FR2616816A1 - Process for the treatment of cellulose fibres optionally mixed with synthetic fibres, process for dyeing a polyester-cotton article and dyed products obtained - Google Patents

Abstract

Dyeing of textile materials. Process for the treatment of cellulose fibres by themselves or mixed with synthetic fibres with a view to improving their dyeing by dyes, according to which these fibres are treated with a salt of a hydroxyhalopropylammonium compound in the presence of an alkali metal borate, followed by performing a thermal binding of the ammonium compound onto the fibres at a temperature of 170-230 DEG C. Application to the dyeing of cotton and cotton-polyester fibres in particular.

Description

 The object of the present invention is to provide an improvement in the dyeing of cellulosic fibers and more particularly in the dyeing of articles made up of a mixture of cellulosic fibers and synthetic fibers such as a polyester-cotton blend.

 Dyeing of polyester-cotton articles can be done with different classes of dyes. Dispersed dyes are frequently applied, for example, to dye the polyester fiber, and reactive or direct dyes to dye the cellulose fiber.

Several dyeing processes can be used to dye these articles. The conditions for fixing dispersed and reactive dyes - their mutual influence often contributing to reducing yields or their sensitivity to pH - make it practically impossible to apply and fix these two classes of dyes simultaneously. during a dyeing process carried out continuously. For these reasons, a continuous dyeing process is adopted in practice which can be illustrated by the following operations
at. Impregnation of the fibers by padding in a bath containing the dispersed and reactive dyes.

 b. Drying, then heat setting carried out at a temperature of around 2000C in order to fix the dyes dispersed on the polyester part.

 vs. New impregnation carried out in a bath containing soda and sodium chloride.

 d. Spray to fix the reactive dyes on the cellulosic part.

 e. Wash to remove loose dyes.

The application of this process leads, as a general rule, to obtaining the following results
- a fixation of the order of 60-65% of the reactive dyes on the cellulosic fiber,
- significant soiling of the washing water due to insufficient fixing of the reactive dyes,
- difficult washing and poor solidity, especially in the case of dark colors, due to the preceding conditions,
- the need to use significant quantities of sodium chloride, of the order of 200 g per liter, which contribute to very highly polluting the waste water.

ou de dérivés hydroxyhalogénés de la formule II

oû R', R" et R"' sont des radicaux alkyle de 1 a 3 atomes de carbone, et X est un anion tel que C1-, S04--, etc...An improved process for dyeing cellulosic fibers with reactive dyes involving the use of additives consisting of salts of epoxy-propyl-ammonium compounds of formula (I)

or hydroxyhalogenated derivatives of formula II

where R ', R "and R"' are alkyl radicals of 1 to 3 carbon atoms, and X is an anion such as C1-, SO4--, etc ...

in the dye bath, has already been proposed in
FR-A-2 096 702. In this process the additives in question are used in conjunction with a caustic agent such as sodium hydroxide or sodium carbonate and, after dyeing the textile material, fixing is carried out at high temperature (150DC) or cold. A solid dye is thus obtained with a good dye yield. It should be noted that the derivatives of formula (II), when they are used, are transformed into compounds of formula (I) under the action of the caustic agent. This process has the disadvantage of giving rise to yellowing when the fixing is carried out at very high temperatures (2000C) like those which are in favor today.

In FR-A-2 303 112 a process has been described for treating cellulosic fibers or mixed fibers such as polyester-cotton, with a view to improving the dyeing of these materials, which involves the attachment of epoxy compounds to these materials. propyl-ammonium similar to those of formula (I) used in FR-A-2 096 702. Unlike, however, the preceding process, the compound of formula
I is used together with boric acid and in the absence of caustic agent. After dyeing the textile material, heat-fixing is carried out at very high temperature (150-2300C). This avoids the yellowing that occurred with the process of FR-A-2,096,702 when using high heat-fixing temperatures.

 The process of FR-A-2 303 112 has, however, the drawback of being able to be used only with the additives of formula I and not with those of formula II, since it is carried out under acidic conditions .

Now, the compounds of formula I are very hydrolyzable compounds which make it difficult to obtain good reproducibility of the dyeing process. In addition, it has been found that the process of FR-A-2 303 112 tends to alter the colors of the dyed materials.

 The invention aims to improve the dyeing of cellulosic fibers and in particular of cellulose fibers mixed with synthetic fibers, while avoiding the drawbacks of the above-mentioned processes.

ou R1, R2 et R3 sont des radicaux alkyle de 1 à 3 atomes de carbone,
R4 est un radical alkyle ou hydroxyalcoyle de 1 à 4 atomes de carbone,

sont H ou un radical alkyle de 1 & 3 atomes de carbone, et
X est un anion d'acide minéral ou organique, en ce qu'on effectue ledit traitement en présence d'un borate de métal alcalin, et en ce qu'on effectue une thermofixation du composé de formule (A) ou (B) sur les fibres à une température de 170 à 2300C environ.More specifically, the invention relates to a process for treating cellulosic fibers, alone or in admixture with synthetic fibers, with a view to improving their dyeing with dyes, according to which these fibers are treated with a salt of a hydroxyhalogeno- compound. propyl ammonium, characterized in that at least one compound of formula (A) or (B) is used as the salt of a hydroxyhalopropyl ammonium compound

or R1, R2 and R3 are alkyl radicals of 1 to 3 carbon atoms,
R4 is an alkyl or hydroxyalkyl radical of 1 to 4 carbon atoms,

are H or an alkyl radical of 1 & 3 carbon atoms, and
X is an anion of mineral or organic acid, in that the said treatment is carried out in the presence of an alkali metal borate, and in that the thermofixing of the compound of formula (A) or (B) is carried out the fibers at a temperature of about 170 to 2300C.

 The process of the invention can be implemented in all dyeing processes, continuous or discontinuous, of articles made wholly or in part of cellulosic fibers, involving reactive dyes or even other dyes of cellulosic fibers such than direct dyes, sulfur or vat.

 The process of the invention has, however, a particular interest in the case of a continuous dyeing process using reactive dyes, since it allows in particular to significantly improve the fixation of the reactive dyes applied. It is exceptionally advantageous in the case of such a process aimed at dyeing articles formed from polyester and mixed cotton fibers.

The invention therefore also relates to a continuous process for dyeing a polyester-cotton article, characterized in that it comprises the following steps
at. padding of the polyester-cotton article in a bath containing at least one dispersed dye, at least one compound of the formulas (A) and (B) defined above, and at least one alkali metal borate
b. drying, then thermofixing of the article obtained in step (a) at a temperature of approximately 170 to 2300C in order to simultaneously fix the dyes dispersed on the polyester fiber, and the compound of formulas (A) and (B) and borate on cotton fiber;
vs. padding impregnation of the article obtained in step (b) in a bath containing at least one reactive dye
d. spraying the article obtained in step (c) in order to fix the reactive dye on the cotton fiber;
e.washing the article obtained in step (d) in order to remove the non-fixed dyes.

The application of this new process results in the following advantages
1. A fixation of the order of 85-90% of the reactive dye on the cotton fiber, corresponding to a significant improvement in the yield of the dye used.

 2. A significant reduction in the soiling of the washing water as a result of better fixing of the applied dyes.

 3. Washing more easily achievable and greater solidity, especially in the case of dark colors.

 4. Non-pollution of waste water due to the removal of sodium chloride.

 It is unexpectedly that we have found that the use of an alkali metal borate makes it possible to fix, with excellent yield, the compounds of formula (A) or (B) mentioned without causing during a heating at high temperature, of the order of 2000C, yellowing of the textile article, or causing alteration of the dispersed dye used to dye the synthetic part of said article.

 - By "alkali metal borate" means, according to the invention, the sodium and potassium salts of metaboric, orthoboric or tetraboric acids. Usually, an amount of the order of 10 to 30 g of borate will be used per liter of bath.

 The proportion of compound of formula (A) or (B) is not very critical and can vary widely, but it will preferably be understood, for economic reasons, between 10 and 50 g per liter. Also for economic reasons, it is preferred to use a compound of formula (A) and in particular that where R1, R2 and R3 represent a radical CH3 and X- represents C1-.

 The heat setting temperature of the compound of formula (A) or (B) may vary depending on the material used and the articles treated. It will however be between 170 and 2300C.

Compared to the method currently used (without compound of formula (A) or (B)) for dyeing, continuously, a polyester-cotton article with dispersed and reactive dyes, the method of the present invention provides the following advantages
an improvement in the fixing of the reactive dye of the order of 20 to 30%, ie a significant saving in the dyes used,
- a reduction in pollution of washing water,
- an improvement in the solidity of the colors produced,
- the possibility of making darker colors,
- the removal of large quantities of sodium chloride.

 The following nonlimiting examples are given in order to illustrate the invention.

(appelé ci-après, en abrégé, HEPA)
B/ 40 g/l HEPA
20 g/l Carbonate de sodium
C/ 40 g/l HEPA
20 g/l Bicarbonate de sodium
D/ 40 g/l HEPA
20 g/l Silicate de sodium
E/ 40 g/l HEPA
20 g/l Tétraborate de sodium
Après exprimage permettant de maintenir sur le tissu une quantité de bain d'imprégnation correspondant à 80% du poids du tissu, on sèche puis on soumet les échantillons pendant une minute à une température de 2000C.EXAMPLE I
A series of cotton fabric samples, previously bleached, are impregnated by padding in each of the following aqueous baths
Al 40 g / l of the compound of formula (A) below

(hereinafter abbreviated as HEPA)
B / 40 g / l HEPA
20 g / l Sodium carbonate
C / 40 g / l HEPA
20 g / l Sodium bicarbonate
D / 40 g / l HEPA
20 g / l Sodium silicate
E / 40 g / l HEPA
20 g / l Sodium tetraborate
After expressing, allowing an amount of impregnation bath corresponding to 80% of the weight of the fabric to be maintained on the fabric, it is dried and then the samples are subjected for one minute at a temperature of 2000C.

Part of the samples are dyed after treatment
Ions treated in a bath containing 3 g / liter of a direct dye referenced in the Color Index under the name of Direct Blue 86. The samples are kept in the dye bath for 30 minutes at 950C and then rinsed with water cold and we dry them,
The following results are observed
Before dyeing, the samples resulting from baths B, C and D show an intense yellow color.

Comparatively, the samples from A and E are not colored.

After dyeing, an intense blue coloration is observed on the samples resulting from baths B, C,
D and E, the colors of samples B, C and D, however, being much duller than that of sample E.

 Co-comparatively the sample resulting from bath A is clearly less colored.

These results therefore highlight
a) that the absence of an alkaline element does not allow HEPA to be fixed on the fiber
b) that the use of sodium carbonate or other alkaline salts makes it possible to fix the HEPA but causes a strong yellowing of the fiber
c) that the use of borate makes it possible to fix the product without causing yellowing or a change in color.

EXAMPLE II
Pieces of a fabric made of 66% polyester and 33% cotton are impregnated by padding in baths having the following composition
1) 30 g / l of a dispersed dye referenced in
the CI under the name of Disperse
Blue 79
2) 30 g / l Previous dye
40 g / l HEPA
3) 30 g / l Previous dye
40 g / l HEPA
20 g / l Baking soda
4) 30 g / l Previous dye
40 g / l HEPA
20 g / l Sodium tetraborate
After expressing as in Example I, it is dried and then the disperse dye is fixed for 1 minute at 2000C.

After treatment, a normal and equivalent color is observed on the samples resulting from the baths
Our. 1, 2 and 4, but a very dull color on the sample resulting from bath No. 3.

 Identical tests, repeated with the dyes indicated below, lead to the same results.

Disperse Blue 56
Disperse Red 73
Disperse Orange 29
This example therefore demonstrates the absence of a harmful influence of the HEPA applied alone or in the presence of borate on the dispersed dyes.

EXAMPLE III
Pieces of polyester fabric are impregnated in baths having the following composition
A. 30 g / l of CI Disperse Red 74 dye

30 g / l of Reactive Red 120 dye
B. 30 g / l of Disperse Red 74 dye
30 g / l of Reactive Red 120 dye
40 g / l HEPA
20 g / l Sodium tetraborate
C. 30 g / l of Disperse Red 74 dye
40 g / l HEPA
20 g / l Sodium tetraborate
After expressing, as in Example I, it is dried and then the samples are subjected for one minute at a temperature of 2000C. We then treat these different samples as follows
A and B samples
These samples are impregnated by padding in a solution containing
20 g / l of a 30% caustic soda solution
200 g / l sodium chloride
After expressing, the samples are subjected to a vaporization for 1 minute at a temperature of 1030C, then rinsing and soaping the dyes produced.

Sample C
This sample is impregnated in a bath containing
30 g / l Reactive Red 120 dye
10 g / l Soda ash
As before, the sample is subjected to a spraying, then rinsed and soaped. The following results are observed after treatment.
Dispersed dye - Equivalent intensity between the three samples.

Reactive dye - Clearly more intense color on sample C.

The determination of the fixed dye leads to the following results
Sample A 60%
Sample B 66%
Sample C 85%
This example makes it possible to demonstrate the improvement in the fixation of reactive dyes in the presence of HEPA.

EXAMPLE IV
Samples of a polyester-cotton fabric are impregnated in baths having the following composition
A - 30 g / l Disperse Red 74 dye
40 g / l HEPA
20 g / l sodium tetraborate
B - 30 g / l Disperse Red 74 dye
After expressing, it is dried and then fixed for 1 minute at a temperature of 2000C.

These samples are then impregnated by padding in a bath containing
30 g / l Reactive Red 120 dye
10 g / l Soda ash
Then proceed to a spray for 1 minute at 103 C, then rinse and soap the dyes made
It is observed after dyeing that the fixation of the reactive dye. is 85% on sample A, and {ot on sample B.

EXAMPLE V
The procedure is as in Example IV, replacing the reactive dye with a direct dye (Direct Red 212).

 After dyeing, a good color yield is observed with excellent fixing of the direct dye on sample A, significant elimination during washing and a poor color yield on sample B.

EXAMPLE VI
The conditions of Example IV are repeated. After fixing at 2000C, the dyeing of the cellulosic fiber is carried out with a reactive dye, adopting the following conditions
Impregnation by padding in a bath containing
30 g / l Reactive Red 120 dye
20 g / l Caustic soda 30%
Expressing, winding and offset for 20 hours at a temperature of 200C.

 We then proceed to rinsing and soaping the dyes made.

 After dyeing, a fixing yield of the order of 85% is observed on sample A and 50% on sample B.

EXAMPLE VII
We use the operating conditions of the example
IV. After dyeing, the dyeing of the cellulosic fiber is carried out according to the exhaustion dyeing procedure with 4% of Reactive Red 120 dye.

 After dyeing, a high binding of the reactive dye is observed on the sample A, of the order of 90%, but much lower on the sample B, of the order of 65%.

EXAMPLE VIII
Samples of a fabric made of 66% polyester and 33% cotton are impregnated in baths having the following composition
1/30 g / l of a corresponding dispersed dye
to Blue 56 of the Color Index
20/30 g / l Blue 56
40 g / l HEPA
30/30 g / l Blue 56
40 g / l HEPA
20 g / l Sodium tetraborate
4/30 g / l Blue 56
40 g / l HEPA
20 g / l Boric acid
50/30 g / l Blue 56
40 g / l HEPA converted to epoxy form
20 g / l Sodium tetraborate
We operate as in Example I.

After dyeing, the following results are observed
Baths Nos. 1, 2 and 4. No modification of the dye dispersed on the polyester, low yield of the direct dye on the cotton.

 Bath No. 3. No modification of the disperse dye, very high yield of the direct dye on cotton.

 Bain No. 5. Significant modification of the disperse dye (tarnishing of the color), high yield of the direct dye on cotton.

This example therefore highlights
a) that the use of boric acid does not ensure the fixation of HEPA on cotton.

 b) that the use of sodium tetraborate with the epoxide form of HEPA causes degradation of the dispersed dye.

Claims (13)

R> SELLING  1. A process for treating cellulosic fibers, alone or in admixture with synthetic fibers, with a view to improving their dyeing with dyes, according to which these fibers are treated with a salt of a hydroxyhalo-propyl-ammonium compound, characterized in that as the salt of a hydroxyhalopropylammonium compound, at least one compound of formula (A)

 ot R1, R2 and R3 are alkyl radicals of 1 to 3 carbon atoms and X is an anion of mineral or organic acid, in that the said treatment is carried out in the presence of an alkali metal borate, and in that the compound of formula (A) is thermofixed on the fibers to a temperature from 170 to 2300 approximately.  2. A method according to claim 1, characterized in that a compound of formula (A) oQ R1, R2 and R3 is used representing a radical CH3 and X- represents C1-.  3. A method according to claim 1 or 2, ca characterized in that one uses, as borate, sodium tetraborate.  4. A method according to any one of claims 1 to 3, characterized in that 10 to 30 g of borate are used per liter.  5. A method according to any one of claims 1 & 4, characterized in that 10 to 50 g of compound of formula (A) are used per liter.  6. A continuous dyeing process for a polyester-cotton article, characterized in that it comprises the following stages  at. padding the polyester-cotton article in a bath containing at least one dispersed dye, at least one compound of formula (A)

 where R1, R2 and R3 are alkyl radicals of 1 & 3 carbon atoms and X is an anion of mineral or organic acid ;;  and at least one alkali metal borate  b. drying, then thermofixing of the article obtained in step (a) & a temperature of 170 & 2300C approximately in order to simultaneously fix the dyes dispersed on the polyester fiber, and the compound of formula (A) and the borate on cotton fiber  vs. padding impregnation of the article obtained in step (b) in a bath containing at least one reactive dye  d. vaporization of the article obtained in step (c) in order to fix the reactive dye on the cotton fiber  e. washing the article obtained in step (d) in order to remove the non-fixed dyes.  7. A process according to claim 6, characterized in that a compound of formula (A) is used in which R1, R2 and R3 represent a CH3 radical and X- represents C1-.  8. A method according to claim 7, characterized in that sodium boron tetrabprate is used as borate.  9. A method according to any one of claims 6 8, characterized in that 10 & BR <30 g of borate per liter are used.  10. A method according to any one of claims 6 9, characterized in that 10 & BR <50 g of compound of formula (A) are used per liter.  11. A method according to any one of claims 6 & 10, characterized in that a reactive or direct dye is used to dye the cellulosic fibers.  12. Fabrics and fibers dyed by a dyeing process involving a treatment process according to any one of claims 1 & 5.  13. Fabrics and fibers dyed by a process according to any one of claims 6 to 11.