EP1504149A2

EP1504149A2 - Method for brightening textile materials

Info

Publication number: EP1504149A2
Application number: EP03717323A
Authority: EP
Inventors: Dieter Weber; Helmut Reichelt; Gerhard Wagenblast
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2002-05-03
Filing date: 2003-04-30
Publication date: 2005-02-09
Anticipated expiration: 2023-04-30
Also published as: AU2003222312A1; ZA200409769B; WO2003093565A3; US20050235429A1; BR0309642A; CN1333129C; KR100973535B1; HRPK20041141B3; ATE302871T1; HRP20041141A2; BR0309642B1; DE50301054D1; ES2246470T3; AU2003222312A8; EP1504149B1; MXPA04010130A; TWI279468B; WO2003093565A2; CN1650064A; JP2005529245A

Abstract

Disclosed is a method for brightening textile materials by treating said materials with optical brighteners in an aqueous bath. The inventive method is characterized by the fact that 20 to 80 percent by weight of compound (I) are used as optical brighteners, the percentage by weight being in relation to the total of all brightening compounds and up to 40 molar percent of (I) being in the form of cis isomer, 80 to 20 percent by weight of at least one compound (II), selected among (II m, p'), (II p, o'), (II o, o'), (II p, p'), and 0 to 30 percent by weight of a compound of general formula (III), in which R is selected among C4-C10 alkyl. The treatment is done in the presence of one or several shading blue or purple dyes from the class of anthrachinones, azo dyes, or methine dyes.

Description

Process for lightening textile materials

description

The present invention relates to a process for lightening textile materials by treatment with optical brighteners in an aqueous liquor, characterized in that 20 to 80% by weight, based in each case on the sum of all brightening compounds, of compound I

where up to 40 mol% of I can be present as the cis isomer, and 80 to 20% by weight of at least one compound II selected from

II p, θ '

II p, p '

and 0 to 30% by weight of at least one compound of the general formula III R

in which R is selected from C -C -oalkyl, is used, the treatment optionally being carried out in the presence of one or more blue or violet shading dyes from the class of the anthraquinones, azo dyes or methine dyes.

Optical brighteners are of great economic importance as aids for the textile industry and for the plastics industry. Numerous compounds are known for their ability to give textiles or plastics a white color. However, most of these known compounds also have disadvantages. So are compounds of general formula 1

known from EP 0 023 026, where, for example, the radicals R ¹ and R ^{2 can be,} for example, hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, alkyl or numerous other radicals and where V is selected from

Compounds of the general formula 1 can be applied at low temperature, but their abundance is limited, ie a lot of product is required to achieve the desired whitening effect. Also known is a process for lightening textiles by treating the textiles with distyrylbenzene compounds, for example from CH-A 366 512, CH-A 382 709, CH-A 388 294, CH-A 389 585, CH-A 411 329 , CH-A 416 078 and CH-A 465 548 are known. EP-A 0 023 027 and EP-B2 0 030 917 and the literature cited in EP-B2 0 030 917 demonstrate the use of mixtures of two or more dicyanostyrylbenzene compounds for the optical brightening of polyesters.

EP 0 023 026 discloses mixtures of optical brighteners which contain 0.05 to 0.95 parts by weight of one or more compounds of the formula 2 p

2p

contain, where A is a phenyl group substituted with an ortho- or para-cyano group, and 0.95 to 0.05

Parts by weight of one or more other compounds selected from a wide variety of other compounds. Mixtures of 2 p, o ^λ are preferred

2 p, o '

with compounds of general formula 1

in which the radicals R ¹ and R ^{2 can} mean: hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, Ci-Cg-alkyl, alkoxy, alkylamino and numerous other radicals, which are listed on page 2, lines 14-21, and V as defined above,

or with compounds of formula 3b-4b

3b 4b where B is a functional group, R ¹ and R ² are as defined above, n is an integer, R ^{3 is} hydrogen and

Cχ-C ₄ alkoxy, R ⁴ from -CC alkoxy groups and R ^{5 is selected} for example from Ci-Cg-alkyl and B is preferably a functional group, or further with compounds of the formulas 5b to 6b

5b 6b, the radicals R ⁶ to R ^{10 are in} each case selected from different groups and V is defined as above.

From this multitude of embodiments, mixtures of 2 p, o * or other isomers with 3c are essentially exemplified in Table 2

3c

and demonstrated with the following derivatives of 4 bl and 4 b.2: CH = COCH3

4 left

4 b.2

The brighteners defined in this way are applied using various methods and give a good degree of whiteness according to CIE.

EP-A 0 023 028 claims mixtures containing 0.05 to 0.95 parts by weight of a mixture consisting of 20 to 100% by weight of 2 p, o '

NC

2 p, o '

and each 0 to 80 wt .-% of the compounds 2 p, p ^λ and 2 o, o ^λ

2 p, p '

2 0.0 '

and 0.05 to 0.95 parts by weight of one or more derivatives of the formulas la and 3a to 6a can be used as optical brighteners, la and 3a to 6a being defined essentially analogously to EP-A 0 023 026. DE-A 197 32 109 shows the optical brightening of polyamide or polyurethane, mixtures of derivatives of compounds of the type la

in which R ¹ and R ² independently of one another denote H or -CC ₆ alkyl, A is selected from N and CH and X is selected from

furthermore from stilbenyl, styryl or imidazolyl, with one or more isomers of 2 or one of the numerous derivatives of 4

or numerous other derivatives, for example with 5 b (see above). Examples (Examples 19-21) of 1 al with 4 bl

1 a. l

COOCH ₃

The mixtures show a synergistic effect with regard to the CIE whiteness and good light fastness.

EP-A 0 321 393 describes the use of compounds of type 1 b,

in which D is a Cχ-C alkyl group, and compounds of formula 2 described in brightener dispersions. The compounds of type 1 b or 2 are disclosed either individually or as special mixtures, referred to in the cited document as mixtures 1 to 6 (page 6-8). It is essential to the invention in EP-A 0 321 393 that the mixture contains a copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid (page 9, line 18).

EP-A 0 682 145 improves the light fastness of textiles by treating them with formulations which contain a fluorescent UV absorber which absorbs at a wavelength of 280 to 400 nm, selected from 4.4 ^λ -bis- Triazinyl-aminostilbene-2, 2'-disulfonic acids, 4, 4 ^v -diphenylstilbenes, 4,4'-distyrylbiphenyls, 4-phenyl-4 ^v -benzoxazyl-stilbenes, stilbenylnaphthotriazoles, 4-styrylstilbenes, coumarins, pyrazolines, naphthalimides Triazinylpyrenes, 2-styrylbenzoxzaol or 2-styrylnaphthoxazole derivatives, benzimidazolbenzofurans, oxanilide derivatives and bis-benzoxazol-2-yl and bis-benzimidazol-2-yl derivatives applies, for example of the formulas 1 c or 1 d ) lc

ld

where the variables mean:

R ^{14 is} independently hydrogen or -CC alkyl or tert. -Butyl or

-C (CH ₃ ) ₂ phenyl or COO -CC-alkyl

R ¹⁵ and R ^{16 are the} same or different and are selected from H, -CC ₄ alkyl and CH ₂ -CH ₂ -OH,

the R ¹⁷ radicals are the same or different and are selected from H and S0 ₃ ^_

X is selected from

and X ^{1 is} selected from

However, other processes usually play a role in improving light fastness than in optically brightening textiles.

A brilliant white is of great economic importance for a wide variety of products, such as textiles and plastic moldings. The numerous mixtures demonstrated above, in particular the mixtures demonstrated in the examples of EP-A 0 023 026 and EP-A 0 023 028 and EP-A 0 682 145, show a white which is often not yet sufficiently bright for demanding customers. Further application properties can also be improved. Finally, for economic reasons, it is desirable that the brighteners have a better spread, i.e. one achieves an effect of the same size or even greater with less brightener.

So the task was

to provide a process for lightening textile materials which provides a particularly brilliant white with improved extensibility and otherwise also improved application properties; To provide formulations for a process for lightening textile materials and - to provide uses for the new formulations.

The method defined at the outset was found accordingly.

Textile materials within the meaning of the present invention include fibers, roving, yarn, twine, woven goods, knitted fabrics,

Nonwovens, garments understood from, for example, polyesters or polyester mixtures. The textile materials preferably consist of synthetic polyester or of mixtures containing 45 to 90% by weight of polyester.

In the context of the present invention, brightening or optically brightening compounds are understood to be fluorescent compounds which can absorb in the range from 280 to 400 nm and emit at a higher wavelength. Examples of compounds from the class of the stilbenes, distyrylbenzenes, diphenyldistyryls, triazinyls, benzoxazoles, bisbenzoxazoles, bisbenzoxazolylthiophenes, bisbenzoxazolylnaphthalenes, pyrenes, coumarins and naphthalene peridicarboximides are mentioned. In particular, brightening or optically brightening compounds are understood to be those of the formulas I, II and III. Data in% by weight relate to the following on the sum of the brightening compounds, unless expressly stated otherwise.

For the purposes of the present invention, aqueous liquors are also understood to mean those liquors which, in addition to water as the main constituent, contain up to 40% by volume of one or more further solvents, for example alcohols such as ethanol. The pH of the liquors used according to the invention is preferably from 3 to 12, preferably 3 to 8.

To carry out the process defined at the outset, textile materials are treated with 20 to 80, preferably 20 to 70% by weight and particularly preferably 30 to 50% by weight of the compound of the formula I.

where up to 40 mol% of I may be in the form of the corresponding cis isomer, and 80 to 20% by weight of at least one of the compounds II

II PP ' and 0 to 30% by weight of a compound of the general formula III

wherein R is selected from C ₄ -Cιo-alkyl, for example n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2 -Dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl; n-butyl and 2-ethylhexyl are preferred.

In addition to 20 to 80% by weight of compound I is preferably used:

0 to 30% by weight of a compound of the general formula III and in each case 20 to 70% by weight of at least one of the compounds II p, o 'or m, p'.

It is particularly preferred to use 20 to 70% by weight of compound I and 0 to 30% by weight of a compound of the general formula III:

20 to 70% by weight of compound II p, o 'and 10 to 50% by weight of compound m, p'.

In another particularly preferred embodiment, 30 to 50% by weight of compound I and 0 to 30% by weight of a compound of the general formula III are used

30 to 60% by weight of compound II p, o ',

10 to 30% by weight of compound II o, o 'and optionally 10 to 50% by weight of compound m, p'.

The synthesis of compound I is carried out, for example, according to US 2,842,545, US 2,875,089 or US 3,147,253. For the purposes of the present invention, I also means mixtures of isomers which contain 0.2 to 40 mol%, preferably 0.7 to 20 mol%, of cis isomer. The proportion of cis isomer is determined by spectroscopic or chromatographic methods familiar to the person skilled in the art, see FIG. for example J. Chromat. 1967, 27 (2), 413-22. The dicyanostyryl compounds II p, o ', II m, p', II p, p 'and II o, o' used are used in the form of their trans isomers. They usually contain 0.01 to 10, preferably 0.1 to 5 mol% of isomers with at least one cis double bond, the proportion of cis isomers being determined by spectroscopic methods known to the person skilled in the art. They are easily accessible through a double Wittig reaction from terephthalaldehyde and the corresponding cyanobenzyl phosphorylides.

When carrying out the process according to the invention, one or more blue or violet shading dyes can advantageously be added. Suitable shading dyes generally come from the class of disperse dyes and vat dyes. These are common names. The color index contains such dyes e.g. listed as Disperse Blue or Disperse Violet or Vat Blue or Vat Violet.

Blue dyes from the class of anthraquinones, azo dyes or methine dyes are particularly suitable.

Dyes from the class of anthraquinones obey, for example, the formulas A 1 to A 4

wherein

Z ¹ Ci-Cio-alkyl, which is optionally interrupted 1 or 2 oxygen atoms in ether function and can be substituted by -C-C ₄ alkoxycarbonyl or cyano or optionally substituted by -C-C ₄ alkoxy, phenyl, substituted phenyl,

Z ² Ci-Cio-alkyl, which is optionally interrupted by 1 or 2 oxygen atoms in ether function and can be substituted by hydroxy, phenyl or Ci-Cs-Al oxycarbonyl, Z ³ oxygen or NH,

Z ⁴ is hydrogen, Ci-Cio-alkyl which may be interrupted by 1 or 2 oxygen atoms in ether function and which may be substituted by C ₁ -C ₄ -alkoxycarbonyl or cyano, or unsubstituted or Cι-C ₄ alkoxy,

Z ^{5 is} hydrogen or halogen or CN,

Z ^{6 is} hydrogen or nitro and

Z ^{7 is} C ₂ -C ₆ alkylene or phenylene.

The dyes mentioned above are generally known dyes. Dyes of the formula A2 are e.g. in US-A 2,628,963, US-A 3,835,154, DE-A 12 66 425 or DE-A 20 16 794. Dyes that obey the formula AI, A3 and A4 are e.g. from K. Venkataraman, "The Chemistry of Synthetic Dyes", Volume 3, pages 391 to 423, 1970.

Suitable azo dyes are in particular monoazo dyes with a diazo component from the aniline or heterocyclic series and a coupling component from the aniline or heterocyclic series.

Suitable heterocycles from which the diazo components are derived are e.g. from the class of aminothiophenes, aminothiazoles, aminoisothiazoles, aminothiadiazoles or aminobenzisothiazoles.

Suitable heterocycles from which the coupling components are derived are e.g. from the class of the thiazoles or diamino-pyridines.

Such azo dyes in particular correspond to one of the formulas B 1 to B 7

wherein

Z ⁸ formyl, cyano, C 1 -C ₄ alkoxycarbonyl or phenylsulfonyl,

Z ^{9 is} hydrogen, halogen, Ci-Cs-alkoxy, phenoxy, Ci-Cβ-alkylthio, phenylthio, Cι-C ₄ alkylsulfonyl, phenylsulfonyl, methyl or optionally substituted by chlorine, methoxy, ethoxy or methyl-substituted phenyl,

Z ¹⁰ cyano, Ci-Cg-alkoxycarbonyl, the alkyl chain of which may be interrupted by one or two oxygen atoms in ether function, carbamoyl or C 1 -C 1 -mono- or dialkylcarbamoyl,

Z ¹¹ and Z ¹² independently of one another each Ci-Cs-alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function and by hydroxy, cyano, chlorine, phenyl, Ci-C _ß -alkoxy, Ci-C _δ -alkoxycarbonyl, Ci -C _δ -alkoxycarbonyloxy or Cχ-Cs-mono- or dialkylaminocarbonyloxy may be substituted, or C ₃ -C ₄ -alkenyl or Z ¹¹ , but not Z ¹² also hydrogen,

Y ^{1 is} hydrogen, Cχ-C ₄ alkyl, C ~ C ₄ alkoxy, chlorine, bromine or a radical of the formula -NH-CO-R ¹¹ , where R ^{11 is} C ₁ -C ₄ alkyl, which is by Cι- C ₄ alkoxy, Cyano, hydroxy, chlorine or -CC ₄ -alkanoyloxy can be substituted, or C ₂ -C -alkenyl is,

Y ^{2 is} hydrogen, -CC ₄ alkyl or -C ~ alkoxy

Z ¹³ optionally substituted by C 1 -C ₄ -alkoxy-C ₄ alkyl, optionally substituted by C 1 -C ₄ -alkoxy benzyl, optionally substituted by chlorine, methyl, methoxy or ethoxy-phenyl, pyrid-2-yl or pyrid-3- yl,

Z ¹⁴ cyano, chlorine or bromine,

Z ¹⁵ optionally substituted by -CC ₄ alkoxy or acetylamino thienyl or pyridyl and

Z ^{16 is} cyano, chlorine or bromine.

The azo dyes mentioned above are known per se. Dyes of the formula B1 and B2 are e.g. in US 5,283,326 or US 5,145,952. Dyes of the formula B3 are known from EP-A 0 087 616, EP-A 0 087 677, EP-A 0 121 875, EP-A 0 151 287 and US 4,960,873. Dyes of the formula B4 are known from US Pat. No. 5,216,139. No. 5,132,412 describes dyes of the type of the formula B5. Dyes of the formulas B6 and B7 are e.g. in US 3,981,883, DE-A 31 12 427, EP-A 0 064 221 or in Venkataraman "The Chemistry of Synthetic Dyes", volume 3, pages 444 to 447, or can be obtained by the methods mentioned therein.

Suitable methine dyes obey e.g. of the formula C.

Y ³ nitrogen or CH,

Z ¹⁸ -CC ₂ o-alkyl, which is optionally substituted and can be interrupted by one or more oxygen atoms in ether function, optionally substituted phenyl or hydroxy, Z ^{19 is} a 5-membered aromatic heterocyclic radical,

Z ^{20 is} hydrogen, cyano, carbamoyl, carboxyl or -CC ₄ alkoxy carbonyl,

Z ^{21 is} oxygen or a radical of the formula C (CN) ₂ , C (CN) COOZ ²³ or C (COOZ ²³ ) ₂ , where Z ²³ each represents C 1 -C ₈ -alkyl, which may be interrupted by 1 or 2 oxygen atoms in ether function is stands

Z ^{22 is} hydrogen or -CC ₄ alkyl.

If substituted alkyl radicals occur in formula C, the following may be used as substituents, unless stated otherwise, for example phenyl, C 1 -C ₄ -alkylphenyl, C 1 -C ₄ -alkoxyphenyl, halophenyl,

Ci-Cg-alkanoyloxy, Ci-Cs-alkylaminocarbonyloxy, Cι ~ C ₂ o-alkoxycarbonyl, Cι-C ₂ o ~ alkoxycarbonyloxy, the alkyl chain of the latter two radicals optionally being interrupted by 1 to 4 oxygen atoms in ether function and / or by Phenyl or phenoxy is substituted, halogen, hydroxy or cyano come into consideration. The alkyl radicals generally have 1 or 2 substituents.

If alkyl radicals which are interrupted by oxygen atoms in ether function occur in formula C, unless otherwise noted, preference is given to those alkyl radicals which are interrupted by 1 to 4 oxygen atoms, in particular 1 to 2 oxygen atoms, in ether function.

If substituted phenyl or pyridyl radicals occur in formula C, the substituents, e.g. Ci-Cs-alkyl, Ci-Cs-alkoxy, halogen, in particular chlorine or bromine, or carboxyl. The phenyl or pyridyl radicals generally have 1 to 3 substituents.

Z ¹⁹ radicals can be derived, for example, from components from the pyrrole, thiazole, thiophene or indole series.

Important Z ¹⁹ radicals are, for example, those of the formulas C 1 to C 4

c 1 C 2

C 4 wherein

m 0 or 1,

Z ²⁴ and Z ^{25 are the} same or different and independently of one another are each hydrogen or -CC-alkyl, which is optionally substituted and can be interrupted by one or more oxygen atoms in ether function, optionally substituted phenyl or together with the nitrogen atom connecting them is a 5- or 6-membered saturated heterocyclic radical which may have further heteroatoms,

Z ^{26 is} hydrogen, halogen, Ci-Cs-alkyl, optionally by

Cχ-C-alkyl or Cι-C ₄ alkoxy substituted phenyl, optionally substituted by Cχ-C ₄ alkyl or Cι-C ₄ alkoxy benzyl, cyclohexyl, thienyl, hydroxy or Ci-Cs-monoalkylamino,

Z ^{27 are the} same or different and are each independently hydrogen, hydroxy, optionally substituted by phenyl or C ₄ -C ₄ -alkylphenyl Ci-Cβ-alkyl, optionally substituted by phenyl or C 1 -C ₄ -alkylphenyl Ci-Cs-alkoxy, Cι- C ₈ -alkanoylamino, Cχ-C ₈ -alkylsulfonylamino or Ci-Cβ-mono- or dialkylaminosulfonylamino, Z ²⁸ cyano, carbamoyl, C 1 -C ₈ -mono- or dialkylcarbamoyl,

-CC ₈ alkoxycarbonyl or optionally substituted phenyl and

₄ -alkylthio optionally substituted by Cι-C ₄ alkyl or Cι-C, Z ²⁹ halogen, are hydrogen, C ₄ -alkyl, C ₄ -alkoxy, C, ₄ alkoxy-substituted phenyl or thienyl.

Such methine dyes are e.g. described in the older German patent application DE-A 44 03 083.

Of particular importance is a procedure in which the treatment of the polyester or polyester mixture is carried out in the presence of one or more blue or violet shading dyes from the class of the anthraquinones, in particular those of the formula A.

Technically, the process can be carried out particularly well in the presence of the dye of the formula A 3.1

who is also known as C. I. Disperse Violet 28 (61102) is known.

Based on the weight of the textile material to be lightened, 0.005 to 0.07, preferably 0.02 to 0.05% by weight of lightening compounds are used according to the invention and the same or even a better white effect is achieved than in the case of the prior art known optically brightening substances.

Based on the weight of the textile material to be lightened, 0.00005 to 0.02% by weight, preferably 0.0005 to 0.002% by weight, of blue or violet shading dye is generally used. But you can also work without using a shading dye.

The lightening of the textile materials is usually done using the pull-out or thermosol process. The pull-out process usually works in aqueous liquors at temperatures of 90 to 135, usually around 130 ° C. In the case of application above 100 ° C, work must be carried out in an autoclave, a high-pressure device or a high-pressure machine. The Thermosol process is used at atmospheric pressure.

In the pull-out process, the textile material to be lightened is generally brought into an aqueous liquor at a temperature of 10 to 35 ° C., which contains the optically brightening compounds, optionally a blue or violet one

Shading dye or a mixture thereof and optionally an additive, e.g. Contains dispersants, carboxylic acids or alkali donors and whose pH is usually 3 to 12, preferably 3 to 8. The liquor ratio (weight ratio of textile material: liquor) is 1: 3 to 1:40, preferably 1: 5 to 1:20. The bath is then heated to a temperature of 90 to 130 ° C., preferably 95 to 100 ° C., within 15 to 30 minutes and held at this temperature for 15 to 60 minutes. Then the lightened textile material is rinsed and dried.

In the thermosol process, the textile material to be lightened is usually padded with an aqueous liquor which contains the optical brightening substances, optionally a blue or violet shading dye or mixtures thereof and optionally an additive (see above). The liquor intake is generally 50 to 100%. The textile material is then dried and fixed at a temperature of 150 to 200 ° C for 5 to 60 seconds.

Dispersants which are colorless and which are stable against yellowing at temperatures of up to at least 210 ° C. are preferably used as dispersants.

Particularly suitable dispersants are e.g. Anionic or nonionic, in particular those from the class of ethylene oxide adducts with fatty alcohols, higher fatty acids or alkylphenols or ethylenediamine-ethylene oxide-propylene oxide adducts.

Particularly preferred dispersants are alkoxylation products which are based on aliphatic or alkylaromatic hydroxy, amine and aminohydroxy compounds under the brand names S nperonic® and Ukanil®, Dehypon®, Neopol®-Ethoxylate, Emulan®, Lutensol®, Plurafac® and Pluronic® or Elfapur® are commercially available. Are particularly preferred oxyalkylated phenols. Particularly preferred dispersants are oxyalkylated phenols of the general formulas IV and V

H C

M) _d (H) ₁ ^)

H ₃ C

IV

HoC

) _d (H) _{] d} )

H ₃ C

V

or their mixtures, in which the variables are defined as follows:

a and b are integers

a is in the range from 0 to 180, preferably from 0 to 125

b is in the range from 20 to 180, in particular from 35 to 125, where b ≥ a;

M is an alkali metal, preferably Na or K and particularly preferably Na;

d is 0 or 1.

The preparation of the compounds IV and V is known and is advantageously carried out by reacting the phenols VI and VII

VI VII with propylene oxide and subsequent reaction of the adduct with ethylene oxide or by reacting VI or VII with ethylene oxide. The adducts can then be completely or partially reacted with chlorosulfonic acid or sulfur trioxide to give half-sulfuric acid and the half-esters obtained can be neutralized with alkaline agents.

The phenols of the formulas VI and VII can be obtained by reacting bisphenol A (2,2- (p, p'-bishydroxydiphenyDropane) or phenol with 4 or 2 mol styrene in the presence of acid as a catalyst the phenols VI and VII are reacted by known processes first with propylene oxide and then with ethylene oxide or only with ethylene oxide in the presence of acidic or alkaline catalysts, for example with NaOCH or with SbCls, to give the corresponding oxyalkylation products IV or V with d = 0. The oxyalkylation can be carried out, for example, by the process described in US 2,979,528.

The sulfuric acid half-esters are prepared by reacting the oxyalkylation products with chlorosulfonic acid or sulfur trioxide, the amount of chlorosulfonic acid or sulfur trioxide being selected such that all free hydroxyl groups or only a certain percentage is sulfated. In the latter case, mixtures are formed from compounds of the formula IV or V which contain free and sulfated hydroxyl groups. For use as surfactants, the half esters of sulfuric acid obtained in the reaction are converted into water-soluble salts. The alkali metal salts, for example the sodium or potassium salts, are advantageously considered as such. Two equivalents are required in the case of chlorosulfonic acid, and one equivalent in the case of sulfur trioxide. The latter is used for moderately aqueous alkali metal hydroxide. The temperature should not exceed 70 ° C during neutralization. The salts obtained can be isolated in the form of aqueous solutions or else as such and used in solid form.

Dispersants IV and V are preferred in which a is 0 to 2.5 on average, b is 25 to 250 on average and d is 0 to 0.5 on average. Dispersants IV and V are particularly preferred in which a is 0 to 2.5 on average, b is 50 to 100 on average and d is 0.5 on average.

Compounds of formula IV and V are known and numerous representatives e.g. in US 4,218,218.

Additional additives to be added are, for example, the biocides or water retention agents commonly used in the textile industry. Further additives to be added optionally are the copolymers of N-vinylpyrrolidone with 3-vinylpropionic acid described in EP-A 0 321 393.

In a preferred procedure, a formulation is used which, in addition to water, in each case based on the weight of the preparation, 1 to 40% by weight, preferably 3 to 10% by weight, of the mixture of brightener and shading dye described in more detail above, 3 to 12 wt .-% anionic or nonionic

Dispersant, 1 to 15% by weight copolymers of N-vinylpyrrolidone with vinyl acetate or vinyl propionate or mixtures thereof, and 1 to 25% by weight of other additives (e.g. water retention agents or biocides).

By means of the process according to the invention, textile materials can be brightened with excellent white effects both in the pull-out and in the thermosol process. The lightened materials show excellent fastness properties.

To prepare the above-described aqueous liquor, the individual predispersed substances having an optically brightening effect, and also the shading dyes, dispersants and / or other additives used, if appropriate, can be metered separately.

In the process according to the invention, however, optically brightening compounds and optionally one or more of the shading dyes, dispersants and other additives described above are preferably used as formulations brought. The present invention therefore furthermore relates to formulations comprising

20 to 80% by weight, based in each case on the sum of all brightening 5 compounds, of compound I,

20 to 80% by weight of at least one compound II,

0 to 30% by weight of at least one compound of the formula III and 10 each optionally

one or more blue or violet shading dyes from the class of the anthraquinones, azo dyes, methine dyes, violanthrones or indanthrones, 15 one or more dispersants, water and other additives.

Formulations according to the invention generally contain water 20 and, based in each case on the weight of the preparation, 1 to 40% by weight, preferably 3 to 25% by weight, of the mixtures of brightening compounds specified above, optionally 0.001 to 0, 1% by weight of shading dye, optionally 0.5 to 40% by weight of dispersant and 5 to 60% by weight, preferably 5 to 25 52% by weight, of additives.

Another object of the present invention is the use of the formulation according to the invention for lightening textile materials, in particular polyester or polyester mixtures.

The following examples are intended to explain the invention in more detail.

General regulations 35

The isomer distribution was as follows: I trans-cis, 95: 5 mol%; II p, o ', II mp'- II o, o', each over 95 mol% trans, determined in each case by ¹ H-NMR spectroscopy.

40 1. High temperature extraction process

In an autoclave, 10 kg of polyester fabric was placed at 25 ° C in 100 liters of a dyebath containing the total concentration of whitening compounds 45 shown in Table 1, which were individually dispersed in water ("finished") and then added. The bath was then heated to 130 ° C. in the course of 30 minutes and at this temperature for a further 30 minutes Temperature maintained. The tissue was then removed from the bath, rinsed and dried. The optical whiteness was determined according to the CIE for analysis.

For the comparative experiments, a mixture of 50% by weight II o, p 'and 50% by weight 4 b.l.

COOCH-:

4 left

from EP 0 023 026, Table 2.

Table 1 Lightening of polyester fabric with various mixtures of optically brightening compounds after the pull-out process

In the process according to the invention, a stronger effect is achieved with a smaller amount of brightening compounds than in the processes known from the literature. The maximum of brightening effect can also be achieved after the achieve methods according to the invention at lower concentrations of optically brightening substances.

2. Thermosol process

For examples 2.1 to 2.8 according to the invention, polyester fabric was padded at room temperature with an aqueous liquor containing a total of 0.8 g / l of optically brightening compounds of the composition given below. The pH was adjusted to 5.5 with acetic acid. The fleet uptake was 60%. The fabric was then dried at 110 ° C. for 20 s and then fixed at the temperature shown in Table 2 for 30 seconds.

The comparative tests V 2.9 to V 2.12 were carried out analogously, but 0.8 g / 1 liquor was a mixture of 50% by weight II o, p 'and 50% by weight

4 left

from EP 0 023 026, Table 2.

The comparative tests V 2.13 to V 2.16 were carried out analogously to the examples according to the invention, but 1.5 g / l of a mixture of 70% by weight II o, p 'and 30% by weight II o, o' were used.

Table 2 Lightening of polyester fabric with various mixtures of optically brightening compounds by the Thermosol process; Fixation at different temperatures.

In the process according to the invention, a stronger effect was achieved with less or the same amount of optically brightening compounds at the same fixing temperature.

Claims

claims

1. A process for lightening textile materials by treatment with optical brighteners in an aqueous liquor, characterized in that 20 to 80% by weight, based in each case on the sum of all brightening compounds, of the compound I

II P, o '

II P, P ' and 0 to 30% by weight of at least one compound of the general formula III

R

in which R is selected from C ₄ -Cιo-alkyl,

is used, the treatment optionally being carried out in the presence of one or more blue or violet shading dyes from the class of the anthraquinones, azo dyes or methine dyes.

2. The method according to claim 1, characterized in that in addition to 20 to 80 wt .-% of compound I and 0 to 30 wt .-% of a compound of general formula III 20 to 70 wt .-% of compound II p, o 'sets in.

3. The method according to claim 1 or 2, characterized in that in addition to 20 to 80 wt .-% of compound I and 0 to 30 wt .-% of a compound of general formula III 20 to 70 wt .-% of compound II m , p 'begins.

4. The method according to claim 1, characterized in that in addition to 20 to 70 wt .-% of compound I and 0 to 30 wt .-% of a compound of general formula III 20 to 70 wt .-% of compound II p, o 'and 10 to 50 wt .-% of the compound II m, p' is used.

5. The method according to claim 1, characterized in that in addition to 30 to 60 wt .-% of compound I and 0 to 30 wt .-% of a compound of general formula III

30 to 60 wt .-% of the compound II p, o 'and

10 to 30 wt .-% of the compound II uses o, o '.

6. The method according to claim 1, characterized in that in addition to 20 to 50 wt .-% of compound I and 0 to 30 wt .-% of a compound of general formula III

5 20 to 60% by weight of compound II p, o ',

10 to 50 wt .-% of the compound II m, p 'and

10 to 30 wt .-% of the compound II uses o, o '.

7. The method according to any one of the preceding claims, character- 10 indicates that R in compound III is 2-ethylhexyl.

8. The method according to any one of the preceding claims, characterized in that an additional 0.5 to 200 wt .-%, based on the sum of all brightening compounds

15 or more dispersants used.

9. The method according to any one of the preceding claims, characterized in that the textile material is polyester.

20

10. The method according to any one of the preceding claims, characterized in that the textile material is mixtures with 45 to 90 wt .-% polyester.

25 11. Formulations containing

20 to 80% by weight, based in each case on the sum of all brightening compounds, of compound I,

30 20 to 70% by weight of at least one compound II,

0 to 30% by weight of at least one compound of the formula III

as well as optional

35 one or more blue or violet shading dyes from the class of the anthraquinones, azo dyes, methine dyes, violanthrones or indanthrones,

one or more dispersants, water and other additives.

12. Use of formulations according to claim 11 for lightening textile materials.

45