KR20040106453A - Method for brightening textile materials - Google Patents

Abstract

The present invention discloses a method of polishing a fiber material by treating the fiber material with an optical brightener in an aqueous bath. The process of the present invention comprises 20% to 80% by weight of a compound of formula (I) wherein up to 40 mol% may be present in the form of cis isomers, formulas (II m, p ', (II p, o'), (II) using at least 80% to 20% by weight of at least one compound of the formula (II) selected from, o 'and a compound of the formula (II p, p'), and 0% to 30% by weight of the compound of the formula Each weight percent is based on the sum of all gloss compounds). The process is carried out in the presence of one or more tinted blue or purple dyes selected from the class of anthraquinone dyes, azo dyes or methine dyes.

[Wherein R is selected from C ₄ -C ₁₀ -alkyl]

Description

METHOOD FOR BRIGHTENING TEXTILE MATERIALS}

Optical brighteners are of great economic importance as an aid to the textile and plastics industries. Many compounds are known to have the ability to impart a white color to fibers or plastics. However, most of these known compounds also have disadvantages. For example, EP 0 023 026 is known as a compound of formula (1), which can be applied at low temperatures but requires a large amount of product to achieve the desired white effeft. Is limited in efficiency.

Wherein R ¹ and R ² may each be for example hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, alkyl or a number of other radicals, and V is selected from the following groups.

Also known, for example, in 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 It is known to gloss fibers by treating the fibers with distyrylbenzene compounds. References cited in EP-A 0 023 027 and EP-B2 0 030 917, and also in EP-B2 0 030 917, disclose the use of mixtures of two or more dicyanostyrylbenzene compounds for optically brightening polyesters. Proof is explained.

EP 0 023 026 discloses mixtures of optical brighteners containing from 0.05% to 0.95% by weight of at least one of the compounds of formula 2p, and from 0.95% to 0.05% by weight of at least one other compound selected from a variety of different compounds. It is.

[Wherein A is a phenyl group substituted by an ortho-cyano group or a para-cyano group]

The mixture is preferably given as a mixture consisting of a compound of formula 2 p, o 'and a compound of formula 1 or a compound of formula 3b to 4b, or further a compound of formula 5b to 6b.

[Wherein R ¹ and R ² are each cited in hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, C ₁ -C ₉ -alkyl, alkoxy, alkylamino and page 2 14-21 line May be an additional radical of wherein V is as defined above]

[Wherein B is any functional group, R ¹ and R ² are each as defined above, n is any integer, R ³ is selected from hydrogen and C ₁ -C ₄ -alkoxy, R ⁴ Is selected from C ₁ -C ₄ -alkoxy, R ⁵ is selected from, for example, C ₁ -C ₆ -alkyl, and B is preferably any functional group]

[Wherein R ⁶ to R ¹⁰ are each selected from various groups, and V is as defined above]

From many of these embodiments, Table 2 shows, for example, what is essentially a mixture of a compound of formula 2 p, o 'or another isomer with a compound of formula 3c and a derivative of formula 4b.1 or 4b.2 Proof is explained.

The defined brighteners are thus applied by various methods to provide excellent CIE whiteness.

EP-A 0 023 028 contains from 20% to about 100% by weight of the compound of formula 2 p, o 'and 0% by weight to 80% by weight of each compound of formula 2 p, p' and compound of formula 2 o, o ' Mixtures containing 0.05 to 0.95 parts by weight of the mixture, and also containing 0.05 to 0.95 parts by weight of one or more derivatives of formulas 1a and 3a to 6a, are claimed as useful optical brighteners, And compounds of formulas 3a to 6a are basically defined analogously to EP-A 0 023 026.

DE-A 197 32 109 discloses one or more isomers of a derivative of a compound of formula 1a and a compound of formula 2 or a plurality of derivatives of formula 4 below, such as a derivative of formula 5b (see above) A method for optically glossing polyamides or polyurethanes with a mixture consisting of For example, inter alia, mixtures consisting of compounds of the general formula (1a.1) with compounds of the general formula (4b.1) are demonstrated (Examples 19-21).

[Wherein, R ¹ and R ² are independently H or C ₁ -C ₆ -alkyl, A is selected from N and CH, and X is Selected from stilbenzene, styryl or imidazolyl]

The mixture shows a synergistic effect on CIE whiteness and also good lightfastness.

EP-A 0 321 393 describes the use of the compounds of the formula (Ib), and of the compounds of the formula (2) in brightener dispersions. Compounds of Formula 1b or Formula 2 are disclosed by themselves or as specific mixtures, mixtures 1 to 6 (pages 6-7) in the references cited above. In EP-A 0 321 393, as mentioned on page 9, line 18, it is essential to the invention that the mixture contains a copolymer of 2-vinylpyrrolidone and 3-vinylpyrrolidone acid.

[Wherein D is a C ₁ -C ₄ -alkyl group]

EP-A 0 682 145 improves the light resistance of the fibers by treating the fibers with a formulation containing a fluorescent UV absorber, which absorbs wavelengths from 280 nm to 400 nm, and 4,4'-bistriazinylaminosteel. Ben-2,2'-disulfonic acid, 4,4'-diphenylstilbene, 4,4'-distyrylbiphenyl, 4-phenyl-4'-benzoxazylstilbene, stilbenylnaphthotriazole, 4-styrylstilbene, coumarin, pyrazoline, naphthalimide, triazinylpyrene, 2-styrylbenzoxazole or 2-styrylnaphthazole derivatives, benzimidazolebenzofuran, oxanilide derivatives and bis Benzoxazol-2-yl and bisbenzimidazol-2-yl derivatives, for example derivatives of formula 1c or 1d (claim 8).

In the above formula,

Each R ¹⁴ is independently hydrogen or C ₁ -C ₄ -alkyl or tert-butyl or -C (CH ₃ ) ₂ -phenyl or COO-C ₁ -C ₄ -alkyl,

R ¹⁵ and R ¹⁶ are the same or different and are selected from H, C ₁ -C ₄ -alkyl and CH ₂ -CH ₂ -OH,

Each R ¹⁷ is the same or different and is selected from H and SO _3- ,

X is Is selected from

X ¹ is Is selected from.

However, improving light resistance generally depends on other factors that play a role in glossing the fibers.

Bright white is of great economic importance for a wide range of products, for example for fibers and for shaped plastic articles. Many of the mixtures demonstrated above, in particular the examples of EP-A 0 023 026 and EP-A 0 023 028, and also the mixtures proven in the examples of EP-A 0 682 145, often do not provide sufficient brightness for demanding customers. Not white. Moreover, further performance characteristics still leave room for improvement. In conclusion, it is desirable to be more efficient in that, for economic reasons, it is required to use less than necessary varnishes to achieve comparable or higher effects.

The present invention relates to a method of glossing a fibrous material by treatment with an optical brightener in an aqueous liquid, the method comprising one or more blue or violet tint dyes selected from the class of anthraquinone dyes, azo dyes or methine dyes ( 20% to 80% by weight of a compound of formula (I), in which up to 40 mol% in the optional presence of shading dye) may be present as cis isomers, formulas (II m, p ', (II p, o'), (II) using 80 wt% to 20 wt% of at least one compound of Formula II selected from o, and compounds of Formula II p, p ', and 0 wt% to 30 wt% of at least one compound of Formula III Each percentage is based on the sum of all gloss compounds).

[In the formula, selected from C ₄ -C ₁₀ -alkyl]

The object of the present invention

A method of glossing fibrous materials, which provides very bright white with improved efficiency and otherwise likewise improved performance characteristics,

Preparations for use in methods of glossing textile materials, and

Use for new formulations

To provide.

The inventors have found that this object is achieved by the method defined above.

Suitable fibrous materials for the purposes of the present invention include, for example, fever, silver, yarn, threads, wovens, knits, nonwovens and garments composed of polyester or polyester blends. The fiber material is preferably composed of synthetic polyester or of blends containing 45% to 90% by weight of polyester.

Gloss compounds or optical gloss compounds suitable for the present invention are fluorescent compounds capable of absorbing wavelengths in the range of 280 nm to 400 nm and emitting more wavelengths. Examples include stilbene, distyrylbenzene, diphenyldistyryl, triazinyl, benzoxazole, bisbenzoxazole, bisbenzoxazolylthiophene, bisbenzoxazolylnaphthalene, pyrene, coumarin and naphthalene peridicarboxamide Included. Gloss compound or optical gloss compound means in particular a gloss compound or optical gloss compound of formulas (I), (II) and (III). The weight percentages are then based on the sum of the gloss compounds unless expressly stated otherwise.

As used herein, the term "aqueous liquor" should also be understood as a liquid that contains not only water but also one or more additional solvents, for example 40% by volume or less of alcohol, such as ethanol, as a major component. . The pH of the liquid used according to the invention is preferably in the range of 3 to 12, more preferably in the range of 3 to 8.

The process defined above is 20% to 80% by weight, preferably 20% to 70% by weight, more preferably 30 to 40% by weight of the compound of formula (I) in which up to 40 mol% may be present in the form of the corresponding cis isomers 80% to 20% by weight of at least one compound of formula II selected from compounds of formula II m, p ', formula II p, o', formula II o, o 'and formula II p, p' By weight, and 0-30% by weight of the compound of the formula III.

[Wherein R is C ₄ -C ₁₀ -alkyl such as n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2 -Dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl, n-butyl and 2 Preference is given to ethylhexyl.

20% to 80% by weight of the compound of formula (I) as well as 0% to 30% by weight of the compound of formula (III) and 20% to about 70% by weight of each of at least one compound of formula (II) p, o 'or m, p' It is preferable to use.

20% to 70% by weight of the compound of Formula I and 0% to 30% by weight of the compound of Formula III as well as 20% to 70% by weight of the compound of Formula II p, o 'and 10% of the compound of Formula m, p' Particular preference is given to using% to 50% by weight.

In another particularly preferred embodiment 30% to 50% by weight of the compound of formula I and 0% to 30% by weight of the compound of formula III as well as 30% to 60% by weight of the compound of formula II p, o ', formula II 10 to 30 weight percent of a compound of o, o 'and optionally 10 to 50 weight percent of a compound of formula II m, p'.

Compounds of formula I are synthesized as described, for example, in US 2,842,545, US 2,875,089 or US 3,147,253. For the purposes of the present invention, it is also to be understood that the definition of formula (I) contains from 0.2 mol% to 40 mol%, preferably from 0.7 mol% to 20 mol%, of the isomeric mixture. The fraction of cis isomers can be determined by spectroscopic or chromatographic methods familiar to those skilled in the art. See, eg, J. Chromat. 1967, 27 (2), 413-22.

Dicyanostyryl compounds of the formula II p, o ', II m, p', II p, p 'and II o, o' are used in the form of the trans isomers. These compounds typically contain from 0.01 mol% to 10 mol%, preferably from 0.1 mol% to 5 mol% of isomers having at least one cis-type double bond, and fractions of the cis-isomers are known to those skilled in the art. By spectroscopic methods. These compounds can be obtained from terephthaldicarboxaldehyde and the corresponding cyinobenzyl phosphorylide by a twofold witting reaction.

In the practice of the process according to the invention, it may be advantageous to add one or more blue or violet tint dyes. Useful color dyes generally belong to the classes of disperse dyes and vat dyes. These dyes are common names. C.I. (Color Index) lists dyes such as disperse dye blue or disperse dye violet or tendonate dye blue or tendonate dye violet.

Particularly suitable are blue dyes belonging to the class of anthraquinone dyes, azo dyes or methine dyes.

Dyes belonging to the class of anthraquinone dyes correspond for example to the compounds of the formulas A1 to A4.

In the above formula,

Z ¹ is C ₁ -C ₁₀ -alkyl with or without one or two oxygen atoms in the ether function and with or without C ₁ -C ₄ -alkoxycarbonyl or cyano substituents, or C ₁ Phenyl with or without -C ₄ -alkoxycarbonyl substituent,

Z ² is C ₁ -C ₈ -alkyl with or without one or two oxygen atoms in the ether function and with or without hydroxyl, phenyl or C ₁ -C ₄ -alkoxycarbonyl substituents,

Z ³ is oxygen or HH,

Z ⁴ is hydrogen, C ₁ -C ₁₀ -alkyl with or without one or two oxygen atoms in the ether function and with or without CC-alkoxycarbonyl or cyano substituents, or C ₁ -C Phenyl with or without ₄ -alkoxycarbonyl substituent,

Z ⁵ is hydrogen or halogen or CN,

Z ⁵ is hydrogen or nitro,

Z ⁷ is C ₂ -C ₆ -alkylene or phenylene.

The dyes mentioned above are generally known dyes. Dyes of formula 2A are described, for example, in US-A 2, 628, 963, US-A 3,835,154, DE-A 12 66 425 or DE-A 20 16 794. Dyes corresponding to formulas A1, A3 and A4 are known, for example, from K. Venkataraman, "The Chemistry of Synthetic Dyes", Volume 3, pages 391-423,1970.

Suitable azo dyes are specifically monoazo dyes having aniline or heterocyclic series diazo components and monoazo dyes having aniline or heterocyclic coupling components.

Suitable heterocycles from which the diazo component is derived are derived, for example, from the class of aminothiophenes, aminothiazoles, aminoisoitazoles, aminothiadiazoles or aminobenzisothiazoles.

Suitable heterocycles from which the coupling component is derived are derived, for example, from the class of thiazoles or diaminopyridine.

More specifically, such azo dyes correspond to one of the compounds of the formulas B1 to B7.

In the above formula,

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

Z ⁹ is hydrogen, halogen, C ₁ -C ₈ -alkoxy, phenoxy, C ₁ -C ₆ -alkylthio, phenylthio, C ₁ -C ₄ -alkylsulfonyl, phenylsulfonyl, methyl, or chlorine, meth Oxy, ethoxy or methyl substituted or unsubstituted phenyl,

Z ¹⁰ is cyano, C ₁ -C ₆ -alkoxycarbonyl, carbamoyl, or mono-C ₁ -C ₄ -with or without one or two oxygen atoms in the ether functional portion of the alkyl chain. Or di-C ₁ -C ₄ -alkylcarbamoyl,

Z ¹¹ and Z ¹² are independently or without one or two oxygen atoms in the ether function, hydroxyl, cyano, chlorine, phenyl, C ₁ -C ₆ -alkoxy, C ₁ -C _6- alkoxycarbonyl, C ₁ -C ₆ - alkoxycarbonyloxy or mono- -C ₁ -C ₆ - or di -C ₁ -C ₆ - alkylamino carbonyloxy substituted or are part Genie boatman C ₁ -C ₈ - alkyl, and when the alkenyl group, or Z ¹¹ and not in the case of Z ¹² H, -, or C ₃ -C ₄

Y ¹ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, chlorine, bromine or a radical of the formula —NH—CO—R ¹¹ , wherein R ¹¹ is C ₁ -C ₄ -alkoxy, cyan No, hydroxyl, chlorine or C ₁ -C ₄ -alkyl, or C ₂ -C ₃ -alkenyl, with or without C ₁ -C ₄ -alkanoyloxy substituents,

Y ² is hydrogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,

Z ¹³ is C ₁ -C ₄ -alkoxy substituted or unsubstituted C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy substituted or unsubstituted benzyl, chlorine, methyl, methoxy or ethoxy substituted or unsubstituted Phenyl, 2-pyridyl or 3-pyridyl,

Z ¹⁴ is cyano, chlorine or bromine,

Z ¹⁵ is C ₁ -C ₄ -alkoxy or acetylamino substituted or unsubstituted thienyl or pyridyl,

Z ¹⁶ is cyano, chlorine or bromine.

The azo dyes mentioned above are known per se. Dyes of formulas B1 and B2 are described, for example, in US 5,283,326 or US 5,145,952, 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 Discloses dyes of formula B3. US 5,216,139 discloses dyes of formula B4. US 5,132,412 discloses dyes of the type B5. Dyes of formulas B6 and B7 are described, for example, 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, pp 444-447. Or by the methods described in these documents.

Suitable methine dyes correspond, for example, to compounds of formula (C).

In the above formula,

Y ³ is nitrogen or CH,

Z ¹⁸ is C ₁ -C ₂₀ -alkyl, substituted or unsubstituted phenyl or hydroxyl, with or without substituents and with or without one or more oxygen atoms in the ether function.

Z ¹⁹ is a 5-membered aromatic heterocyclic radical,

Z ²⁰ is hydrogen, cyano, carbamoyl, carboxyl or C ₁ -C ₄ -alkoxycarbonyl,

Z ²¹ is oxygen or a radical of the formula C (CN) ₂ , C (CN) COOZ ²³ or (COOZ ²³ ) ₂ , wherein Z ²³ is in each case interrupted or interrupted by one or two oxygen atoms in the ether function Unsubstituted C ₁ -C ₈ -alkyl,

Z ²² is hydrogen or C ₁ -C ₄ -alkyl.

Substituted alkyl in formula (C) is, for example, phenyl, C ₁ -C ₄ -alkylphenyl, C ₁ -C ₄ -alkoxyphenyl, halophenyl, C ₁ -C ₈ -alkanoyloxy, C ₁ -C ₈ -alkylaminocarbonyloxy, C ₁ -C ₂₀ -alkoxycarbonyl, C ₁ -C ₂₀ -alkoxycarbonyloxy (alkyl in the last two radicals mentioned is one to one in the ether function) Four oxygen atoms are optionally interrupted and / or substituted by phenyl or phenoxy), halogen, hydroxyl or cyano may be retained as a substituent. The number of substituents in substituted alkyl is generally one or two.

The alkyl radical represented by the formula (C) with an oxygen atom interposed in the ether functional moiety is an alkyl radical having 1-4 oxygen atoms, especially one or two oxygen atoms intercalated in the ether functional moiety, unless otherwise specified. It is preferable.

Substituted phenyl or pyridyl represented by the formula (C) may have, for example, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy, halogen, in particular chlorine or bromine, or carbonyl as substituents. The number of substituents in substituted phenyl or pyridyl is generally from 1 to 3.

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

Important Z ¹⁹ radicals include, for example, radicals of the formulas C1 to C4.

In the above formula,

m is 0 or 1,

Z ²⁴ and Z ²⁵ are the same or different and are each independently hydrogen, C ₁ -C ₂₀ -alkyl, substituted or unsubstituted phenyl, with or without substituents and interrupted by one or more oxygen atoms in the ether function; or In combination with an intervening nitrogen atom to form a 5- or 6-membered saturated heterocyclic radical with or without additional heteroatoms,

Z ²⁶ is hydrogen, halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy substituted or unsubstituted phenyl, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -Alkoxy substituted or unsubstituted benzyl, cyclohexyl, thienyl, hydroxyl or C ₁ -C ₈ -monoalkylamino,

Each Z ²⁷ is the same or different and is independently hydrogen, hydroxyl, phenyl or C ₁ -C ₄ -alkylphenyl substituted or unsubstituted C ₁ -C ₈ -alkyl, phenyl or C ₁ -C ₄ -alkylphenyl Substituted or unsubstituted C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkanoylamino, C ₁ -C ₈ -alkylsulfonylamino or mono-C ₁ -C ₈ -or di-C ₁ -C ₈ -Alkylaminosulfonylamino,

Z ²⁸ is cyano, carbamoyl, mono-C ₁ -C ₈ -or di-C ₁ -C ₈ -alkylcarbamoyl, C ₁ -C ₈ -alkoxycarbonyl, or substituted or unsubstituted phenyl ,

Z ²⁹ is halogen, hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted Or unsubstituted phenyl, or thienyl.

Such methine dyes are described, for example, in the conventional German patent application DE-A 44 03 083.

Of particular interest is the process of treating the polyester or polyester blend in the presence of at least one blue or violet tint dye selected from the class of anthraquinone-based dyes, in particular the dyes of the formula (A).

The method is named C.I. It is carried out technically very well when carried out in the presence of a dye of formula A 3.1, also known as dispersion purple 28 (6112).

The gloss compound is used according to the invention in an amount of 0.005% to 0.07% by weight, preferably 0.02% to 0.05% by weight, based on the weight of the fiber material to be polished. It provides a white effect that is comparable to or even better than that provided by it.

The amount of blue or purple tint dye is generally present in the range of 0.00005% to 0.02% by weight, preferably 0.005% to 0.002% by weight, based on the weight of the fiber material to be polished. However, the use of the color dye is not essential.

Fiber materials are generally polished by an exhaust process or a thermosol prcoess.

The consumption process is carried out mostly in aqueous liquid at 90-135 ° C., usually about 130 ° C. For applications above 100 ° C, use autoclaves, high pressure equipment or high pressure equipment. The thermosol process is carried out at atmospheric pressure.

The consuming process generally comprises a fiber material to be polished, containing an optical gloss compound, optionally a blue or purple tint dye or mixtures thereof and optionally additives such as dispersants, carboxylic acids or alkali donors and usually having a pH in the range of 3-12. , Preferably by introducing at 10 ° C. to 35 ° C. in an aqueous liquid in the range of 3 to 10. The liquid ratio (weight ratio of liquid to fiber material) is in the range from 3: 1 to 40: 1, preferably in the range from 5: 1 to 20: 1. The batch is then heated to 90-130 ° C., preferably 95-100 ° C., over 15 to 30 minutes and held at that temperature for 15 to 60 minutes. The fiber material is then cleaned and dried.

In a thermosol process, the fiber material to be polished is typically pad-mangled with an aqueous liquid containing an optical gloss material, optionally a blue or purple tint dye or mixtures thereof and optionally additives (see above). Wet pickups are generally in the range of 50% to 100%. The fiber material is then dried and fixed at 150 ° C. to 200 ° C. for 5 to 60 seconds.

The dispersant used is preferably colorless and stable to yellowing up to at least 210 ° C.

Examples of very suitable dispersants are anionic or nonionic dispersants, especially anionic or nonionic dispersants derived from the class of ethylene oxide adducts with fatty alcohols, higher fatty acids or alkylphenols, or ethylenediamine-ethylene oxide-propylene oxide adducts. There is.

Particularly preferred dispersants include aliphatic or alkylaromatic hydroxy, amino or aminohydroxy compounds, with the brand names Synperonic® and Ukanil®, Dehypon®, Neopol® ethoxyl. There are alkoxylation products commercially available under Rate, Emulan (R), Lutensol (R), Plurafac (R) and Pluronic (R) or Elfapur (R). Especially preferred are alkoxylated phenols. Very preferred dispersants are alkoxylated phenols of the formulas IV and V or mixtures thereof.

In the above formula,

a and b are

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

b is in the range of 20 to 80, preferably in the range of 35 to 125, provided that b is an integer such that

M is an alkali metal, preferably Na or K, more preferably Na,

d is 0 or 1;

The preparation of compounds of formulas IV and V is known and the phenols of formulas VI and VII are reacted with propylene oxide, respectively, followed by subsequent reaction with ethylene oxide, or oxidation of compounds of formulas VI and VII, respectively. It is advantageous to carry out by reacting with ethylene. It is then possible to convert all of these adducts to all or part of the acid sulfuric acid esters with chlorosulfonic acid or sulfur trioxide and neutralize the resulting acid esters with alkalis.

The phenols of formulas VI and VII can be obtained by reacting bisphenol A (2,2 '-(p, p'-bishydroxydiphenyl) propane) or phenol with 4 or 2 moles of styrene, respectively, in the presence of an acid as a catalyst. have. The phenols of formulas VI and VII are reacted with propylene oxide first in the presence of an acidic or basic catalyst, for example NaOCH ₃ or SbCl ₅ , and then with ethylene oxide, or only with ethylene oxide, where d = 0. Conversion to the corresponding alkoxylation products of respective formulas IV and V. Alkoxylation can be carried out by the process described, for example, in US 2,979,528.

Acid sulfate esters are prepared by reacting the alkoxylation product with chlorosulfuric acid or sulfur trioxide, wherein the amount of chlorosulfuric acid or sulfur trioxide is selected to sulfate all free hydroxyl groups or only a certain percentage of their hydroxyl groups. The latter case results in a mixture of compounds of formula VI or V containing free hydroxyl groups and sulfated hydroxyl groups. For use as a surfactant, the As-synthesized acid ester of sulfuric acid is converted to a water soluble salt. Advantageous acid-soluble salts include alkali metal salts such as sodium salts or potassium salts. Cholosulfonic acid requires 2 equivalents of an alkali compound, and sulfur trioxide requires 1 equivalent of an alkali compound. The alkali compound used is advantageously an aqueous alkali metal hydroxide. The temperature should not exceed 70 ° C on neutralization. The salts obtained can be used in the form of an aqueous solution or alternatively can be separated and used as such in solid form.

Preferred are dispersants of formulas IV and V wherein a is from 0 to 2.5 on average, b is from 25 to 250 on average and d is from 0 to 0.5 on average. Particularly preferred are dispersants of formulas IV and V wherein a is from 0 to 2.5 on average, b is from 25 to 100 on average and d is from 0 to 0.5 on average.

Compounds of formulas (IV) and (V) are known and many representatives are described, for example, in US Pat. No. 4,218,218.

Optionally, additives to be added further include, for example, fungicides or water retention aids commonly used in the textile industry. Optionally further additives include copolymers of N-vinylpyrrolidone and 3-vinylpropionic acid described in EP-A 0 321 393.

Preferred embodiments of the process of the present invention comprise 1% to 40% by weight, preferably 3% to 10% by weight, and 3% by weight of anionic or nonionic dispersant, as well as water, into a particulate mixture of the brightener and color dye To 12% by weight, 1% to 15% by weight of copolymers of N-vinylpyrrolidone with vinyl acetate or vinyl propionate or mixtures thereof, and 1% by weight of additional additives (e.g., moisture retention aids or fungicides) Formulations containing from 25 to 25 weight percent are used, each percentage based on the weight of the formulation.

The process of the present invention provides a very good white effect on the fiber material in the consumption process as well as in the thermosol process. This polished material has very good service fastness.

The aqueous liquids described above can be prepared by separately weighing the individual pre-dispersed optical gloss material and also each or all optionally used color dyes, dispersants and / or other additives.

However, the process of the invention is preferably carried out by applying the optical gloss compound and optionally one or more of the above-mentioned color dyes, dispersants and other additives as a preparation. Thus, the present invention also

20 wt% to about 80 wt% of a compound of Formula I,

20% to 80% by weight of one or more of the compounds of Formula II,

0% to 30% by weight of one or more compounds of Formula IIID

And in each case at least one blue or violet tint dye, at least one dispersant, water and optionally selected from the class of anthraquinone dyes, azo dyes, methine dyes, bioanthrone dyes or indanthrone dyes. Formulations comprising additional additives, each percentage above being based on the sum of all gloss compounds, are provided.

The formulations of the present invention are generally from 1% to 40% by weight, preferably from 3% to 25% by weight, optionally from 0.001% to 0.1% by weight of a pigmented mixture of water and the gloss compound, optionally 0.5% of a dispersant. Wt% to 40 wt%, and also 5 wt% to 60 wt%, preferably 5 wt% to 52 wt% of the additive, each percentage based on the weight of the formulation.

The present invention furthermore provides the use of the preparations according to the invention for the polishing of fibrous materials, in particular polyesters or polyester blends.

The following examples are intended to illustrate the invention.

General description

The isomer distribution is 95: 5 mol% of the trans form: cis for compounds of formula (I) and each trans form for compounds of formula (II p, o ', formula (II m, p', formula o, o '). It was at least 95 mol%, each determined by ¹ H NMR spectroscopy.

1. High pressure consumption process

10 kg of the polyester fabric was immersed at 25 ° C. in 100 liters of the dye bath in the autoclave containing the total concentration of the gloss compounds reported in Table 1 added separately (“finally”) after being dispersed in water. The bath was then heated to 130 ° C. over 30 minutes and held at 130 ° C. for 30 minutes. The fabric was then removed from the bath, washed and dried. Optical CIE whiteness was measured for analysis in each case.

Comparative Example V The test used a mixture consisting of 50% by weight of the compound of formula II o, p 'and 50% by weight of the compound of formula 4b.1, derived from Table 2 of EP 0 023 026, respectively.

TABLE 1

How to polish a polyester fabric with a mixture of optical brightening compounds by a consuming process

The method of the invention provided in each case a stronger effect than the prior art methods while using less amounts of gloss compounds. Similarly, the method of the present invention achieved the maximum gloss effect at lower concentrations of the optical gloss material.

2. Thermosol process

Examples 2.1 to 2.8 of the present invention were carried out by pad mangle treatment of the polyester crop at room temperature using an aqueous liquid containing a total of 0.8 g / l of the optical brightening compound of the composition reported below. pH was adjusted to 5.5 using acetic acid. Wet pickup was 60%. The fabric was then dried at 110 ° C. for 20 seconds and then fixed for 30 seconds at the temperatures shown in Table 2 below.

Comparative Examples V 2.9 to V 2.12 were prepared in a similar manner, with the exception of 50% by weight of compounds of formula II o, p 'and 50% by weight of compounds of formula 4b.1 derived from Table 2 of EP 0 023 026 A mixture consisting of 0.8 g / l of liquid was used.

Comparative Examples V.13 to V 2.16 were carried out similarly to the examples of the present invention, except that a mixture of 70% by weight of the compound of formula II o, p 'and 30% by weight of the compound of o, o' of formula II 1.5 g / l was used.

TABLE 2

Method for polishing polyester fabrics with various mixtures of optical components by thermosol process and fixing at different temperatures

The method of the present invention provided a stronger effect at the same fixed temperature when using the same or less amount of optical gloss compound.

Claims (12)

20% by weight of a compound of formula (I) in which, in the presence of one or more blue or purple tint dyes selected from the class of anthraquinone dyes, azo dyes and methine dyes, up to 40 mol% may be present in the form of cis isomers To 80% by weight, from 80% to 20% by weight of at least one compound of formula II selected from compounds of formula II m, p ', formula II p, o', formula II o, o 'and formula II p, p' Such optics in an aqueous liquid, including the use of 0% to 30% by weight of one or more of the compounds of Formula III, wherein each percentage is based on the sum of all glossing compounds To polish fiber materials with a varnish: [Wherein R is selected from C ₄ -C ₁₀ -alkyl] The process according to claim 1, wherein 20% to 80% by weight of the compound of the formula (I) and 0% to 30% by weight of the compound of the formula (III) are used as well as 20% to about 70% by weight of the compound of the formula (II) p, o ' Way. A compound according to claim 1, wherein from 20% to 80% by weight of the compound of formula (I) and from 0% to 30% by weight of compound of formula (III) as well as from 20% to about 70% by weight of compound of formula (II m, p ') How to use%. A compound according to claim 1, wherein 20% to 70% by weight of the compound of formula I and 0% to 30% by weight of the compound of formula III as well as 20% to about 70% by weight of the compound of formula II p, o 'and 10 to 50 weight percent of a compound of m, p '. A compound according to claim 1, wherein 30% to 60% by weight of the compound of formula I and 0% to 30% by weight of the compound of formula III as well as 30% to about 60% by weight of the compound of formula II p, o 'and 10 to 30% by weight of o, o 'compound. A compound according to claim 1, wherein 20% to 50% by weight of the compound of formula I and 0% to 30% by weight of the compound of formula III as well as 20% to about 60% by weight of the compound of formula II p, o ', 10 to 50 weight percent of a compound of m, p 'and 10 to 30 weight percent of a compound of formula II o, o'. The method of claim 1, wherein R in the compound of Formula III is 2-ethylhexyl. 8. The process according to claim 1, further comprising from 0.5% to 200% by weight of at least one dispersant, based on the sum of all the gloss compounds. 9. The method of claim 1, wherein the fibrous material is polyester. The method according to any one of claims 1 to 9. The fiber material is a blend containing 45% to 90% by weight of polyester. 20% to 80% by weight of the compound of formula I, 20% to 70% by weight of one or more of the compounds of Formula II, 0% to 30% by weight of one or more compounds of Formula III (The respective percentages are based on the sum of all the gloss compounds), and in each case optionally also an anthraquinone dye, an azo dye, a methane dye, a bioanthrone dye or an indanthrone dye A formulation comprising at least one blue or purple tint dye selected from the class of, at least one dispersant, water and additional additives. Use of the formulation of Claim 11 for glossing a fibrous material.