EP1183418A1

EP1183418A1 - Use of polyalkoxylated terpene derivatives for treating textile fibres

Info

Publication number: EP1183418A1
Application number: EP00938892A
Authority: EP
Inventors: Gilles Lorentz; André van der Spuy
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 1999-06-07
Filing date: 2000-06-06
Publication date: 2002-03-06
Also published as: CN1358246A; FR2794476B1; CO5210971A1; KR20020019067A; AR024303A1; FR2794476A1; AU5412000A; WO2000075416A1; JP2003528988A

Abstract

The invention concerns the use, during the treatment of textile fibres, of polyalkoxylated terpene derivatives of formula: Zi - X - [CH(R<3>) CH(R<4>)-O]n A; wherein Zi represents a bicyclo[a,b,c]heptenyl or bicyclo[a,b,c]heptyl radical, optionally substituted by at least a C1-C6 alkyl radical; a, b, and c being such that a + b + c = 5, a = 2, 3 or 4, b = 1 or 2, c = 0 or 1; X represents -CH2-C(R<1>)(R<2>)-O- or -O-CH(R'<1>)-CH(R'<2>)-O- wherein the radicals R<i> represent hydrogen or a hydrocarbon radical; R<3> and R<4> represent hydrogen or an alkyl or alkenyl group; n is a mean value ranging between 1 and 200; A represents hydrogen, an alkyl, (alkyl)aryl radical, a halogen, -CH2-CH(OH)R<5>, -SO3M, -OPO3(M)2, -(CH2)a-COOM, -(CH2)b-SO3M, or a mixture of said compounds. The use of said compound is particularly advantageous in dyeing operations.

Description

USE OF TERPENIC POLYALCOXYL DERIVATIVES IN THE TREATMENT OF TEXTILE FIBERS

The present invention relates to the use, during the treatment of textile fibers, of derivatives of polyaicoxylated terpene compounds, and more particularly during dyeing operations.

First of all, it is specified that in what follows, reference will only be made to textile fibers, knowing that this term will designate at the same time fibers, threads, knits, fabrics and nonwovens.

In addition, the present invention is equally applicable to the treatment of natural textile fibers (natural and regenerated cellulosic fibers (cotton), wool) as well as synthetic fibers (polyester, polyamide (nylon), polyacrylonitrile (acrylic)).

The treatment of textile fibers includes various stages, such as, inter alia, roasting, destacking, cleaning, bleaching, mercerization, f) dyeing stages, finishing. And during these stages, it is necessary to use wetting and / or penetrating agents so as to make effective the agent used during the stage concerned. Conventionally, ethoxylated nonylphenols are used. They are very effective agents, but they have the disadvantage of producing a large amount of foam. It is possible to use them combined with an anti-foaming agent, such as, for example, anti-foaming agents based on silicone emulsions. Unfortunately, under very high shear conditions, as can be encountered during dyeing operations, anti-foaming agents are often destabilized and a silicone gel is formed which is deposited on the fibers, which causes the appearance of permanent stains on the fabric.

The object of the present invention is therefore to propose the use of a wetting / penetrating agent which is as effective as the compounds usually used in the stages of the treatment of textile fibers, but which does not have the drawbacks due to the appearance of moss. Thus, the subject of the present invention is a process for treating textile fibers comprising at least one of the following steps: (a) toasting, (b) de-embedding, (c) cleaning, (d) bleaching, (e) mercerization, ( f) dyeing steps, (g) finishing, in which a compound of formula (I) Zj - X - [CH (R ³ ) - CH (R ⁴ ) is used in at least one of the above-mentioned steps -O] _n - A;

Formula in which: Z represents a bicyclo [a, b, c] heptenyl or bicyclo [a, b, c] heptyl radical, optionally substituted by at least one CC ₆ alkyl radical, preferably methyl, a, b and c being such that ^* a + b + c = 5,

^* a = 2, 3 or 4,

^* b = 1 or 2, c = 0 or 1, and comprising a backbone chosen from those indicated below (Zi to Z), as well as from their heptyl correspondents without double bond:

1

[3.2.0] [3.2.0] [2.2.1]

[4.1.0]

- X represents -CH ₂ -C (Ri) (R2) -O- or -O-CH (R'i) -CH (R'2) -O- in which:

° R ¹ and R2, identical or different, represent hydrogen or a hydrocarbon radical, saturated or not, linear, branched or cyclic, in Ci-Cβ, ^a R ' ¹ and R'2, identical or different, represent the hydrogen or a hydrocarbon radical, saturated or unsaturated, linear, branched or cyclic, C1-C-22.

- R ³ and R ⁴ , identical or different, represent a hydrogen atom or a linear or branched (cyclo) alkyl or (cyclo) alkenyl group at CC ₂₂ , - n is an average value between 1 and 200

- A represents a hydrogen atom, an alkyl radical in an aryl or alkylaryl radical, a halogen atom, a group -CH ₂ -CH (OH) R ⁵ , where R ⁵ represents a linear or branched or cyclic alkyl radical in CC ₂₂ or aryl, or a group chosen from -SO ₃ M, -OPO ₃ (M) _2, - (CH2) _a -COOM, - (CH ₂₎ _b -SO ₃ M, with a and b ranging from 1 to 6, M represents H, Na, K, Li, N (R ₄ ) ⁺ where the radicals R, which are identical or different, represent a hydrogen atom or a linear or branched or cyclic alkyl radical in CC ₂₂ optionally hydroxylated, or a mixture of these compounds. The compounds (hereinafter called terpene compounds) used will first be described.

As indicated above, the derivatives of terpene compounds used in the process according to the invention correspond to the formula mentioned above. In this formula, the radical Zj is preferably attached to the rest of the chain via any one of its carbon atoms numbered 1 to 6. According to a more particular mode, the radical Zj is attached to the remainder of the chain through carbon atoms 1, 5 and 6.

According to an advantageous variant of the invention, the compounds are such that the radical Zj is substituted on at least one of its carbon atoms, by at least two alkyl groups in OpCβ, preferably by two methyl radicals. More particularly, the substituents are located on the carbon atom 7.

A first family of compounds corresponds to that in which X represents -CH2-C (R) (R2) -O-. In such a case, the radicals Zj more particularly correspond to the radicals Z ₃ to Z ₇ . In addition, the cycles include ethylenic unsaturation. In addition, they carry two substituents, preferably methyl, on the carbon atom 7. The preferred compounds are defined by the radicals Z and Z ₅ , carrying two methyls on carbon 7.

A second family of compounds corresponds to that in which X represents -O-CH (R'i) -CH (R'2) -O-. More particularly, the cycles do not contain ethylenic unsaturation and are represented by the radical Z ₃ . Note that in the case of this family, it is expected that at least R ¹ or R ² is not hydrogen.

Thus, a preferred embodiment consists of compounds in which R ¹ or R ′ ² is a methyl radical. According to another particular characteristic of this family of compounds, the carbon atom 7 carries two methyl substituents as well as a C ₁ -C ₆ alkyl substituent, preferably a methyl, located on the carbon atom 2 or the carbon atom. 5. Regarding the reasons - [CH (R ³ ) - CH (R) -O] -, it was clarified that R ³ and

R ⁴ , identical or different, represent a hydrogen atom or a group

(cyclo) alkyl or (cyclo) alkenyl linear or branched in CC ₂₂ , preferably in C C- ₆ .

More particularly, the radicals R ³ and R ⁴ , which may or may not be identical, represent a hydrogen atom, a methyl radical, or an ethyl radical.

If the motifs - [CH (R ³ ) - CH (R ⁴ ) -O] - are different, their distribution is statistical or sequenced. According to this latter possibility, it is possible to envisage having two or more different blocks. For example, suitable compounds can comprise the following sequences: - [CH2-CH2θ] q- [CH (R ³ ) -CH (R ⁴ ) -O] r or - [CH (R ³ ) -CH (R ⁴ ) -O] _r [CH2-CH2θ] _q - sequences in which R ³ or R ⁴ is different from hydrogen, and n = q + r.

One type of block compound which may also be suitable for implementing the invention are those having the following sequence:

- [CH (R ³ ) - CH (R ⁴ ) -O] _p - [CH ₂ - CH ₂ -O] _q - [CH (R ³ ) - CH (R ⁴ ) -O] _r - sequence in which R ³ or R ⁴ is different from hydrogen, and n = p + q + r.

According to a particular embodiment, said units correspond to oxyethylenated units and / or to oxypropylenated units. n is an average value between 1 and 200. It corresponds to the total sum of the motifs - [CH (R ³ ) - CH (R ⁴ ) -O] -. Preferably, the number of oxyethylenated units is between 1 and 200, preferably between 1 and 50, and even more particularly, between 1 and 20.

As regards the number of oxypropylenated units, their average number is between 0 and 20, more particularly between 1 and 10, preferably between 1 and 4. It can be very advantageous to have a terpene compound corresponding to a mixture of compounds of formula (I) in which at least one of them is such that it has the sequence mentioned above.

These compounds, as well as their method of preparation are described in particular in international applications WO 96/01245 and WO 98/28249. We can therefore refer to it with regard to the definition and obtaining of said compounds. The method according to the invention therefore consists in using the compounds which have just been described, in one or more stages carried out during the treatment of textile fibers.

It has in fact been found that said compounds have quite interesting wetting properties of textile fibers, thereby favoring the penetration of the textile fibers by the treating reagent.

In addition, the compounds used in the invention exhibit good resistance under the often very harsh conditions encountered during the treatment of the fibers. Indeed, many stages are carried out in very alkaline medium. In addition, the compounds according to the invention have the advantage of having their structure adapted according to the requirements of the operation in which they are used. Thus, on a common basis, it is possible to have an effective nonionic or ionic compound, compatible with the various compounds present in the solution intended for the treatment of fibers.

The textile fibers subject to the treatments include residual additives, originating from the previous stages, such as lubricants (sizing additives (lubricants for dies in the case of synthetic fibers), polyvinyl alcohol, carboxymethylcellulose), cohesion of fibers (starch), film-forming agents (hydrocolloids). It is necessary to rid the fibers of these compounds. This operation is carried out during a step called de-interlining (step (b)).

The desizing operation can be carried out enzymatically (aiming to depolymerize the starch, if it is present) and / or by chemical oxidation and / or by an alkaline washing. More particularly, the oxidation reaction is carried out with an oxidizing agent chosen from hydrogen peroxide, persulfates, perborates for example. It is also implemented in an alkaline medium, such as alkaline washing. The alkali metal hydroxides (such as sodium hydroxide) but also the alkali metal carbonate and bicarbonate can be used; soda being preferred. Usually the concentration of alkaline agent is of the order of 2 to 5 g / l, so as to obtain a pH of between 10 and 12. The de-oiling medium can also comprise usual additives (chelating agents, etc.).

This step is carried out in solution comprising 70 to 80% of water. In addition, it is carried out hot. Thus temperatures above 50 ° C are conventional.

In addition, the désooilage can be carried out in the presence of the terpene compound described whose use is the subject of the invention.

The content of this compound in the stabilizer bath varies more particularly between 1 and 5 g / l. Generally, the textile fibers are impregnated in the solution, either continuously

(steam cabin) or discontinuously (rotating rollers).

This step can take place in one or more passes.

Depending on the nature of the textile fiber, it may be necessary or simply advantageous to implement a prior step, called toasting (step (a)). The purpose of this step is to give a smoother surface to the textile fiber. Indeed, it consists in burning the fibers which protrude from the surface thereof.

Note that the implementation of this roasting step does not facilitate that of the désooilage stage. Indeed, the textile fiber having undergone such a treatment is overdried and therefore, it is necessary to be able to have a solution having a high wetting power if one wants to maintain good efficiency at the de-embedding stage.

Once the désooilage stage carried out, one can implement a cleaning stage (stage (c)). This step is more generally used when the textile fibers include cotton. The purpose of this operation is to eliminate the compounds naturally present on cotton fibers, such as, for example, cellulose residues (hemicellulose, immature cellulose), natural oils or waxes which are the cause of heterogeneities in the fabric. final dyed or not. This cleaning operation is carried out in a strongly alkaline medium.

Conventionally, the concentration of alkaline agent in the bath is 20 to 40 g / l.

Advantageously, soda is used.

The medium can likewise comprise the terpene compound. The content of this compound can advantageously be between 1 and 5 g / l. The step is more particularly carried out at a temperature of the order of 60-

80 °.

This step is generally carried out in a steam cabin.

At the end of this operation, the textile fibers can be directly dyed as soon as the colors are dark. But conventionally, the process for treating textile fibers continues with a bleaching step (step (d)).

The operation takes place by means of an oxidizing agent which is more particularly hydrogen peroxide.

It may be advantageous to use a stabilizer, such as silicates, hypochlorites, polyphosphonic acid.

The bleaching step is carried out at high temperatures, of the order of 70 to 80 ° C.

At the end of the bleaching step, a step called mercerization or caustization can optionally be implemented (step (d)). This step consists of soaking the textile fibers in an alkaline solution; the textile fibers being possibly subjected, during this step, to a mechanical tension. The purpose of this operation is to improve the yield of the dyeing operation of the fibers, as well as their resistance to tearing.

Several possibilities are possible for this operation. According to a first possibility, the soaking is carried out with a solution whose concentration of alkaline agent and of the order of 200 to 300 g / l. The step, according to this variant, is carried out at a temperature of the order of 15 to 25 ° C. According to another variant, it is possible to carry out the soaking with a solution whose concentration of alkaline agent is approximately 200 g / l, knowing that the operation is carried out at a temperature between 55 and 70 ° C., followed by '' a step of cooling and rinsing at room temperature, by exerting a tension on the textile fibers.

It is also possible to carry out this step with a solution of which the content of alkaline agent is 100 -160 g / l, while not exerting tension tension on the textile fibers, and at a temperature ranging between approximately 20 and 40 ° vs. In such a case, we no longer speak of "mercerization" but of "caustization". The alkaline solution can likewise comprise the terpene compound, with a concentration varying more particularly between 1 and 5 g / l.

The textile fibers are then dyed, in a series of steps (e). These steps are well known in the art.

We can use so-called "dispersed" dyes, that is to say using pigments that are insoluble in water, or else say "reactive", that is to say using water-soluble pigments but binding to reactive sites present on the fibers.

By way of example, and when the fibers are a mixture of synthetic fibers / natural fibers (for example polyester / cotton), the dyeing can comprise the following stages: coloring of the synthetic fibers (stage (e1)), fixing of these pigments

(step (e2)), salting out of the non-fixed pigments (step (e3)), coloring of the natural fibers (step (e4)), washing of the non-fixed pigments (step (e5)).

When the fibers comprise only one or the other of the types of fibers, then the steps specific to this type of fibers are only implemented. Preferably, the dyeing operations are carried out at a pH of at least 7, preferably at least 8.

Such pHs are obtained through the use of alkaline compounds such as alkali metal hydroxides.

The solutions or dispersions used are aqueous. In addition to the pigments or dyes, the solutions or dispersions comprise various surfactants, which are preferably anionic or nonionic. For example, it is possible to use ether sulfates of fatty alcohols, optionally alkoxylated (ethoxylated and / or propoxylated), esters of phosphoric acid optionally alkoxylated, mono- and di-alkylsulfosuccinates, polyaicoxylated fatty alcohols, lignosulfonates , condensation products of formaldehyde and aromatic sulfonic acids (naphthalene sulfonic acid for example), etc.

It is likewise possible to use, as additis for the dye baths, colloids such as polysulfonates, polycarboxylates (polyacrylate, acid copolymer acrylic / maleic acid), polyvinylsulfonates, alginates, polysaccharides, cellulose derivatives.

These surfactants and colloids have the role of stabilizing the dispersion but also of preventing impurities from precipitating or agglomerating in the bath. The solutions or dispersions can also comprise the terpene compounds. They are preferably of the nonionic type.

The use of terpene compounds as defined above is very advantageous in the context of the dyeing stages. In fact, they have very little or no foaming or even defoaming properties, even under dyeing conditions, in which the shearing is very high.

Thus, the use of the abovementioned terpene compounds no longer makes the presence of large quantities of anti-foaming agent necessary. It may even be possible to dispense with the employment of such agents.

The content of these terpene compounds advantageously varies between 1 and 5 g / l.

The actual dyeing operations are carried out in a conventional manner, and more particularly in a closed loop (jet type, in a cassette (jigger)).

They can be carried out continuously, or discontinuously, preferably.

The dyeing is generally carried out hot, that is to say at temperatures between 50 and 90 ° C. Higher temperatures are possible if the operation is carried out under pressure.

In continuous processes, the textile fibers are first impregnated in the dye bath, then passed through rollers to remove the excess bath. The fibers can follow several passages before having their dyes fixed. It is more particularly during the impregnation steps that we are in the presence of significant shearing conditions, which are the cause of the appearance of foam.

In batch processes implemented in Gigger cassette) the fabric is unwound from one cassette to another with, in the meantime, immersion in the bath. In this case, the agitation is average. Therefore, the levels of foam created are also average. However, it may happen that the foam is deposited on the textile fibers and is the cause of the appearance of stains.

In batch type jet processes, the appearance of foam is very important. Indeed, the fabric is driven by water jets. However in these conditions where centrifugal pumps are used, the shearing is very high and the stirring very strong. Conventional anti-foaming agents, which are compulsory, can be destabilized and lead to a deposit of the said agent on the fabric, with the result of the appearance of stains. Once the impregnations have been carried out, the dyes are fixed to the textile fibers under the action of heat.

When the textile fibers are dyed, a finishing step can be carried out, with the aim of giving the textiles special properties according to the end use for which they are intended.

Thus, the textile fibers can be treated with softeners (anionic, cationic, silicone), agents making the fabric more or less stiff (resins), anti-stain agents (fluorocarbons), agents making it possible to transform the appearance of the fabric (polyurethanes on which we can apply flocks in order to obtain a velvet appearance, for example).

A concrete but nonlimiting example of the invention will now be presented.

EXAMPLE

The tests below have the effect of showing the effect of the terpene compound in a step of desizing of polyester textile microfibers (fabric), compared with a usual surfactant.

Test conditions:

The désooilage bath includes:

Sodium hydroxide (scales): 2 g / l

Chelating agent (Neocrystal 70, sold by the company Nicca) 1 g / l

Desizing agent (terpene compound, or usual surfactant) 1 g / l

The fabric is spread on a support then a drop of oil is deposited (paraffinic mineral oil HN100), esterified oil (methyl ester of rapeseed oil), and wax (ethylene bis stearamide). The whole is then treated at 180 ° C for 1 minute.

The fabric is then immersed in the désooilage bath at 110 ° C for 20 minutes. The weight ratio of the part to be treated in the stabilizer bath is 1:20.

Then the fabric is rinsed with excess water for 30 seconds, and drained for 30 seconds. The resulting fabric is then dyed with a disperse dye

(1% by weight of Palanil Violet 3RL - BASF). The part is immersed in the bath comprising the dye at room temperature, then the temperature is increased to 80 ° C., with stirring.

The places where the deposited oil is not removed will be dyed differently. The descaling agents tested are as follows:

Comparative test 1: Igepal NP8.5, which is a nonylphenol with 8.5 moles of ethylene oxide;

Test according to the invention: compound corresponding to cycle 4), carbon 3 carrying two methyl radicals, and in which X represents -CH2-CH2-O-, and comprising

5 moles of propylene oxide and 9 moles of ethylene oxide.

Comparative test 2 corresponds to compositions free from de-stabilizing agents.

Desoiling test (removal of oil stain)

The results are numbered from 1 (very bad) to 7 (excellent).

Extraction test after desizing. Part of the treated fabrics are used to measure the percentage of residues

(oil, descaling agent) remaining on the fabric.

The residue is extracted with ethyl ether.

The residue corresponds to 100 x dry weight of the extract / weight of the piece of fabric.

For this measurement, the désooilage bath includes 3 g / l of désooilage agent.

Foam level measurement

The stabilizer bath used is that of test 1.

The foam is obtained by stirring 900 g of solution using a turbine agitator (40mm turbine, speed 2000 rpm) for 5 minutes. The temperature is 50 ° C.

The foam level is read in a test tube after 5 minutes of rest.

The results are collated in the following table:

It is found that the agent according to the invention is as effective as the agent of Comparative Example 1 with regard to the de-embedding, and surprisingly, with regard to the level of residue remaining on the fibers after the treatment . On the other hand, the release agent according to the invention is much more efficient than the agent according to Comparative Example 1, as regards the level of foam.

Claims

1. A process for treating textile fibers comprising at least one of the following steps: (a) toasting, (b) de-scaling, (c) cleaning, (d) bleaching, (e) mercerization, (f) dyeing steps, (g) finishing, characterized in that a compound of formula (I) Zj -X - [CH (R ³ ) - CH (R ⁴ ) -O is used in at least one of the aforementioned steps ] _n - A; Formula in which:

- Zj represents a bicyclo [a, b, c] heptenyl or bicyclo [a, b, c] heptyl radical, optionally substituted by at least one C 6 -C 6 alkyl radical, preferably methyl, a, b and c being such that ^* a + b + c = 5,

^* a = 2, 3 or 4,

^* b = 1 or 2, ^* c = 0 or 1, and comprising a skeleton chosen from those indicated below (Zi to Z ₇ ), as well as from their heptyle correspondents without double bond:

1) 2) 3)

[3.2.0] [3.2.0] [2.2.1]

[4.1.0]

- X represents -CH ₂ -C (Ri) (R2) -O- or -O-CH (R'i) -CH (R'2) -0- in which: ^a R1 and R2, identical or different, represent hydrogen or a hydrocarbon radical, saturated or unsaturated, linear, branched or cyclic, in ^α R'1 and R'2, identical or different, represent hydrogen or a hydrocarbon radical, saturated or not, linear, branched or cyclic, C-1-C22,

- R ³ and R ⁴ , identical or different, represent a hydrogen atom or a linear or branched (CtC ₂ ) (cyclo) alkyl or (cyclo) alkenyl group,

- n is an average value between 1 and 200

- A represents a hydrogen atom, a C _r C ₆ alkyl radical, an aryl or alkylaryl radical, a halogen atom, a group -CH ₂ -CH (OH) R ⁵ , where R ⁵ represents a radical linear or branched or cyclic CC ₂₂ or aryl alkyl, or a group chosen from -SO ₃ M, -OPO ₃ (M) ₂ , - (CH2) _a -COOM, - (CH ₂ ) _b -SO ₃ M, with a and b going from 1 to 6, M representing H, Na, K, Li, N (R ₄ ) ⁺ where the radicals R, identical or different, represent a hydrogen atom or a linear or branched or cyclic alkyl radical in CC ₂₂ optionally hydroxylated, or a mixture of these compounds.

2. Method according to the preceding claim, characterized in that a compound of formula (I) is used in which the radical Zj is preferably attached to the rest of the chain via any of its atoms of carbon numbered 1 to 6, and more particularly through the carbon atoms 1, 5 and 6.

3. Method according to any one of the preceding claims, characterized in that the compound is such that in formula (I), the radical Z is substituted by two C1-C6 alkyl groups, on at least one of its carbon atoms, more particularly, on the carbon atom 7.

4. Method according to any one of the preceding claims, characterized in that a compound of formula (I) is used in which X represents -CH2-C (R ¹ ) (R ² ) -O- and the radicals Zj correspond to the radicals Z ₃ to Z ₇ , preferably to the radicals Z ₄ and Z ₅ .

5. Method according to any one of the preceding claims, characterized in that a compound of formula (I) is used in which X represents

-O-CH (R ' ¹ ) -CH (R'2) -0-, the radical Zj corresponds to the radical Z ₃ not comprising ethylenic unsaturation.

6. Method according to the preceding claim, characterized in that the compound is such that in formula (I), the radical Z is substituted by an alkyl radical in C ^ -CQ, preferably a methyl radical on carbon 2 or 5 of the bicycle.

7. Method according to any one of the preceding claims, characterized in that a mixture of compounds of formula (I) is used in which at least one of them is such that the group [CH ( R ³ ) - CH (R ⁴ ) -O] corresponds to the following sequence: - [CH (R ³ ) - CH (R ⁴ ) -O] _p - [CH ₂ - CH ₂ -O] _q - [CH ( R ³ ) - CH (R ⁴ ) -O] _r - sequence in which R ³ or R ⁴ is different from hydrogen and n = p + q + r.

8. Method according to any one of the preceding claims, characterized in that the compound of formula (I) is used during the dyeing steps (e).

9. Method according to any one of the preceding claims, characterized in that the compound of formula (I) is used with a concentration of between 1 and 5 g / l.