EP1266064A2

EP1266064A2 - Use of mixtures of optical brighteners to improve the wash fastness of brightened textiles

Info

Publication number: EP1266064A2
Application number: EP01905707A
Authority: EP
Inventors: Thomas LÜTKENHORST; Thomas Martini; Joseph Thomas Craddock
Original assignee: Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2000-02-09
Filing date: 2001-01-30
Publication date: 2002-12-18
Also published as: DE10005595A1; US20010031806A1; CN1398307A; WO2001059198A2; WO2001059198A3; JP2003522843A

Abstract

The invention relates to the use of a mixture of optical brighteners comprising A) at least one anionic brightener selected from the group consisting of pyrazolin derivatives comprising sulfonic acid or sulfonate groups, and anionic brighteners as represented in formulae 1-12, in addition to B) at least one anionic brightener which is a derivative of stilbene, respectively comprising a sulfonic acid or sulfonate group in both phenyl groups and which is also substituted by an aromatic heterocycle which includes nitrogen in both phenyl groups of stilbene. The inventive mixture is used to produce brightened polyamide and/or polyurethane fibers exhibiting improved wash fastness with respect to said optical brightening.

Description

description

Use of mixtures of optical brighteners to improve the wash fastness of lightened textiles

The present invention relates to the use of optical brighteners to improve the wash fastness of lightened textiles.

The authenticity profile of optically brightened textile articles made of polyamide and polyamide / polyurethane blends includes high demands on light and weather fastness as well as high demands on wash resistance.

Lightened items such as swimwear or underwear should suffer as little loss of white as possible during the washing process even after multiple washes. These requirements are primarily met by those polyamide (PA) or polyamide / polyurethane (PU) materials in which the brightener is applied during polymer production or using masterbatch technology. The brighteners used here generally have a high fastness profile.

In order to achieve peak white effects and to meet changing fashion requirements with regard to the nuance, however, textile application processes such as e.g. Pull-out process, block thermosol process, block / steam or block washing process or acid shock process with and without reducing agents used. These processes are known to the person skilled in the art and can be found in relevant literature references. (e.g. R.Williamson, "Fluorescent Brightening Agents" in Textile Science and Technology pp. 63-69, Elsevier Scientific Publishing Company, Amsterdam, Oxford, New York 1980).

The brighteners used in the textile application have the disadvantage, depending on their different affinities for the fiber, that they can be partially washed out again by subsequent washing processes. Surprisingly, it has now been shown that the wash-fastness of optical brighteners on polyamide and polyamide / polyurethane articles can be significantly improved if mixtures of certain optical brighteners are used.

The invention thus relates to the use of a mixture of optical brighteners, which comprises

A) at least one anionic brightener, selected from the group consisting of derivatives of pyrazoline, which carry sulfonic acid or sulfonate groups, and those anionic brighteners, which in the

Formulas 1 to 12 are shown, and

B) at least one anionic brightener, which is a derivative of stilbene, which carries a sulfonic acid or sulfonate group on each of the two phenyl groups of the stilbene, and is likewise substituted on both phenyl groups of the stilbene with a nitrogen-containing, aromatic heterocycle, for the preparation of brightened polyamide - And / or polyurethane fibers, which show an improved wash fastness of the optical brightening.

It has been shown that even small amounts of component B), which are preferably in the mixture at 25% by weight or less, based on the total brightener weight, are sufficient to achieve an improvement in the fastness to washing of the lightening effects of component A).

The application of the brightener mixture takes place according to the state of the art, in the present case the extraction process was used. All structures made of polyamide or polyamide / polyurethane mixtures can be used as the textile material, the mixing ratio being uncritical.

A precise definition of the chemical nature of the fibers can be found in "Winnacker-Küchler", Chemical Technology, Volume 6, Organic Technology S.690 - 700, and S 710. Karl Hanser Verlag Munich Vienna 1982. The quantities of brightener used are not critical and are based on the recommendations of the technical information leaflets of the brightener manufacturers.

Component A) of the brightener mixture is preferably a derivative of pyrazoline which carries substituents with sulfonic acid or sulfonate groups. These substituents are preferably aromatic substituents which carry halogen or alkyl radicals. The alkyl radicals can include heteroatoms. The sulfonic acid or sulfonate groups are either on the aromatic substituents or on the alkyl radicals. Among aromatic

Here, substituents are understood in particular to mean phenyl, naphthyl, biphenyl and anthracenyl.

The compounds of formulas 1 to 15 are as follows:

in which Ar ¹ and Ar ² independently of one another are sulfonated and further substituted or unsubstituted aryl radicals, in particular sulfonated phenyl, biphenyl or naphthyl radicals, which are further substituents such as hydroxy, (Ci-CβJ-alkyl, (Cι-C ₆ ) alkoxy, Halogen, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, alkoxycarbonyl, sulfonic acid ester, alkylsulfonyl, arylsulfonyl, sulfonyl and sulfonamide groups, and R ¹⁵ and R ¹⁵ , which may be the same or different, Hydrogen, (-CC ₄ ) alkyl or phenyl mean.

wherein R ^{16 is} halogen or (CrC ₆ ) alkyl, R ^{17 is} a substituted or unsubstituted (CrC ₆ ) alkoxycarbonyl, Sulfonamide or sulfonic acid group, m is zero, 1, 2 or 3.

Preferred pyrazoline brighteners are shown in the formulas (3) to (5):

S0 ₂ CH ₂ CH, SO ₃

S0 ₂ CH ₂ CH, S0 ₃ M

Further preferred optical brighteners as component A of the mixture are as follows:

with R ¹⁸ = H, alkyl, oxalkyl, halogen, CN, COO- (dC ₄ ) -alkyl or CO-N [(CC ₄ ) -alkyl] ₂ , and n = 0.1.

Component B of the mixture of optical brighteners is a stilbene derivative which generally corresponds to formula (13):

where R stands for an aromatic, nitrogen-containing heterocycle. This heterocycle is preferably derived from triazole or triazine. Particularly preferred compounds for component B are:

Examples

All percentages are percentages by weight, unless stated otherwise.

Example 1 Recipe for lightening PA6 woven goods after the pull-out process

1 g / l Sandoclean PCJ fl (non-ionic detergent and wetting agent)

1% commercial optical brightener or brightener mixture of the formulas 16 up to 21 based on the amount of PA woven fabric pH 4 used (acetic acid)

98 ° C / 40 min.

Fleet ratio 1:10

Formula structures of the optical brighteners 16 to 21 used

SO, CH, CH, SO, Na

Results:

The following degrees of whiteness are achieved according to Ganz (standard brighteners)

1% brightener of formula 16 (approx. 13% active content) 230

1% brightener of formula 17 (approx. 13% active content) 227

1% brightener of formula 18 (approx. 20% active content) 233

1% brightener of formula 19 (approx. 15% active content) 226 (laboratory setting)

1% brightener of formula 20 (approx. 20% active content) 221

1% brightener of formula 21 (approx. 12% active content) 222 Example 2

The samples brightened according to Example 1 are five times as follows

The recipe is washed and the white effects are determined after each wash:

Fleet ratio 1:20

1% H ₂ O ₂ 35% based on the weight of the goods 5 g / l commercial, brightener-free detergent 55 ° C / 30 min

It is then rinsed cold.

Results from Example 2

Example 3

As described in Example 1, 0.8% of the brightener of the formula 16 and 0.2% of the brightener of the formula 20 are used for the brightening. The whiteness achieved is 230. After 5 washes according to Example 2, 213 whiteness are still obtained, a significant improvement over the white effects using brightener 16 alone. Example 4

For brightening, as described in Example 1, 0.8% of the brightener of the formula 17 and 0.2% of the brightener of the formula 20 are used. The whiteness achieved is 223. After 5 washes according to Example 2, 214 whiteness are still obtained, a significant improvement over the whitening effects of brightener 17 alone.

Example 5

For brightening, as described in Example 1, 0.8% of the brightener of formula 18 and 0.2% of the brightener of formula 20 are used. The scored

The degree of whiteness is 233. After 5 washes in accordance with Example 2, 220 degrees of whiteness are still obtained, a marked improvement over the whitening effects of the brightener of formula 18 alone.

Example e

For brightening, as described in Example 1, 0.9% of the brightener of formula 19 and 0.1% of the brightener of formula 20 are used. The whiteness achieved is 223. After 5 washes according to Example 2, 201 whiteness are still obtained, a significant improvement over the whitening effects of brightener 19 alone.

Example 7

For brightening, as described in Example 1, 0.8% of the brightener of the formula 16 and 0.2% of the brightener of the formula 21 are used. The whiteness achieved is 229.

After five washes according to Example 2, 195 degrees of whiteness are still obtained, a significant improvement over the washing effects of Example 2 when brightener 16 is used alone.

Example 8

For brightening, as described in Example 1, 0.5% of the brightener of the formula 16, 0.25% of the brightener of the formula 20 and 0.25% of the brightener of the formula 18 are used. The whiteness achieved is 226. After five washes according to Example 2, 216 whiteness are obtained.

Claims

claims:

1. Use of a mixture of optical brighteners, which comprises

A) at least one anionic brightener, selected from the group consisting of derivatives of pyrazoline, which are sulfonic acid or

Carrying sulfonate groups, and those anionic brighteners, which are shown in the formulas 1 to 12, and

B) at least one anionic brightener, which is a derivative of stilbene, which carries a sulfonic acid or sulfonate group on both phenyl groups of stilbene, and also on both phenyl groups of

Stilbens is substituted in each case with a nitrogen-containing, aromatic heterocycle for the production of brightened polyamide and / or polyurethane fibers, which show an improved wash fastness of the optical brightening.

2. Use according to claim 1, wherein component A) is a derivative of pyrazoline which carries substituents with sulfonic acid or sulfonate groups, these substituents being aromatic groups which carry halogen, alkyl or heteroalkyl radicals.

3. Use according to claim 2, wherein component A) is a compound selected from formulas 3 to 5

see 2 CH ₂ C (CH ₃ 3) '2 SO, M

SO, CH, CH, S0 ₃ M

^S0 2 CH ₂ CH ₂ SO ₃ M

4. Use according to one or more of claims 1 to 3, wherein component B is a stilbene derivative of the formula 13

and wherein R represents a substituent derived from triazole or triazine.

5. Use according to claim 4, wherein component B) is a compound selected from formula (14) or (15)

6. Use according to one or more of claims 1 to 5, wherein the amount of component B) is 25% by weight or less of the total lighter weight.