 9. The method of claim 8, wherein sodium hydrosulfite is used in the reductive post-treatment step.