EP1149945A1 - Composition for the pretreatment of fibrous materials - Google Patents

Abstract

Compositions that include a mixture of three different ethoxylated alcohols with or without further products are useful for pretreating textile materials, especially cotton fabrics. The compositions have acceptable viscosities and are preferably used in the form of aqueous solutions or dispersions. These have little if any tendency to form foam, are highly compatible with enzymes and impart very good rewettability to textiles treated therewith.

Description

The invention relates to a composition which is at least three different contains ethoxylated alcohols. It also relates to the use of such compositions for the treatment of fiber materials.

Fiber materials in the form of textile fabrics, such as woven or knitted fabrics, in particular fabrics containing cotton, normally have to be subjected to a so-called pretreatment before they are dyed. The pretreatment serves, among other things, to achieve trouble-free, uniform coloring. Depending on the history and provenance of the textile fabrics or machine conditions, the pretreatment can include the measures desizing, degreasing / cleaning and bleaching the textiles, whereby these measures can be carried out separately. However, in individual cases it is also possible to have several of these measures run in a single process in order to save costs.
In order to meet the requirements for a suitable pretreatment process, various chemical products are used for the pretreatment. Depending on the task, these can include wetting agents, detergents, enzymes, bleaching agents, stabilizers, complexing agents, etc. Of particular importance here is surfactants, which bring about good wettability of the textile fabrics and good washing and cleaning effects. It is advantageous if the products which bring about good wettability bring about no or only an insignificant increase in the tendency to foam formation in baths in which the pretreatment products are contained. This requirement plays a major role, both when the pretreatment is carried out as a discontinuous process, for example in so-called jet systems, and in continue processes. The products used for the pretreatment are often required to have a low tendency to foam, because it is often undesirable to suppress an increased tendency to foam by adding anti-foaming agents such as silicones.

After classic pretreatment steps such as desizing, degreasing / cleaning, bleaching in a number of cases combined into a combined pretreatment process , there was also the demand for compositions which are suitable for such combined pretreatment processes can be used. The compositions are normally aqueous systems, which ensure good wettability of the textile goods Initiate the pretreatment, but also good hydrophilicity after the end. This good hydrophilicity leads to good rewettability with regard to the dyeing process is required.

Products which are suitable for pretreating fiber materials in the form of textile fabrics and which contain ethoxylated alcohols or terminated derivatives thereof as surfactants are known, for example from EP-A 274 350 , EP-A 360 736 , EP-A 462 059 , EP- A 114 788 . Compositions which contain mixtures of alkoxylated alcohols or derivatives thereof have also been described, for example in EP-A 696 661 and WO 92/15664 .

The compositions described in the above documents have, though they are suitable in principle for textile pretreatment, but not yet optimal in every respect Properties on. Prepares in particular for known compositions for Pretreatment of textiles the foaming tendency, the too high viscosity, the Compatibility with enzymes and / or a strongly acidic pH in a number of cases Problems. The foaming tendency is evident in both continue and Discontinue processes for pre-treatment are noticeably noticeable, e.g. with discontinuous Pretreatment in jet equipment. A damping of the foam with silicones is admittedly possible, but undesirable in many cases.

The object of the present invention was to develop a composition which is excellent for the pretreatment of fiber materials, especially textiles Fabrics containing cotton are suitable for good rewettability of the textiles Goods carry, well compatible with enzymes, an acceptable for easy handling Has viscosity and even without the use of highly effective anti-foaming agents such as silicones no unacceptably high tendency to foam formation.

A) einen ethoxilierten Alkohol der allgemeinen Formel (I)

B) einen ethoxilierten Alkohol der allgemeinen Formel (II)

C) einen ethoxilierten Alkohol der allgemeinen Formel (III)

wobei R¹ für einen linearen oder verzweigten Alkylrest mit 6 bis 14 Kohlenstoffatomen, R² und R³ jeweils für einen linearen oder verzweigten Alkylrest mit 10 bis 18 Kohlenstoffatomen stehen, wobei m für eine Zahl von 3 bis 12, vorzugsweise von 4 bis 10 steht,

n für eine Zahl von 3 bis 18

und x für eine Zahl von 5 bis 20

steht, jeder der beiden Reste R² und R³ mindestens 2 Kohlenstoffatome mehr enthält als der Rest R¹ und wobei x - n gleich oder größer als 2 ist.

The object was achieved by a composition which contains the following components A), B) and C):

A) an ethoxylated alcohol of the general formula (I)

B) an ethoxylated alcohol of the general formula (II)

C) an ethoxylated alcohol of the general formula (III)

where R ^{1 is} a linear or branched alkyl radical having 6 to 14 carbon atoms, R ² and R ^{3 are} each a linear or branched alkyl radical having 10 to 18 carbon atoms, where m is a number from 3 to 12, preferably from 4 to 10 ,

n for a number from 3 to 18

and x for a number from 5 to 20

is, each of the two radicals R ² and R ^{3 contains} at least 2 more carbon atoms than the radical R ¹ and where x - n is equal to or greater than 2.

Compositions according to the invention are preferably in the form of aqueous solutions or Dispersions before, thus contain water as component D). In this case it can be an advantage be if the compositions additionally contain as component E) an aliphatic diol with 2 contain up to 10 carbon atoms, preferably a diol with a branched hydrocarbon chain with 4 to 8 carbon atoms, in which the two OH groups are not adjacent Carbon atoms are bound.

The compositions according to the invention are very suitable for the treatment of Fiber materials, in particular textile fabrics such as woven or knitted fabrics (Knitwear). A preferred use of the compositions is in Pretreatment. They are particularly suitable for the pretreatment of fiber materials, which consist of 50 to 100% by weight of cellulose, in particular cotton.

It is possible to provide compositions according to the invention in a form which does not have too high a viscosity and can therefore be handled well without the addition of water.
Compositions according to the invention in the form of aqueous dispersions or solutions, even if they contain ingredients other than the three ethoxylated alcohols mentioned above, with a pH in the range from 3 to 5 can be used for the pretreatment. They are therefore superior to known products with a more acidic pH because at a strongly acidic pH there is a risk of incompatibility with enzymes.
The pretreatment of textile fabrics with compositions according to the invention means that the textiles have excellent rewettability after completion of the pretreatment. This has a positive effect on a subsequent dyeing process.
Compositions according to the invention can be used for the pretreatment without the addition of phosphorus compounds. This is an advantage in terms of the environment, especially when it comes to waste water.
Compositions according to the invention in the form of aqueous solutions have only a slight tendency to form unwanted foam, so that the pretreatment process is not disturbed by foam formation.
Finally, provided that no further components are added that are poorly compatible with enzymes, compositions according to the invention can be combined well with enzymes. This is advantageous if enzymes, such as α-amylase, which cause the enzymatic degradation of size products are to be added during the pretreatment process. With compositions according to the invention, textiles, in particular cotton articles, can be wetted quickly and easily. This means that the pretreatment process can run smoothly right from the start.

Compositions according to the invention must have at least those mentioned above Components A), B) and C) included. All three components are available on the market. she can generally by reacting the corresponding alcohols with ethylene oxide known methods are produced.

Component A) is an ethoxylated alcohol of the general formula (I)

Here R ^{1 represents} a linear or branched alkyl radical having 6 to 14 carbon atoms.

R ¹ is preferably a branched alkyl radical having 8 to 12, in particular 9 to 11, carbon atoms. The value of m, which indicates the degree of ethoxylation, is in the range from 3 to 12, preferably from 4 to 10.

Component B) is an ethoxylated alcohol of the general formula (II)

Here R ^{2 represents} a linear or branched alkyl radical having 10 to 18 carbon atoms, preferably a branched alkyl radical having 10 to 16 carbon atoms. The degree of ethoxylation n is a number in the range from 3 to 18, preferably from 4 to 10.

Component C) is an ethoxylated alcohol of the general formula (III)

The radical R ³ here represents a linear or branched alkyl radical having 10 to 18 carbon atoms, preferably a branched alkyl radical having 10 to 16 carbon atoms. The degree of ethoxylation x is 5 to 20, preferably 6 to 16.

Instead of chemically pure products, each of the three components A), B) and C) can be a mixture of ethoxylated alcohols. Technical or naturally occurring alcohol mixtures, the individual molecules of which differ in the chain length of the radical R ¹ or R ² or R ³ , can thus be used for the production of each of these three components. The ethoxylation of these alcohols leads to mixtures, the constituents of which differ not only in the chain length of R ¹ or R ² or R ³ , but also in the degree of ethoxylation, ie in the values of m or n or x. It is important, however, that for a mixture of ethoxylated alcohols to be used as component A), the majority of the molecules, ie at least 80% of all molecules, have an alkyl chain which contains 6 to 14 carbon atoms and a degree of ethoxylation of 3 to 12 . Analogously, both in component B) and in component C) each have at least 80% of all molecules of alkyl groups with 10 to 18 carbon atoms and a degree of ethoxylation of 3 to 18 (component B)) or 5 to 20 (component C)).

Furthermore, it is important and indispensable for achieving the advantages of compositions according to the invention that both the radical R ² and the radical R ³ contain at least 2 more carbon atoms than the radical R ¹ . In addition, the degree of ethoxylation x of component C) must be at least a greater number than the degree of ethoxylation n of component B), ie x - n must be equal to or greater than 2.
The two conditions mentioned for the differences in the number of carbon atoms in the alkyl radicals and in the degree of ethoxylation must both be fulfilled. It has been shown in studies that the use of a mixture of three ethoxylated alcohols, which on average all three have the same number of carbon atoms in the alkyl radical or on average all three have the same degree of ethoxylation, is inferior to the use of compositions according to the invention, which is the result of pretreatment effects obtainable from textiles.
Since each of the three components A), B) and C) is normally a mixture of ethoxylated alcohols, not all of the R ² and R ³ radicals present in the individual molecules will have at least 2 more carbon atoms than all of the R ¹ radicals present. But this condition mentioned above must be fulfilled for the average number of carbon atoms in the respective radicals R ¹ , R ² and R ³ . Analogously to this, not every single molecule of component C) must have a degree of ethoxylation which is at least 2 higher than that of any molecule of component B). The average degree of ethoxylation of C) must be at least 2 higher than that of B).
If, for example, a mixture of ethoxylated alcohols is to be used as component A) in a particular composition according to the invention, which on average has an alkyl radical (R ¹ ) with 12 carbon atoms, the average length of the alkyl radicals (R ² and R ³ ) must be in the Components B) and C) each have at least 14 carbon atoms. Similarly, the average degree of ethoxylation x of component C) must be at least 16 if component B) used has an average degree of ethoxylation of 14.

All three components A), B) and C) contain no propoxylated units
-CH (CH ₃ ) -CH ₂ -O- and have an alkyl group on one chain end and an OH group on the other. This distinguishes them from a number of products known from the prior art for the pretreatment of textiles.

Compositions according to the invention preferably contain components A), B) and C) in the following quantitative ratios relative to one another: 10 to 40 Parts by weight A) 3 to 30 Parts by weight B) 0.1 to 10 Parts by weight C)

D) Wasser

E) ein aliphatisches Diol mit 2 bis 10 Kohlenstoffatomen

F) eine oder mehrere aliphatische, ein- oder mehrwertige Carbonsäuren mit 3 bis 8 Kohlenstoffatomen oder Alkalimetallsalze dieser Säuren

G) hydrolysiertes Polymaleinsäureanhydrid

H) ein Alkylpolyglykosid

In a preferred embodiment, compositions according to the invention contain, in addition to components A), B) and C), one or more of the following components D), E), F), G) and H):

D) water

E) an aliphatic diol with 2 to 10 carbon atoms

F) one or more aliphatic, mono- or polyvalent carboxylic acids with 3 to 8 carbon atoms or alkali metal salts of these acids

G) hydrolyzed polymaleic anhydride

H) an alkyl polyglycoside

Component E) has already been described above.

Component G) is a hydrolyzed polymaleic anhydride. This can be a product in which all anhydride groups of a polymaleic anhydride have been hydrolyzed to acid groups, that is to say polymaleic acid. Component G) can also be a partial hydrolyzate in which only some of the anhydride groups have been hydrolyzed. Component G) can also be a copolymer which contains hydrolyzed maleic anhydride groups. For example, a copolymer of maleic anhydride and another monomer unit, which may also contain aromatic units, can be used as component G) after partial or complete hydrolysis. The molecular weight of polymers suitable as component G) is preferably in the range from 400 to 1000. Like component F) described below, component G) can serve as a complexing agent for metal ions.
Products suitable as component G) are available on the market, for example the product "BELCLENE 200" from Great Lakes, GB, which is an aqueous solution of polymaleic acid.
Component F) is an aliphatic, mono- or polyvalent carboxylic acid with 3 to 8 carbon atoms or an alkali metal salt of such an acid, in particular a sodium or potassium salt. Instead of a single compound, component F) can also be a mixture of such compounds, for example a mixture of an acid and an alkali metal salt of another acid. Component F), like component G), can serve as a complexing agent for metal ions in the pretreatment of textiles. Citric acid or gluconic acid or alkali metal salts of these acids or a mixture of such compounds are particularly suitable as component G).
Component H) is an alkyl polyglycoside. It can help to improve the stability of compositions according to the invention against the action of alkaline substances. Alkylplyglycosides are known products available on the market that can be produced by acid-catalyzed reaction of the corresponding sugars with alcohols. As component H), for example, the product Glucopon 600 CS UP from Cognis, Germany, is suitable, an aqueous solution of an oligomeric alkyl glucopyranoside.

A preferred embodiment of compositions according to the invention is characterized in that it contains components A) to H) in the following relative proportions: 10 to 40 Parts by weight A 3 to 30 Parts by weight B 0.1 to 10 Parts by weight C 0 to 100 Parts by weight D 0 to 20 Parts by weight E 0 to 20 Parts by weight F 0 to 10 Parts by weight G 0 to 15 Parts by weight H

The compositions according to the invention can normally be produced without problems by mixing components A) to C) and, if appropriate, further desired components in any order with stirring at room temperature. In individual cases, adherence to a certain mixing sequence and / or an increase in temperature can bring advantages in terms of storage stability. These statements also apply if compositions according to the invention are to contain further components, for example components D) to H) described in more detail above.
If desired, compositions according to the invention can contain further additives, in particular with regard to special pretreatment processes and requirements. Such additives can be, for example, enzymes, complexing agents or other surfactants; they can be used in the amounts customary for the pretreatment processes. Before using such additives, however, it is advisable to check whether this does not reduce the stability or the above-mentioned advantages of compositions according to the invention to an unacceptable extent.

Compositions according to the invention are extremely suitable for the treatment of Fiber materials, in particular for the pretreatment of textile fiber materials in the form of Woven or knitted. The fiber materials can be textile fabrics that consist of cellulose, regenerated cellulose or synthetic polymers or the Mixtures of such fibers are. The invention is particularly suitable Compositions for the pretreatment of textile fabrics, 50 to 100 Weight percent consist of cotton. The rest of the fibers consist here, for example made of synthetics. Compositions of the invention are for continue processes, however also for discontinue pretreatment processes, e.g. in jet equipment, excellent suitable.

The compositions according to the invention can be applied to the textile material by methods customary in pretreatment processes, for example by immersion application, padding, etc. Appropriately, the aqueous liquors used for pretreatment have concentrations as are customary, for example from 0.03 to 2 percent by weight the sum of components A, B and C, based on the total fleet.
After the pretreatment, the textile material is further treated in the usual, known manner, for example dyed, if appropriate after drying beforehand.

The invention is now illustrated by means of exemplary embodiments.

Compositions were made from the ingredients according to Table I below prepared, the numbers below the respective examples each used Share of the constituent in question in% by weight.

Composition a) is a comparative example not according to the invention. The compositions b), c) and d) each contain surfactant 1, surfactant 2 and surfactant 3 and are therefore examples according to the invention.

Surfactant 1 is a branched aliphatic alcohol with an average of 11 carbon atoms and an average degree of ethoxylation of 5.
Surfactants 2 to 5 are ethoxylated isotridecyl alcohols with the following average degrees of ethoxylation: Surfactant 2 5 Surfactant 3 9 Surfactant 4 7 Surfactant 5 10

Citric acid and D-gluconic acid were partly in the form of their sodium salts. they provide Complexing agents for metal ions.

The aliphatic diol used was a 6 carbon atom branched carbon chain diol. The two hydroxyl groups are not attached to adjacent carbon atoms here.
The polymeric acid used for compositions b), c) and d) was a hydrolyzed polymaleic anhydride (Belclene 200 from Great Lakes).
A D-glucopyranoside with an attached alkyl radical with 10 to 16 carbon atoms (Glucopon 600 CS UP from Cognis, Germany) was used as the alkyl polyglycoside. The compositions were prepared by simple mixing with stirring at room temperature.

The compositions a) to d) were viscosity, (telquel) pH, (telquel) Wetting capacity, foaming and enzyme compatibility tested on the compositions a), c) and d) additionally the rewettability.

Viscosity:

The determination was carried out at room temperature using the Rheomat RM 180 and is based on the shearing method.

Foaming tendency:

The determination was made with the Ahiba Texomat foam device. For this purpose, aqueous liquors were used prepared, each containing 3 g / l of the compositions a) to d). In a second A series of tests were additionally added to the liquors in each case 10 g / l sodium hydroxide solution. Each 200 ml of the aqueous liquor were heated to 30 ° C and then in a 1000 ml measuring cylinder given. Foam was generated by mechanical action and the foam height visually read on the measuring cylinder. A higher value for the tendency to foam (in Table II in cm) means a higher foaming tendency.

Network assets

This includes the primary wettability of textile materials with the tested ones Understand compositions. Fleets such as those above were used for the determination were described under "Foaming tendency". The time was measured in seconds, in who completely immersed a sample of cotton fabric after immersing it in a fleet Ground has sunk. So a lower value for this time means better / faster Wettability of the fabric by the corresponding fleet.

Rewettability

This is a measure of the wettability of textile fabrics after a pretreatment process has been carried out. In practice, the aim is that after the pretreatment, the fabrics can be rewetted quickly and easily in order to enable a trouble-free dyeing process.
Aqueous liquors were prepared, each containing 0.5 g / l of water in compositions a), c) or d). They also contained an alkaline bleaching formulation.
Samples of cotton tricot were treated with the above-mentioned aqueous liquors, washed several times with water, then mechanically kneaded in water, squeezed and dried. The rewettability was then measured in seconds. For this purpose, strips of the samples treated in this way were partially immersed in an aqueous dye solution. The time was measured in which the dye solution had risen 1 cm into the non-immersed zone of the tissue. A lower value for the (in seconds) rewetting time in Table II means faster / better rewetting.

Enzyme tolerance:

In pretreatment processes, enzymes are often used in the pretreatment liquor to enable enzymatic removal of sizing products from the tissues. It is desirable that the effectiveness of these enzymes is not reduced by other components of the pretreatment liquor. There is a risk of reducing enzyme activity, especially in the presence of strongly acidic products.
The enzyme compatibility of compositions a) to d), ie any restriction of the enzymatic activity, was determined in an indirect manner. The method is based on the fact that if a composition is poorly compatible with enzymes, the enzymatic effect is greatly reduced and size products can only be removed from the tissue with difficulty. In the method used, the content of residual size on fabrics was measured after appropriate treatment with liquors, each containing 10 g / l of one of the compositions a) to d). In addition, the liquors each contained 5 ml / l of an aqueous preparation of α-amylase.
With these enzyme-containing liquors of the compositions a) to d), fabrics made of 100% cotton, on which a size based on starch was based, were treated at room temperature. The liquors were stored for 8 hours before the treatment of the tissues, so that a possible reduction in the enzymatic activity could take place. After the fabrics had been impregnated with the liquors, the fabrics were stored at room temperature for 16 hours to allow the size to be removed. The tissues were then washed with hot water and then the degree of desizing after the treatment was assessed using a calibration scale. In Table II below, "poor" in the "enzyme compatibility" column means that there was still a considerable proportion of the size originally present on the fabrics. "Good" means a small amount of residual size on the fabric.

The results of the tests are given in Table II below.

Claims (14)

Composition containing the following components A), B) and C): A) an ethoxylated alcohol of the general formula (I)

B) an ethoxylated alcohol of the general formula (II)

C) an ethoxylated alcohol of the general formula (III)

where R ^{1 is} a linear or branched alkyl radical having 6 to 14 carbon atoms, R ² and R ^{3 are} each a linear or branched alkyl radical having 10 to 18 carbon atoms, where m is a number from 3 to 12, preferably from 4 to 10, n for a number from 3 to 18 and x for a number from 5 to 20 is, each of the two radicals R ² and R ^{3 contains} at least 2 more carbon atoms than the radical R ¹ and where x - n is equal to or greater than 2. Composition according to Claim 1, characterized in that R ^{1 is} a branched alkyl radical having 8 to 12 carbon atoms. Composition according to Claim 1 or 2, characterized in that R ² and R ³ each independently represent a branched alkyl radical having 10 to 16 carbon atoms. Composition according to one or more of Claims 1 to 3, characterized in that n is a number from 4 to 10 and x is a number from 6 to 16. Composition according to one or more of Claims 1 to 4, characterized in that it contains components A), B) and C) in the following relative proportions: 10 to 40 Parts by weight A 3 to 30 Parts by weight B 0.1 to 10 Parts by weight C Composition according to one or more of claims 1 to 5, characterized in that it additionally contains one or more of components D), E), F), G), H) D) water E) an aliphatic diol with 2 to 10 carbon atoms F) one or more aliphatic, mono- or polyvalent carboxylic acids with 3 to 8 carbon atoms or alkali metal salts of these acids G) hydrolyzed polymaleic anhydride H) an alkyl polyglycoside Composition according to Claim 6, characterized in that component E) is a diol with a branched saturated alkyl radical in which the two OH groups are not bonded to adjacent carbon atoms. Composition according to Claim 6 or 7, characterized in that component F) is a citric acid or an alkali metal salt of this acid. Composition according to Claim 6 or 7, characterized in that component F is gluconic acid or an alkali metal salt of this acid. Composition according to one or more of claims 1 to 9, characterized in that it contains components A) to H) in the following relative proportions: 10 to 40 Parts by weight A 3 to 30 Parts by weight B 0.1 to 10 Parts by weight C 0 to 100 Parts by weight D 0 to 20 Parts by weight E 0 to 20 Parts by weight F 0 to 10 Parts by weight G 0 to 15 Parts by weight H Use of a composition according to one or more of claims 1 to 10 for the treatment of fiber materials, especially textile fabrics. Use according to claim 11, characterized in that the fiber materials are woven or knitted. Use according to claim 11 or 12, characterized in that the fiber materials consist of 50 to 100% by weight of cellulose, in particular cotton. Use according to one or more of claims 11 to 13, characterized in that the treatment of the fiber materials is a pretreatment of textile fabrics.