WO2000022227A1

WO2000022227A1 - Method for finishing textiles

Info

Publication number: WO2000022227A1
Application number: PCT/EP1999/007275
Authority: WO
Inventors: Terese Copete Vidal; Rafael Pi Subirana
Original assignee: Cognis Deutschland Gmbh
Priority date: 1998-10-09
Filing date: 1999-10-01
Publication date: 2000-04-20
Also published as: EP1123436A1; DE19846531A1

Abstract

The invention relates to a method for finishing textiles. According to said method, dyed cotton fabrics are treated with epichlorhydrin-cross-linked polyamidoamines. The polymers, known as fibrabones, are characterised in that reliably prevent loss of colour and bleeding in the wearing and washing of cotton fabrics, especially dark denim.

Description

Textile finishing process

Field of the Invention

The invention is in the field of textile treatment and relates to a process for finishing dyed cotton fabrics against staining and bleeding and the use of special polymers as fixatives.

State of the art

In the production of numerous cotton fabrics, in particular jeans made from colored denim fabric, there is a desire among consumers to give these textiles a used look and at the same time to improve their comfort. For this purpose, the fabrics are treated with pumice stones and cellulases in the "stonewash process". However, a distinction must be made between this targeted aging effect and the undesired bleeding of the dye during washing, which not only leads to an uneven and therefore unattractive color distribution, It can also discolor other textiles that have been washed in. It is also undesirable if the jeans become damp when worn as a result of body sweat or moisture and then rub off on the skin or underwear. It is obvious that a consumer who is inferior in such an underworked manner Make goods to the manufacturer claims for recourse and refrain from further purchases.

Accordingly, the object of the present invention was to provide dyed cotton fabric, in particular denim, in such a way that the dyes used are reliably fixed and bleeding or staining as described above is reliably avoided. Description of the invention

The invention relates to a textile finishing process in which dyed cotton fabric is treated with epichlorohydrin-crosslinked polyamidoamines.

Surprisingly, it was found that the polymers, also known as "fibrabones" from paper production, are also suitable as fixatives for dyes, in particular for indigo and sulfur dyes. When cotton fabrics finished with these polymers, in particular dark denim, are worn and washed, the dyeing and Bleeding of the dye reliably prevented.

Epichlorohydrin-crosslinked polvamidoamines

The epichlorohydrin-crosslinked polyamidoamines to be used in the context of the process according to the invention are known substances which are used under the name “fibrabones” or “wet strength resins” in paper processing. From the extensive prior art, reference is made in this connection to US Pat. Nos. 5,116,887, 5,120,773, 5,239,047 and 5,350,796 (Henkel Corp.) and to European patent application EP-A1 0 553 575 (Hercules). In a preferred embodiment of the invention, polymers are used which are obtained by one of the two following processes:

1. Polyaminoamides are first (a) reacted with an amount of 5 to 30 mol% - based on the nitrogen available for quaternization - of a quaternizing agent, and (b) then the resulting quaternized polyaminoamides with a content of non-quaternized nitrogen corresponding molar amount of epichlorohydrin crosslinked, or

2. Polyaminoamides are (a) first reacted at 10 to 35 ° C. with an amount of 5 to 40 mol% - based on the nitrogen available for the crosslinking - epichlorohydrin, and (b) the intermediate product to a pH in the range from 8 to 11 and crosslinked at a temperature in the range from 20 to 45 ° C. with a further amount of epichlorohydrin, so that the molar application ratio in total 90 to 125 mol%, based on the nitrogen available for the crosslinking - is.

The polyaminoamides which are suitable for production as starting materials are preferably commercially available polycondensation products which are derived from dicarboxylic acids of the formula (I) HOOC- [A] -COOH (I) in which A represents a linear or branched, aliphatic, cycloaliphatic and / or aromatic, optionally hy d roxy-substituted alkylene group having 1 to 52 and preferably 1 to 10 carbon atoms . Typical examples of dicarboxylic acids from which the polyaminoamides can be derived are, for example, succinic acid, azelaic acid, dodecanedioic acid, phthalic acid and technical dimer or trimer fatty acids. They are preferably polyaminoamides based on adipic acid. The polyamidoamines can also be derived from polyamines of the formula (II)

H ₂ N- (B) -NH - [(C) NH] _Z H (II)

in which B and C independently of one another represent linear or branched, optionally hydroxyl-substituted alkylene groups having 1 to 4 carbon atoms and z is 0 or numbers from 1 to 10. Typical examples are polyamines of the formula (II) in which B and C are ethylene groups and z is 2 or 3. Accordingly, the preferred polyamines to be used are diethylenetriamine and triethylene-tetramine. In total, preference is given to polyaminoamides based on adipic acid and diethylene triamine.

If cationic polyamidoamines are used, their quaternization can be carried out in the manner known from the production of conventional cationic surfactants. Examples of suitable quaternizing agents are alkyl halides, such as, for example, methyl bromide, butyl chloride and in particular methyl chloride. Dialkyl compounds such as, for example, diethyl sulfate, dibutyl sulfate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate and in particular dimethyl sulfate can also be used. Finally, 2,3-epoxypropyltrimethylammonium chloride, 3-chloro or 3-bromo-2-hydroxypropyltrimethylammonium chlorides, which are sold by Degussa AG, Hanau / FRG under the name QUAB®, can also be used as quaternizing agents. To carry out the quaternization, the polyamidoamines are dissolved in aqueous or alcoholic solution and the quaternizing agent is added in portions at temperatures in the range from 40 to 70.degree. The reaction time is usually 0.5 to 3 hours. It has proven to be advantageous to relate the amount of the quaternizing agent - 5 to 30 and preferably 15 to 25 mol%, based on the nitrogen available for the quaternization - to the amine number. The quaternization is preferably carried out using dimethyl sulfate or a QUAB reagent. Following the quaternization, it has also proven to be advantageous to adjust the pH of the intermediate to 9 to 11 by adding aqueous alkali base. The polyaminoamides can be crosslinked in aqueous or alcoholic solution. It is advisable to add the epichlorohydrin in portions in both stages and, because of the considerable exotherm, the reaction should not be carried out above 40 ° C. at the lowest possible temperatures. The amount of epichlorohydrin to be used usually corresponds to the molar amount of nitrogen groups available for crosslinking. For practical reasons, it is therefore advisable to determine the amine number of the polymer before crosslinking. In a preferred embodiment, after adding the first part of the epichlorohydrin, the pH of the reaction mixture is adjusted by adding aqueous alkali bases and adjusted to 9 to 11. Following the addition of epichlorohydrin in the second process stage, the product is usually stirred for a period of 12 to 48 and preferably 24 to 36 hours. Towards the end of the reaction time, it is also advisable to raise the temperature to about 40 ° C and to stop the crosslinking by adding mineral acid and setting a pH in the range from 2 to 4 as soon as the viscosity reaches a critical range of about 500 mPas ( measured using the Brookfield method, 40 ° C, spindle 1). Corresponding methods are known from the two publications DE-A1 19517047 and DE-C1 19604176 (Henkel).

Other auxiliaries and additives

The fixation of the dye can go hand in hand with desizing. Accordingly, the polymers can also be used together with desizing agents, in particular enzymes and nonionic surfactants, preferably fatty alcohol polyglycol ethers.

Equipment procedure

A preferred embodiment of the method according to the invention relates to the treatment of denim, preferably dark denim, which is used for the production of jeans. It is possible to finish the dyed fabric or to treat the finished product, i.e. the jeans, accordingly. As already explained above, a major advantage of the method is that the dye can be fixed both before, after and in particular during desizing. The polymers are usually used in amounts of 1 to 10 and preferably 3 to 5% by weight, based on the cotton fabric. If the fixation is carried out as a separate step, the liquor ratio is preferably 1:10, the temperature 50 to 80 ° C. and the treatment time 50 to 15 min, it being possible to treat the tissue by soaking or with circulation. Be fixation and desizing are carried out together, about 1 to 5 g of enzymes, preferably amylases, and 10 to 50 g of nonionic surfactants are added to the solution under the same conditions. The fabrics treated in this way can then be washed, hydrophilized with cationic surfactants and subjected to the stonewash process in a known manner. For a particularly secure fixation of the dye, it has proven to be very advantageous to dry the tissues after fixation / desizing and before further treatment.

Industrial applicability

Another object of the invention finally relates to the use of epichlorohydrin-crosslinked polyamidoamines as fixatives for dyes on cotton fabrics, preferably in amounts of 1 to 10 and in particular 3 to 5% by weight, based on the cotton fabrics.

Examples

Preparation example Hl in a 1 liter stirring apparatus 450 g of a polyaminoamide based on adipic acid and diethylene triamine (amine number 101 mg KOH / g corresponding to 0.81 equivalents of nitrogen, sales product of Henkel Corp., Gulph Mills / US) were suspended in 100 ml of water and 44 g (0.2 mol) of 2,3-epoxytrimethylammonium chloride (70% by weight in water, QUAB® 151 Degussa AG, Hanau / FRG) were added in portions. After the addition was complete, the reaction mixture was heated to 60 ° C over a period of 2 hours. The mixture was then cooled to 17 ° C. and the pH was adjusted to 9.5 to 10 by adding 50% by weight sodium hydroxide solution. The resulting intermediate had an amine number of 81 mg KOH / g. A further 115 ml of water were added to the reaction mixture, and 80 g (0.96 mol) of epichlorohydrin were added in portions, so that the temperature did not rise above 20.degree. The mixture was then stirred at 30 ° C. for 36 h. The mixture was then heated to 40 ° C. and the mixture was stirred further until a sufficient viscosity of about 500 mPas was reached. The reaction was then stopped by adding aqueous hydrochloric acid and adjusting to a pH of 2 to 3. The resulting cross-linked cation polymer had a dry residue of 13% by weight.

Manufacturing example H2. 450 g of a polyaminoamide based on adipic acid and diethylenetriamine (amine number 101 mg KOH / g corresponding to 0.81 equivalents of nitrogen, sales product from Henkel Corp., Gulph Mills / US) were suspended in 105 ml of water in a 1 l stirring apparatus and suspended in portions with 25 mol% - based on the amine number - epichlorohydrin added so that the temperature did not rise above 20 ° C. The mixture was then stirred at 17 ° C. over a period of 4 h and finally adjusted to a pH of 9.5 by adding aqueous 25% by weight sodium hydroxide solution. The reaction mixture was then mixed with a further 95 mol% of epichlorohydrin and stirred first at 20 ° C. and then at 30 ° C. for 21 hours. The mixture was then stirred further until a sufficient viscosity of about 500 mPas was reached. Finally the reaction was stopped by adding aqueous hydrochloric acid and adjusting to a pH of 2.5. The resulting crosslinked polymer was adjusted to a dry residue of 13% by weight by adding water. Example 1. A pair of brand new blue jeans were placed in a Siemens Siewamat 3573 washing machine with a capacity of 5.5 kg of laundry and approx. 60 l of water. 220 g (corresponding to 4% by weight, based on denim) of the polyamidoamide from preparation example 1 were added to the wash liquor. After a treatment time of 10 min at 60 ° C, the jeans were spun dry. The wash liquor was then practically colorless.

Example 2. 5 kg of non-pretreated black denim fabric was soaked for 10 min at 60 ° C. in a solution of 100 g amylase and 200 g of the polyamidoamide from preparation example 2 and then dried. The wash liquor was practically colorless.

Comparative Example V1. Example 2 was repeated, but the addition of the polyamidoamide was dispensed with. The wash liquor was colored brown-black.

Claims

claims

1. Textile finishing process, characterized in that dyed cotton fabric is treated with epichlorohydrin-crosslinked polyamidoamines.

2. The method according to claim 1, characterized in that one uses polymers which are obtained by using polyaminoamides

(a) first of all with an amount of 5 to 30 mol% - based on the nitrogen available for quaternization - of a quaternizing agent, and

(b) then crosslinking the resulting quaternized polyaminoamides with a molar amount of epichlorohydrin corresponding to the non-quaternized nitrogen content.

3. The method according to claim 1, characterized in that polymers are used which are obtained by using polyaminoamides

(a) first reacting epichlorohydrin at 10 to 35 ° C. in an amount of 5 to 40 mol%, based on the nitrogen available for the crosslinking, and

(b) the intermediate product is adjusted to a pH in the range from 8 to 11 and crosslinked with a further amount of epichlorohydrin at a temperature in the range from 20 to 45 ° C., so that the molar ratio in total is 90 to 125 mol. % - based on the nitrogen available for crosslinking - is.

4. The method according to at least one of claims 1 to 3, characterized in that the polymers are used in amounts of 1 to 10 wt .-% - based on the cotton fabric.

5. The method according to at least one of claims 1 to 4, characterized in that the polymers are used together with enzymes and / or nonionic surfactants.

6. The method according to at least one of claims 1 to 5, characterized in that denim is treated.

7. The method according to at least one of claims 1 to 6, characterized in that the cotton fabrics are treated at 50 to 80 ° C.

8. The method according to at least one of claims 1 to 7, characterized in that the cotton fabrics are treated over a period of 5 to 15 minutes.

9. The method according to at least one of claims 1 to 8, characterized in that drying the cotton fabric after the treatment.

10. Use of epichlorohydrin-crosslinked polyamidoamines as fixatives for dyes on cotton fabrics.