DE10105143A1 - Process for UV protective equipment of textile material - Google Patents

Abstract

The invention relates to a method for providing textile material with UV protection, whereby (a) zinc oxide and/or titanium oxide are applied to the textile material as constituent A, and (b) at least one organic UV absorber is applied to the textile material as constituent B. Constituent B preferably contains at least one compound from the group consisting of phenylbenzotriazoles, dibenzoylmethanes, p-aminobenzoic acid esters, cinnamic acid esters, salicylic acid esters, nitrogen-free 2-hydroxybenzophenones, phenylbenzimidazoles, acrylates, diarylbutadienes, amino-substituted hydroxybenzophenones, and triazines.

Description

The invention relates to a method for UV protective finishing of textile material, Textile detergent, laundry treatment and laundry care formulations, Equipment for UV protective equipment of textile material, the so-equipped textile material itself and the use of zinc oxide and / or titanium dioxide together with organic UV absorbers.

The harmful effects of UV radiation from sunlight on human beings Skin is not limited to premature aging and the formation of Skin erythema (reddening of the skin, sunburn). If the skin becomes too long and too intense Exposed to UV radiation, the risk of developing skin cancer is also increased. He is primarily responsible for the reddening of the skin and the increased risk of skin cancer UV-B portion of UV radiation, d. H. the range from approx. 280 to approx. 315 nm The maximum erythema effect is 308 nm.

Textiles scatter or absorb UV radiation and thus protect as physical Barrier the skin from the damaging effects of sunlight ("textile Skin protection "). However, the skin protecting effect of the textiles is due to many factors such as type of fiber, fabric construction, fabric weight, color, moisture content or type of Equipment or finishing dependent. Summer clothing in the form of light and light cotton textiles only a weak and therefore inadequate Protection from UV radiation.

Too high a dose of UV radiation can not only cause skin damage, it is also largely responsible for the fading of colored light induced by sunlight Textiles. Therefore there is a high level of interest, both in colored textiles and in protect human skin from the damaging effects of UV radiation.  

So far, mainly optical brighteners have been used for refinement and protection the textiles themselves and also used for textile skin protection, especially those based on Stilbene and triazine bases, as in EP-A 682 145, GB-A 2 313 375 or EP-A 728 749 described. However, the effectiveness of the agents is still in need of improvement have a number of disadvantages. The main disadvantages are their bad ones Formulation and its lack of solubility in the respective application medium.

From WO 97/44422 it is known that sunscreens, in particular from the group phenylbenzotriazoles, dibenzoylmethanes, p-aminobenzoic acid esters, cinnamic acid esters, Salicylic acid esters, nitrogen-free 2-hydroxybenzophenones, phenylbenzimidazoles and 2- Cyano-3,3-diphenylacrylic acid esters and mixtures thereof - but without any indication to the respective mixing ratios - dyed textile material before fading protect the color. In WO 96/03486 essentially the same Sunscreen, as they are called in WO 97/44422, as well Means for protecting dyed textile material from color fading described. However, these agents are still effective in need of improvement and have a number of disadvantages. An essential one The disadvantage is that the UV stability of the above-mentioned agents is often too low.

The incorporation of pigments such as titanium dioxide or zinc oxide in fibers is a problem Means to provide textiles made from these fibers with UV protection. Especially Synthetic fibers made of polyamide, polyester or polyacrylonitrile are suitable for this type of UV Protective gear. Cellulose fibers are not very suitable for this.

JP 03/277699 describes solid detergents, especially soaps, containing zinc oxide from 0.1 to 15% by weight. The soaps show good UV absorption and have one deodorant effect.

WO 98/42909 describes the UV protective finish of textile fabrics Treatment with inorganic particles that absorb, reflect or reflect UV radiation can spread in combination with a binder. The application of these particles can also done while washing textiles.

The object of the present invention is to improve its effect and to provide more photostable UV absorber systems.  

The task is solved by a process for UV protection of textile material, in which one

• a) zinc oxide and / or titanium oxide as component A and
• b) one or more organic UV absorbers as component B.

onto the textile material.

It was surprisingly found that the combined use of organic UV Absorbers and inorganic pigments made of zinc oxide and / or titanium dioxide Textile finishing agents, detergents or laundry care products to a more effective UV protection of textiles treated with these agents leads as the only one Use of organic UV absorbers or inorganic pigments. You get both a higher and more stable protection of the skin from damaging UV radiation, as Even with colored fabrics, increased protection against UV-induced Color fading.

Zinc oxide and / or titanium dioxide are used as component A as UV radiation absorbent inorganic pigments used. Component A can be made of zinc oxide or Titanium dioxide alone or from mixtures of both pigments.

Titanium dioxide can be used in its three modifications rutile, anatase or brookite are preferably used as rutile. The particle size is generally from 0.01 to 100 µm, preferably from 0.02 to 0.25 µm.

Zinc oxide is generally used with a particle size of 0.01 to 100 microns. The particle size is preferably in the range from 0.02 to 2 μm, particularly preferably in the range of 0.08 to 0.25 µm.

The titanium dioxide and zinc oxide pigment particles can have a passivation layer have inorganic oxides, in particular of silicon dioxide or aluminum oxide. The pigment surface can also be treated with organic compounds or Silicones are specifically hydrophilized or hydrophobized. For surface modification For example, amines and cationic polymers such as amino groups are used containing polymers, polyols, organophosphates, alkyl phthalates, stearic acid, Lauric acid or silicone oils.  

For example:
Uvinul® TiO ₂ (from BASF AG),
Z-COTE® (from BASF AG) and
Z-COTE HP1® (from BASF AG).

Commercially available sunscreens can be used as component B, which have at least one UV absorption maximum in the range from 280 to 450 nm. In a preferred embodiment, component B contains those compounds which have at least one UV absorption maximum in the range from 290 to 375 nm. In a further preferred embodiment, component (B) contains compounds which have at least one UV absorption maximum in the range from 280 to 315 nm (UV-B range) with an E ¹ ₁ value of at least 200, in particular at least 250, and have at least one UV absorption maximum in the range from 315 to 400 nm (UV-A range) with an E ¹ ₁ value of at least 200, in particular of at least 250.

Organic UV absorbers (B) have one or more in the UV absorption spectrum Gangs on. The UV absorption maxima here are those for the corresponding local ones or absolute maxima in the UV spectrum of the band belonging to the respective compound, measured in conventional organic solvents such as dichloromethane or methanol Room temperature, to understand.

The E ¹ ₁ value denotes the absorbance of the organic UV absorber (B), which is measured in solution at a concentration of 1% by weight and a layer thickness of 1 cm. Dichloromethane is usually used as the solvent, the use of other solvents customary for such UV measurements does not produce fundamentally different values.

In a further preferred embodiment, the mixture according to the invention contains those organic UV absorbers as component (B) which contain an n-octanol / water Distribution coefficients log P of at least 1.9, in particular of at least 2.5 all of at least 3.3. Log P can be determined or calculated experimentally become. Both procedures are described in Chemical Reviews Volume 71, No. 5, pages 52-5-616 (1971).  

Organic UV absorbers (B) which are selected from the group consisting of are preferably used

• A) phenylbenzotriazoles,
• B) dibenzoylmethanes,
• C) esters of p-aminobenzoic acid,
• D) esters of cinnamic acid,
• E) esters of salicylic acid,
• F) nitrogen-free 2-hydroxybenzophenones,
• G) Phenylbenzimidazolesulphonic,
• H) acrylates,
• I) diarylbutadienes,
• J) amino-substituted hydroxybenzophenones and
• K) triazines

are selected.

Typical UV-absorbing phenylbenzotriazoles (I) are:
2,2'-hydroxy-5-methylphenylbenzotriazole,
2,2'-hydroxy-5-tert-octylphenylbenzotriazol,
2-hydroxy-3-sec-butyl-5-tert-butylbenzotriazole (Tinuvin® 350),
2-hydroxy-3-dodecyl-5-methylphenylbenzotriazole (Tinuvin® 571),
2- (2H-benzotriazol-2-yl) -4-methylphenol (Tinuvin® P),
2- (2H-benzotriazol-2-yl) -4-n-octylphenyl (Tinuvin® 329),
2- (2H-benzotriazol-2-yl) -4,6-di (2'-phenylisopropyl) phenol (Tinuvin® 234),
2- (2H-benzotriazol-2-yl) -4,6-di (tert-butyl) phenol (Tinuvin® 320),
2- (6-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol (Tinuvin® 326),
2- (6-chloro-2H-benzotriazol-2-yl) -2,6-di-tert-butylphenol (Tinuvin® 327),
2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -2H-benzotriazole (Tinuvin® 328),
Mixture of β- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid, polyoxyethylene glycol ester and polyoxyethylene glycol to β- [3- (2H-benzotriazol-2-yl) -5- tert-butyl-4-hydroxyphenyl] propionate with an average molecular weight <600 (Tinuvin® 1130),
Cocoyl-2- [2'-hydroxy-3 '- (cocoyldimethylbutanoat) -5'-methylphenyl] benzotriazole,
Cocoyl-3- [3 '- (2H-benzotriazol-2'-yl) -5-tert-butyl-4'-hydroxyphenyl] propionate,
2,2'-methylene bis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl)] phenol (Tinuvin® 360),
2- (2H-1,2,3-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- {1,3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxanyl} propyl) phenol.

Typical UV-absorbing dibenzoylmethanes (II) are:
3- (4-isopropylphenyl) -3-phenylpropane-1,3-dione (Eusolex® 8020),
1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (Uvinul® BMBM),
1,3-bis (4-methoxyphenyl) propane-1,3-dione.

Typical UV-absorbing esters of p-aminobenzoic acid (III) are:
Ethyl 4-bis (hydroxypropyl) aminobenzoate (Amerscheen® P),
2,3-dihydroxypropyl-4-aminobenzoate (Nipa® GMPA),
Menthyl 2-aminobenzoate (Sunarome® UVA),
2-ethylhexyl-4-dimethylaminobenzoate (Escalol® 507),
Amyl 4-dimethylaminobenzoate,
Ethyl 4-dimethylaminobenzoate,
Butyl 4-dimethylaminobenzoate,
Octyl 4-dimethylaminobenzoate,
Lauryl-4-dimethylaminobenzoate,
Oleyl 4-dimethylaminobenzoate,
4-bis- (polyethoxy) -4-aminobenzoic acid polyethoxyethyl ester (Uvinul® P-25),
N-propoxylated ethyl 4-aminobenzoate.

Typical UV-absorbing esters of cinnamic acid (IV) are:
2-ethylhexyl-4-methoxycinnamate (Uvinul® MC80, Parsol® MCX),
2-ethoxyethyl 4-methoxycinnamate,
Propyl 4-methoxycinnamate,
iso-amyl 4-methoxycinnamate,
Cyclohexyl-4-methoxycinnamate,
iso-propyl-4-methoxycinnamate,
octyl,
Ethyl-4-isopropyl cinnamate,
Ethyl-α-cyano-β-phenylcinnamate,
2-ethylhexyl α-cyano-β-phenylcinnamate.

Typical UV-absorbing esters of salicylic acid (V) are:
2-ethylhexyl salicylate (Sunarome® WMO),
3,3,5-trimethylcyclohexyl 2-hydroxybenzoate,
3,3,5-trimethylcyclohexyl 2-acetamido,
2-Ethylhexyl-2- (4-phenylbenzoyl) benzoate,
4-isopropylbenzyl,
amyl salicylate,
menthyl,
homomethyl salicylate,
phenyl salicylate,
benzyl salicylate,
iso-Decylsalicylat.

Typical UV-absorbing nitrogen-free 2-hydroxybenzophenones (VI) are:
2-hydroxy-4-methoxybenzophenone (Uvinul® M40),
2,2'-dihydroxy-4-methoxybenzophenone (Spectra-Sorb® UV-24),
2,4-dihydroxybenzophenone (Uvinul® 3000),
2,2 ', 4,4'-tetrahydroxybenzophenone (Uvinul® D-50),
2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinul® D-49),
2,2-dihydroxy-4,4-dimethoxybenzophenone (Uvinul® 3049),
2-hydroxy-4- (2-ethylhexyloxy) benzophenone,
2-hydroxy-4- (n-octyloxy) benzophenone (Uvinul® 3008),
2-hydroxy-4-methoxy-4'-methylbenzophenone (Mexenone®),
2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate,
2-hydroxy-3-carboxybenzophenone,
Benzophenone-3-cocoylacetatether,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (Uvinul® MS 40) and its sodium salt,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bissulfonic acid and its sodium salt (Uvinul® DS 49).

Typical UV-absorbing phenylbenzimidazoles (VII) are:
2-phenylbenzimidazole-5-sulfonic acid (Eusolex® 232) and its potassium, sodium and triethanolamine salts,
2- [5,6-disulfo (1H-benzimidazol-2-yl) phenyl] -1H-benzimidazole-5,6-disulfonic acid.

Typical UV-absorbing various acrylates (VIII) are:
3-imidazol-4-yl-acrylic acid,
3-imidazol-4-yl-acrylic acid ethyl ester,
2-cyano-3- (4-methoxyphenyl) acrylic acid,
2-cyano-3- (4-methoxyphenyl) acrylsäurehexylester.

Preferred acrylates are C ₆ to C ₁₈ alkyl esters or C ₅ to C ₈ cycloalkyl esters of 2-cyano-3,3-diphenylacrylic acid. The C ₆ to C ₁₈ alcohol residue in the cyano-3,3-diphenylacrylic acid esters can be linear or mono- or polydranched, it can be of natural or synthetic origin. Such alcohols can be, for example, fatty alcohols, oxo alcohols, Ziegler alcohols or Guerbet alcohols. Typical examples of such compounds are n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl or eicosyl ester. Unsaturated alcohol residues such as the oleyl, linolyl or linolenyl residue can also occur. Mixtures of such esters can also be present.

As C ₅ - to C ₈ -cycloalkanol residues in the cyano-3,3-diphenylacrylic acid esters are, for example, cyclopentyl, 2- or 3-methylcyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl, dimethylcyclohexyl, cycloheptyl or cyclooctyl radicals into consideration.

Linear or mono- or poly-branched C ₈ to C ₁₃ alkyl esters of 2-cyano-3,3-diphenylacrylic acid are preferred. The corresponding 2-ethylhexyl ester is commercially available as Uvinul® N-539 T from BASF Aktiengesellschaft.

Typical UV-absorbing diarylbutadienes (IX) are in particular 4,4-diarylbutadienes of the formula (1), as described in DE-A 198 28 463 for cosmetic and pharmaceutical preparations:

in which the diene system in the Z, Z-; Z, E; E, Z or E, E configuration or a mixture thereof and in which the variables have the following meaning independently of one another:
R ¹ and R ^{2 are} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₁ -C ₁₂ alkoxy, C ₁ - C ₂₀ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino, C ₁ -C ₁₂ dialkylamino, aryl, heteroaryl, optionally substituted, and water-solubilizing substituents selected from the group consisting of carboxylate, sulfonate or ammonium radicals;
R ^{3 is} hydrogen, COOR ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN;
R ⁴ COOR ⁶ , COR ⁶ , CONR ⁵ R ⁶ ;
R ^{5 is} hydrogen, [X] _o -R ⁷ , C ₁ -C ₆ alkylene-SO ₃ Y, C ₁ -C ₆ alkylene-PO ₃ Y, C ₁ -C ₆ alkylene- N (R ⁸ ) ₃ ⁺ A ^- ;
R ⁶ [X] _o -R ⁷ , C ₁ -C ₆ alkylene-SO ₃ Y, C ₁ -C ₆ alkylene-PO ₃ Y, C ₁ -C ₆ alkylene-N (R ⁸ ) ₃ ⁺ A ^- ;
X -CH ₂ -CH ₂ -Z-, -CH ₂ -CH ₂ -CH ₂ -Z-, -CH (CH ₃ ) -CH ₂ -Z-, -CH ₂ -CH ₂ -CH ₂ -CH ₂ - Z-, -CH ₂ - CH (CH ₂ -CH ₃ ) -Z-;
A Cl, Br, J, SO ₄ R ⁹ ;
Y is hydrogen, Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Li ⁺ , Al ³⁺ , N (R ⁸ ) ₄ ⁺ ;
ZO, NH;
R ⁷ and R ^{8 are} hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₆ acyl;
R ^{9 is} hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl;
n 1 to 3;
o 1 to 150.

With regard to the further specification of the structures of the 4,4-diarylbutadienes of the formula (1) and examples of such compounds (1) is expressly based on the disclosure of the DE-A 198 28 463. As a typical example of a representative of one Compound (IX) is called 1,1-bis (neopentyloxycarbonyl) -4,4-diphenyl-1,3-butadiene become.

Typical UV-absorbing amino-substituted hydroxybenzophenones (X) are, in particular, those of the formula (2) as described in German Patent Application No. 199 17 906.9 for cosmetic and pharmaceutical preparations:

in which the variables have the following meaning independently of one another:
R ¹ and R ^{2 are} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, where the substituents R ¹ and R ² together with the Nitrogen atom to which they are attached can form a 5- or 6-membered ring;
R ³ and R ^{4 are} C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₁ - C ₁₂ alkoxy, C ₁ -C ₂₀ Alkoxycarbonyl, C ₁ -C ₁₂ alkylamino, C ₁ -C ₁₂ dialkylamino, aryl, heteroaryl, optionally substituted, and water-solubilizing substituents selected from the group consisting of a nitrile group, carboxylate, sulfonate or ammonium radicals;
X is hydrogen, COOR ⁵ , CONR ⁶ R ⁷ ;
R ⁵ to R ^{7 are} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, - (YO) _o -Z, aryl;
Y - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH (CH ₃ ) -CH ₂ -;
Z -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ ;
m 0 to 3;
n 0 to 4;
o 1 to 20

Regarding the detailed specification of the structures of the amino-substituted Hydroxybenzophenones of formula II and examples of such compounds II is in this connection expressly to the disclosure of the German patent application Ref. 199 17 906.9. As a typical example of a representative of one Compound (X) becomes 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester called.

Typical UV-absorbing triazines (XI) are:
2,4,6-trianilino-4- (carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine (Uvinul® T-150),
2-ethylhexyl-4 - {[4- {4- [tert-butylamino] carbonyl] anilino} -6- (4 - {[2-ethylhexyl) oxy] carbonyl} anilino) -1,3,5-triazine 2-yl] amino} benzoate,
2- (4-methoxyphenyl) -4,6-di [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -1,3,5-triazine.

Representatives of compounds B of types (I) to (VIII) and (XI) are otherwise in WO 97/44422 and WO 96/03486.

In addition to the compounds of types (I) to (XI), the following can also be used as organic UV absorbers B:
3- (4-methylbenzylidene) bornan-2-one (Eusolex® 6300),
5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one,
3-benzylidenebornan-2-one,
digalloyltrioleate,
2-hydroxy-1,4-naphthalendion,
5-Methyl-2-phenylbenzoxazole,
Dibenzaldehydamin,
dianisoylmethane,
methyl eugenol,
2-amino-6-hydroxypurine,
N- (4-ethoxycarbonylphenyl) -N'-methyl-N'-phenylformamidine (Givosorb® UV1),
N- (4-ethoxycarbonylphenyl) -N'-ethyl-N'-phenylformamidine (Givosorb® UV2),
3- (4'-methylbenzylidene) camphor (Uvinul® MBC95),
N ¹ - (2-ethoxyphenyl) -N ² - (2-ethylphenyl) ethanediamide,
N ¹ - (2-ethoxyphenyl) -N ² - (4-dodecaphenyl) ethanediamide,
2-ethylhexyl-2-cyano- (3-oxo-2,3-dihydro-1H-isoindol-1-ylidene) ethanoate,
1,1-dicyano-2- (4-butyloxy) phenyl-2-phenyl-ethene.

Particularly preferred organic UV absorbers B which are used together with zinc oxide and / or titanium dioxide are the compounds:
1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (Uvinul® BMBM),
4-bis- (polyethoxy) -4-aminobenzoic acid polyethoxyethyl ester (Uvinul® P-25),
2-ethylhexyl-4-methoxycinnamate (Uvinul® MC80),
2-hydroxy-4-methoxybenzophenone (Uvinul® M40),
2,4-dihydroxybenzophenone (Uvinul® 3000),
2,2 ', 4,4'-tetrahydroxybenzophenone (Uvinul® D-50),
2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinul® D-49),
2,2-dihydroxy-4,4-dimethoxybenzophenone (Uvinul® 3049),
2-hydroxy-4- (2-ethylhexyloxy) benzophenone,
2-hydroxy-4- (n-octyloxy) benzophenone (Uvinul® 3008),
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (Uvinul® MS 40) and its salts,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bissulfonic acid and its salts (Uvinul® DS49),
2'-ethyl-2-cyano-3,3-diphenylacrylic acid (Uvinul® N 539 T),
Ethyl 2-cyano-3,3-diphenylacrylate (Uvinul® 3035),
1,1-bis (neopentyloxycarbonyl) -4,4-diphenyl-1,3-butadiene,
2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester,
2,4,6-trianilino-4- (carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine (Uvinul® T-150),
3- (4'-methylbenzylidene) camphor (Uvinul® MBC95).

Sometimes it can be advantageous if the components A and B together with Antioxidants and / or radical scavengers are used. Antioxidants and Radical scavengers that can be used here count all the compounds that Usually for the stabilization of food and feed but also for Stabilization of plastics or lubricants can be used. A list of such Connections can be found e.g. B. in Kirk-Othmer, Encyclopedia of Chemical Technology, fourth edition, volume 3, p. 424-447 or in Ullmann's Encyclopedia of Industrial Chemistry, sixth edition, 2000 Electronic Release, chapters antioxidants and food additive.

However, these include in particular:

• - Substituted phenols, hydroquinones, pyrocatechols and gallates such as 2,6-di-tert. butylphenol, 2,4,6-tri-t-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert.- butyl-4-methylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 3-tert-butyl-4- methoxyphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), propyl, octyl and Dodecyl gallate or tert-butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT),
• - Irganox® antioxidants (from Ciba-Geigy) such as Irganox® 1010 (Tetrakis methylene (3,5-di-tert-butyl-4-hydroxycinnamate)) methane), Irganox® 1035 (Thiodiethylenebis (3,5-di-tert-butyl-4-hydroxycinnamate)) and Irganox® 1076 (Octadecylpropane (3-benzene-3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) phosphonate),
• Trihydroxybutyrophenone (THBP),  
• - α-tocopherol and its natural or synthetic derivatives such as acetyl-α- tocopherol,
• - Ascorbic acid and ascorbic acid derivatives, especially esterification products with long chain fatty acids like ascorbyl palmitate,
• Diazabicyclooctane (DABCO),
• - Chroman derivatives such as long-chain esters of 2,5,7,8-tetramethyl-6- hydroxychroman-2-oic acid,
• Aromatic amines such as ethoxyquin,
• Organic sulfides such as 3,3'-thiodipropionic acid and dilaurylthiodipropionate,
• - Sterically hindered amines, e.g. B. of the tetramethylpiperidine type such as Uvinul® 4049H, Uvinul® 4050H and Uvinul® 5050H from BASF AG,
• - Free radicals of the N-oxyl type such as 4-hydroxytetramethylpiperidine-N-oxide, the Esterification products with carboxylic acids and other derivatives,
• Hydroxylamines such as those of dialkylamines and hydroxylamine ethers Derivatives of tetramethylpiperidine compounds,
• - Ascorbic, lactic, citric and tartaric acid and their salts.

The inorganic pigments A and organic UV absorber B have an excellent effect Way together as textile fiber-affine UV absorbers and reinforce each other in their effect. On the one hand, they protect the in the form applied to textile material human skin from damaging UV radiation. On the other hand, they protect colored things textile material before the color fades. Both protective effects preferably occur at the same time.

Textile materials, on which components A and B mount and theirs there Develop protective effect, in particular include clothing items, i. H. Textiles on  worn on human skin, but also home and garden items made of or with dyed textiles such as awnings and parasols, the more intense sun exposure are exposed. This textile material to be protected preferably consists of cellulose (Cotton) or contains cellulose, for example cotton clothing textiles or from cotton-polyester blends.

The present invention also relates to the use of zinc oxide and / or Titanium dioxide together with organic UV absorbers on textile material for protection the human skin from damaging UV radiation and / or to protect dyed textile material before the color fades.

The mixture containing components A and B is usually in the form of a aqueous liquor containing components A and B and other ingredients may contain, on the textile material, for example by spraying or dipping and Squeeze, applied. Components A and B can be used in textile finishing during the manufacture of the textile material, during textile washing, during the Textile laundry pretreatment and / or the textile laundry post-treatment on the textile Material are applied.

The UV protection equipment makes the UV protection factor UPF of the textile material elevated.

The UV protection factor UPF ("Ultraviolet Radiation Protection Factor") of textiles is tuned according to the Australian / New Zealand standard AS / NZS 4399: 1996 using an in vitro method. The UV permeability of the textile object is measured. The protection factor can be determined directly from the spectral transmission using the following equation:

in which:
S _{λ is} the spectral radiation of the sun in the UV range at the wavelength λ,
E _{λ is} the spectral erythema effectiveness of UV radiation at the wavelength λ, and
T _λ the spectral transmission of the textile object at the wavelength λ
is.

The present invention also relates to a textile detergent formulation, which 0.01 to 20 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-% of components A and B contains, among other usual components. The weight ratio of component A to component B is preferably from 20: 1 to 1:10, particularly preferably from 8: 1 to 1: 5 and particularly preferably from 3: 1 to 1: 1. The addition of components A and B can be added separately to the formulation take place or it can be the pre-made mixture of A and B in the formulation be incorporated.

Textile detergent formulations according to the invention can be solid or liquid Formulations.

Solid detergent formulations according to the invention generally contain further customary constituents

• a) 0.1 to 40 wt .-% of at least one nonionic and / or anionic Surfactant as component C,
• b) 0 to 50% by weight of one or more inorganic builders as component D,
• c) 0 to 20% by weight of one or more organic cobuilders E,
• d) 0 to 60% by weight of other customary ingredients, such as cationic surfactants, adjusting agents, Enzymes, perfume, complexing agents, corrosion inhibitors, bleach, Bleach activators, bleach catalysts, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes, resolution improvers and / or Disintegrant as component F,

the sum of components A to F being 100% by weight.  

The solid detergent formulations according to the invention are usually in the form of Powder, granules, extrudate or in tablet form.

Liquid detergent formulations according to the invention generally contain further customary constituents

• a) 0.1 to 40 wt .-% of at least one nonionic and / or anionic surfactant as Component C,
• b) 0 to 20% by weight of one or more inorganic builders as component D,
• c) 0 to 10% by weight of one or more organic cobuilders as component E,
• d) 0 to 40% by weight of other customary ingredients, such as cationic surfactants, soda, Enzymes, perfume, complexing agents, corrosion inhibitors, bleach, Bleach activators, bleach catalysts, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes, non-aqueous solvents Hydrotropes, thickeners and / or alkanolamines as component F and
• e) 0 to 99.85% by weight of water as component G,

the sum of components A to 6 being 100% by weight.

Suitable anionic surfactants are in particular:

• - (Fat) alcohol sulfates of (fatty) alcohols with 8 to 22, preferably 10 to 18 carbon atoms, e.g. B. C ₉ to C ₁₁ alcohol sulfates, C ₁₂ to C ₁₄ alcohol sulfates, C _{12 to} C ₁₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;
• - sulfated alkoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates). Compounds of this type are prepared, for example, by firstly using a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation;
• linear C ₈ to C ₂₀ alkyl benzosulfonates (LAS), preferably linear C ₉ to C ₁₃ alkyl benzene sulfonates and alkyl toluenesulfonates,
• Alkanesulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkanesulfonates,
• - Soaps such as the Na and K salts of C ₈ to C ₂₄ carboxylic acids.

The anionic surfactants mentioned are preferably in the form of Added salts. Suitable cations in these salts are alkali metal ions such as Sodium, potassium and lithium and ammonium ions such as hydroxyethylammonium, Di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium.

Suitable nonionic surfactants are in particular:

• - Alkoxylated C ₈ - to C ₂₂ alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These can be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of one of the above-mentioned alkylene oxides added can be used as surfactants. Here, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. The nonionic surfactants generally contain 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide per mole of alcohol. These preferably contain ethylene oxide as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the preparation, the alkoxylates have a broad or narrow alkylene oxide homolog distribution;
• Alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 alkylene oxide units;
• - Alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the Alkyl chain and generally 1 to 20, preferably 1.1 to 5 glucoside units;
• - N-alkyl glucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and Block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

Suitable inorganic builders are in particular:

• - Crystalline or amorphous aluminosilicates with ion exchange properties such as especially zeolites. Suitable zeolites are in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially against others Cations such as Li, K, Ca, Mg, or ammonium are exchanged;
• - Crystalline silicates such as, in particular, disilicate or layered silicates, e.g. B. δ-Na ₂ Si ₂ O ₅ or β-Na ₂ Si ₂ O ₅ . The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates;
• - amorphous silicates such as sodium metasilicate or amorphous disilicate;
• - carbonates and hydrogen carbonates. These can be in the form of their alkali metal, Alkaline earth metal or ammonium salts are used. Na, Li and Mg carbonates or bicarbonates, especially sodium carbonate and / or sodium hydrogencarbonate;
• - Polyphosphates such as pentasodium triphosphate.

Suitable organic cobuilders are in particular low molecular weight, oligomeric or polymeric carboxylic acids.

• Suitable low-molecular carboxylic acids are, for example, citric acid, Hydrophobically modified citric acid such as B. agaricic acid, malic acid, Tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, Oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetra carboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids such as z. B. nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, Serine diacetic acid, isoserine diacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, Ethylenediamine disuccinic acid and methyl and ethylglycinediacetic acid;
• Suitable oligomeric or polymeric carboxylic acids are, for example, homopolymers of acrylic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid, C ₂ -C ₂₂ olefins such as. B. isobutene or long-chain α-olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, vinyl acetate, vinyl propionate, (meth) acrylic esters of C ₁ -C ₈ alcohols and styrene. The homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid are preferably used. Polyaspartic acids are also suitable as organic cobuilders. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.

Suitable bleaches are, for example, adducts of hydrogen peroxide inorganic salts such as B. sodium perborate monohydrate, sodium perborate tetrahydrate or sodium carbonate perhydrate or percarboxylic acids such as phthalimidopercaproic acid.

The present invention also relates to laundry treatment and Laundry care products, which 0.01 to 20 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 0.1 to 5% by weight of components A and B in addition to other customary ones Ingredients included. The weight ratio of component A is preferably to component B from 20: 1 to 1:10, particularly preferably from 8: 1 to 1: 5, in particular from 3: 1 to 1: 1. The addition of components A and B can be carried out separately in the formulation or it can be the pre-made mixture of A and B in the Formulation to be incorporated.

The laundry aftertreatment and laundry care compositions according to the invention generally contain further customary constituents

• a) 0.1 to 40% by weight of at least one cationic surfactant as component C,
• b) 0 to 30% by weight of one or more nonionic surfactants as component D,
• c) 0 to 30% by weight of other customary ingredients, such as fragrances and colorants, Stabilizers, fiber and color protection additives, viscosity modifiers, soil Release additives, graying inhibitors, color transfer inhibitors, Complexing agents, corrosion protection additives, bactericides, preservatives, non-aqueous solvent, hydrotropes and / or alkanolamines as component E,
• d) 0 to 25% by weight of cationic polymers as binders as component F, and
• e) water to make up to 100% by weight as component G.

All natural or synthetic can be used as cationic polymers (component F) cationic polymers are used, the amino and / or ammonium groups contain and are water soluble or water dispersible. Examples of such cationic polymers are polyethyleneimines, amidated, alkoxylated and / or alkylated Polyethyleneimines, crosslinked polyethyleneimines, polyamidoamines, alkoxylated and / or alkylated polyamidoamines, crosslinked polyamidoamines, grafted with ethyleneimine cross-linked polyamidoamines, amine-epichlorohydrin polycondensates, polyvinylamines, alkoxylated polyvinylamines, partially hydrolyzed polyvinylformamides, polyallylamines, Polydimethyldiallylammonium chloride, polymers containing 1-vinylimidazole units such as poly-1-vinylimidazole or poly- (1-vinylimidazole-co-1-vinylpyrrolidone), quaternary Polymers containing vinylimidazole units, condensates of imidazole and Epichlorohydrin, basic (meth) acrylamide or (meth) acrylic ester units containing Polymeric, basic quaternary (meth) acrylamide or (meth) acrylic ester units containing polymers, and / or lysine condensates.

Cationic polymers are also understood to mean amphoteric polymers, the one have net cationic charge, d. H. the polymers contain both anionic and also cationic monomers in polymerized form, however the molar fraction is the cationic units contained in the polymer are larger than that of the anionic units.

Preferred cationic surfactants (component C) are selected from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamidoammonium salts, the amidoamine esters and imidazolium salts. These are preferably contained in the laundry detergent in an amount of 3 to 30% by weight. Examples are quaternary diester ammonium salts which have two C ₁₁ -C ₂₂ -alk (en) yl carbonyloxy (mono- to pentamethylene) radicals and two C ₁ -C ₃ -alkyl or hydroxyalkyl radicals on the quaternary N atom and as Counterion, for example, wear chloride, bromide, methyl sulfate or sulfate.

Quaternary diesterammonium further include in particular those having a C ₁₁ - a trimethylene moiety to C ₂₂ -alk (en) ylcarbonyloxytrimethylen radical, on the central carbon atom, are a C ₁₁ - transmits to C ₂₂ -alk (en) ylcarbonyloxy radical , and three C ₁ - to C ₃ - alkyl or hydroxyalkyl radicals on the quaternary N atom and, for example, carry chloride, bromide, methyl sulfate or sulfate as counterion.

Quaternary tetraalkylammonium salts are in particular those which have two C ₁ to C ₆ alkyl radicals and two C ₈ to C ₂₄ alk (en) yl radicals on the quaternary N atom and, for example, chloride, bromide, methyl sulfate or Wear sulfate.

Quaternary diamidoammonium salts are in particular those which have two C ₈ - to C ₂₄ -alk (en) ylcarbonylaminoethylene radicals, a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene with up to 5 oxyethylene units and as the fourth radical a methyl group on the quaternary N. -Atom and have as counterion, for example, chloride, bromide, methyl sulfate or sulfate.

Amidoamino esters are, in particular, tertiary amines which have a C ₁₁ to C ₂₂ alk (en) ylcarbonylamino (mono- to trimethylene) radical, a C ₁₁ to C ₂₂ alk (en) ylcarbonyloxy (mono - to trimethylene) residue and a methyl group.

Imidazolinium salts are in particular those in which the 2-position of the heterocycle, a C ₁₄ - to C ₁₈ -alk (en) yl radical, the neutral N-atom form a C ₁₄ - to C ₁₈ -alk (en) ylcarbonyl (oxy or amino) carry the ethylene radical and hydrogen, methyl or ethyl on the N atom carrying the positive charge; counterions here are, for example, chloride, bromide, methyl sulfate or sulfate.

The present invention also relates to the use of zinc oxide and / or Titanium dioxide together with organic UV absorbers in textile detergents, Laundry aftercare and laundry care products.

The present invention also relates to equipment for UV Protective equipment for textile materials containing components A and B.

The finishing agents according to the invention can be used, for example, as finishing agents in the narrower sense in the manufacture of textiles or in the form of an aqueous Wash liquor or as a liquid textile treatment agent. For example possible to connect the textiles with the Treat equipment. Textiles that are not yet or only insufficiently Equipment has been treated, for example in front of or in the home after washing, with a textile treatment agent that contains the inorganic pigments A and the organic UV absorber B contains are treated. It is also possible to wash the textiles in the main wash cycle or after the main wash cycle in the  or treating the washing machine with fabric softener with components (A) and (B), partially using the formulations described above.

The following examples are intended to illustrate the present invention, but without it to restrict.

example 1 Use of UV protection agents in textile laundry aftertreatment Fabric softener and determination of the UPF UV protection factor

White cotton fabric with a basis weight of 100 g / m ² and a UV protection factor (UPF) of 4.1 was washed at a water hardness of 3 mmol / l. The washing process consisted of a main wash at 40 ° C (Ariel® Color as a detergent) followed by a fabric softener. A commercial formulation (Downy from Lenor®) in a dose of 1000 ppm, based on the liquor, was used as the fabric conditioner. Either no UV absorber or in each case 100 or 200 ppm, based on the liquor, of a UV absorber combination according to the invention had been added to the fabric conditioner formulation before the fabric softener / conditioner. The liquor ratio was 1: 12.5. After the fabric softener / conditioner, the fabric was removed and its UV protection factor determined in the dried state. The fabric was then checked for light stability. The tissue sample was exposed in a table exposure device SUNTEST® CPS (from Heraeus, Hanau) for 4 and 24 hours (under out-door conditions with filter WG 295) at maximum radiation power of the device. After 4 and 24 hours of exposure, the UV protection factor was determined again.

The following were used as inorganic pigments:

• - Z-COTE®, an amphiphilic zinc oxide from BASF AG
• - Uvinul® TiO ₂ from BASF AG

The following were used as organic UV absorbers:
A = 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester (Uvinul® N-539 T)
B = 2-hydroxy-4- (n-octyloxy) benzophenone (Uvinul® 3008)

The results are summarized in Table 1.  

Table 1

The results clearly show the synergistic effect when using the UV absorber A or B with zinc oxide or titanium dioxide. The is also clearly visible positive influence of pigment oxides on the photostability of organic UV absorbers A and B. Zinc oxide and titanium dioxide increase the UV protection factor of the cotton fabric only insignificant if they are used alone.

Example 2 Use for textile laundry aftertreatment in fabric softener / conditioner and determination of the light stability of the dyed cotton fabric used

Cotton fabric dyed with Reaktiv Schwarz 5 (1/3 directional depth type) was used in Fabric softener with a commercially available formulation (Downy from Lenor®, 1000 ppm based on the fleet) with the addition of a UV absorber combination according to the invention (each 200 ppm based on the liquor) treated in the liquor ratio 1: 12.5. After this The colored fabrics were removed and dried in the dry condition Light stability checked.  

The light stabilities (photostabilities) were measured as follows:
The samples were exposed in a table exposure device SUNTEST® (from Heraeus, Hanau) for 8 or 24 hours (under out-door conditions with filter WG 295) at maximum radiation power of the device. The reflectance spectra of the dyeings were measured before and after exposure using a spectrophotometer with an integration sphere ("Lambda 900" from Perkin Elmer); these reflectance spectra were converted into K / S spectra according to the Kubelka-Munk theory (K = absorption coefficient, S = scattering coefficient). The photostabilities were assessed on the basis of the K / S values remaining after 8 or 24 hours of exposure, based on the K / S values before exposure (K / S in each case at the maximum of the K / S spectra). The greater the value given in Table 2 in%, the greater the photostability.

Z-COTE® from BASF AG was used as the inorganic pigment.

The following were used as organic UV absorbers:
C = 2- (4'-Diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester
D = 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (Uvinul® BMBM)

Table 2

The results clearly show the synergistic effect when using C or D with zinc oxide.

Claims (12)

1. Method for UV protective equipment of textile material, in which one

• a) zinc oxide and / or titanium oxide as component A and
• b) one or more organic UV absorbers as component B.

onto the textile material. 2. The method according to claim 1, characterized in that component A UV- Contains absorbers with an absorption maximum in the range of 280 to 450 nm. 3. The method according to claim 1 or 2, characterized in that component B one or more compounds selected from the group consisting of
phenylbenzotriazoles,
dibenzoylmethanes,
Esters of p-aminobenzoic acid,
Esters of cinnamic acid,
Esters of salicylic acid,
nitrogen-free 2-hydroxybenzophenones,
Phenylbenzimidazolen,
acrylates,
diarylbutadienes
amino-substituted hydroxybenzophenones,
triazines
contains. 4. The method according to any one of claims 1 to 3, characterized in that the Weight ratio of component (A) to component (B) from 20: 1 to 1:10 is. 5. The method according to any one of claims 1 to 4, characterized in that the Components A and B in the form of an aqueous liquor containing components A and  B contains and may also contain other ingredients on the textile material applies. 6. The method according to any one of claims 1 to 5, characterized in that the Components A and B in textile equipment during the manufacture of the textile Materials, in textile washing and / or in textile washing aftertreatment applies the textile material. 7. Textile detergent formulation containing 0.01 to 20 wt .-%, based on their Sum, the components A and B as defined in one of claims 1 to 4, among other common ingredients. 8. Laundry aftertreatment and laundry care formulation, containing 0.01 up to 20 wt .-%, based on their sum, the components A and B as in one of claims 1 to 4 defined, among other usual ingredients. 9. laundry aftertreatment and laundry care formulation according to claim 8, containing 1 to 50 wt .-% of one or more cationic surfactants selected from the group consisting of quaternary diesterammonium salts, quaternary Tetraalkylammonium salts, quaternary diamidoammonium salts, Amido amino esters and imidazolines. 10. Equipment for UV protective equipment of textile material containing one Mixture of components (A) and (B) as in one of claims 1 to 4 Are defined. 11. Textile material containing a mixture of components (A) and (B), as in one of claims 1 to 4 defined. 12. Use of zinc oxide and / or titanium dioxide together with organic UV Absorbers on textile material to protect human skin from harmful UV radiation and / or to protect dyed textile material before the color fades.