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EP1383952A2 - Method for providing textile material with uv protection - Google Patents

Method for providing textile material with uv protection

Info

Publication number
EP1383952A2
EP1383952A2 EP02704685A EP02704685A EP1383952A2 EP 1383952 A2 EP1383952 A2 EP 1383952A2 EP 02704685 A EP02704685 A EP 02704685A EP 02704685 A EP02704685 A EP 02704685A EP 1383952 A2 EP1383952 A2 EP 1383952A2
Authority
EP
European Patent Office
Prior art keywords
textile material
acid
textile
component
components
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02704685A
Other languages
German (de)
French (fr)
Inventor
Thomas Heidenfelder
Jürgen Detering
Gerhard Wagenblast
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1383952A2 publication Critical patent/EP1383952A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/1845—Aromatic mono- or polycarboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/2035—Aromatic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/335—Amines having an amino group bound to a carbon atom of a six-membered aromatic ring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments

Definitions

  • the invention relates to a method for UV protective finishing of textile material, textile detergent, laundry treatment and laundry care formulations, finishing agent for UV protective finishing of textile material, the finished textile material itself and the use of zinc oxide and / or titanium dioxide together with organic UV absorbers.
  • UV radiation from sunlight on human skin are not limited to premature skin aging and the formation of skin erythema (reddening of the skin, sunburn). Exposing the skin to UV radiation for too long and too intensely increases the risk of developing skin cancer. Primarily responsible for the reddening of the skin and the increased risk of skin cancer is the UV-B portion of the UV radiation, i.e. 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 the skin as a physical barrier against the damaging effects of sunlight (“textile skin protection").
  • textile skin protection the skin-protecting effect of the textiles depends on many factors such as the type of fiber, fabric construction, fabric weight, color, moisture content or type of finishing or finishing. For example, summer clothing in the form of light and light cotton textiles offers only weak and therefore inadequate protection against 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 textiles caused by sunlight. There is therefore a great interest in protecting both colored textiles and human skin from the damaging effects of UV radiation.
  • Stilbene and triazine bases as described in EP-A 682 145, GB-A 2 313 375 or EP-A 728 749.
  • the effectiveness of the agents is still in need of improvement have a number of disadvantages.
  • Significant disadvantages are their poor formulability and their poor solubility in the respective application medium.
  • sunscreens in particular from the group of 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, but also without mixtures here Notes on the respective mixing ratios - protect dyed textile material from fading of the color.
  • WO 96/03486 describes essentially the same sunscreens as they are mentioned in WO 97/44422 as means for protecting dyed textile material from color fading.
  • the effectiveness of these agents is also in need of improvement and has a number of disadvantages.
  • a major disadvantage is the often too low UV stability of the above-mentioned agents.
  • pigments such as titanium dioxide or zinc oxide in fibers
  • Synthetic fibers made of polyamide, polyester or polyacrylonitrile are particularly suitable for this type of UV protective equipment. Cellulose fibers are not very suitable for this.
  • JP 03/277699 describes solid detergents, especially soaps, with a zinc oxide content of 0.1 to 15% by weight.
  • the soaps show good UV absorption and have a deodorising effect.
  • WO 98/42909 describes the UV protective finish of textile fabrics by treatment with inorganic particles which can absorb, reflect or scatter UV radiation, in combination with a binder. These particles can also be used during the washing of textiles.
  • the object of the present invention is to provide improved and more photostable UV absorber systems in their effect.
  • the task is solved by a process for UV protection of textile material, in which one
  • component A Zinc oxide and / or titanium oxide as component A and (b) applying one or more organic UV absorbers as component B to the textile material.
  • Zinc oxide and / or titanium dioxide are used as component A as inorganic pigments absorbing UV radiation.
  • Component A can consist of zinc oxide or titanium dioxide either alone or from mixtures of the two pigments.
  • Titanium dioxide can be used in its three modifications rutile, anatase or brookite; it is preferably used as rutile.
  • the particle size is generally from 0.01 to 100 ⁇ m, preferably from 0.02 to 0.25 ⁇ m.
  • 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 ⁇ m, particularly preferably in the range from 0.08 to 0.25 ⁇ m.
  • the titanium dioxide and zinc oxide pigment particles can have a passivation layer made of inorganic oxides, in particular of silicon dioxide or aluminum oxide.
  • the pigment surface can also be specifically hydrophilized or hydrophobized by treatment with organic compounds or silicones.
  • Be used for surface modification ⁇ for example, amines, cationic polymers such as amino-containing polymers, polyols, organophosphates, alkyl phthalates, stearic acid, lauric acid or silicone oils.
  • component B which have at least one UV absorption maximum in the range from 280 to 450 nm.
  • component B contains those compounds which have at least one UV absorption maximum in the range from 290 to 375 nm.
  • 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 EV value of at least 200, in particular at least 250, and at least one UV absorption maximum Range from 315 to 400 nm (UV-A range) with an E ⁇ value of at least 200, in particular at least 250.
  • Organic UV absorbers B have one or more bands in the UV absorption spectrum.
  • UV absorption maxima are to be understood here as the bands belonging to the corresponding local or absolute maxima in the UV spectrum of the respective compound, measured in conventional organic solvents such as dichloromethane or methanol at room temperature.
  • the E ⁇ 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.
  • the mixture according to the invention contains, as component B, those organic UV absorbers which contain an n-octanol / water
  • Log P have distribution coefficients log P of at least 1.9, in particular at least 2.5, especially at least 3.3. Log P can be determined or calculated experimentally. Both procedures are described in Chemical Reviews Volume 71, No. 5, pages 52-5-616
  • Organic UV absorbers B which are selected from the group consisting of
  • esters of p-aminobenzoic acid (III) esters of p-aminobenzoic acid, (IV) esters of cinnamic acid,
  • Typical UV-absorbing phenylbenzotriazoles (I) are:
  • Typical UV-absorbing dibenzoylmethanes are: 3- (4-isopropylphenyl) -3-phenylpropane-1,3-dione (Eusolex® 8020), l- (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:
  • Typical UV-absorbing esters of cinnamic acid are:
  • Typical UV-absorbing esters of salicylic acid (V) are:
  • Typical UV-absorbing phenylbenzimidazoles are:
  • Typical UV-absorbing acrylates 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) acrylic acid hexyl ester.
  • 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.
  • 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 are in particular 4,4-diarylbutadienes of the formula (1), as described in DE-A 198 28 463 for cosmetic and pharmaceutical preparations:
  • C 2 -alkyl C 2 -C 10 alkenyl, C 3 -C 10 cycloalkyl, C 3 -C ⁇ 0 cycloalkenyl, CC ⁇ alkoxy, C 1 -C 2 o-alkoxycarbonyl, C ⁇ - C 2 alkylamino, CrC ⁇ dialkylamino, aryl, heteroaryl, optionally substituted, and water-solubilizing substituents selected from the group consisting of
  • 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] 0 -R 7 , Cj- -alkylene-SOsY, -C-C 6 -alkylene-PO 3 Y, CC 6 -alkylene- N (R 8 ) 3 + A " ;
  • Y is hydrogen, Na + , K + , Mg 2+ , Ca 2+ , Li + , Al 3+ , N (R 8 ) 4 + ;
  • R 9 is hydrogen, -CC 6 alkyl, C 2 -C 6 alkenyl; n 1 to 3;
  • Typical UV-absorbing amino-substituted hydroxybenzophenones are, in particular, those of the formula (2) as described in German patent application No. 199 17 906.9 for cosmetic and pharmaceutical preparations:
  • R ⁇ d R 2 is 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 Ci- jo-Al yl, C -C ⁇ 0 alkenyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkenyl, d- C 12 alkoxy, C 1 -C 2 o-alkoxycarbonyl , Ci-C ⁇ -alkylamino, Ci-C ⁇ - dialkylamino, aryl, heteroaryl, optionally substituted, and water-solubilizing substituents selected from the group consisting of a nitrile group, carboxylate, sulfonate or ammonium residues;
  • 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 ⁇ o cycloalkyl, C 3 -C 10 cycloalkenyl, - (YO) 0 -Z, aryl;
  • Typical UV-absorbing triazines 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) -l, 3,5-triazin-2-yl] amino ⁇ benzoate,
  • organic UV absorbers B In addition to the compounds of types (I) to (XI), the following can also be used as organic UV absorbers B:
  • Particularly preferred organic UV absorbers B which together with zinc oxide and / or
  • the compounds used are titanium dioxide:
  • antioxidants and / or radical scavengers include all compounds that are usually used to stabilize food and feed but also to stabilize plastics or lubricants.
  • a list of such connections can be found e.g. 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 additives.
  • 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),
  • TBHQ butylated hydroxyanisole
  • BHT butylated hydroxytoluene
  • Irganox® antioxidants from Ciba-Geigy
  • TBP Trihydroxybutyrophenone
  • ⁇ -tocopherol and its natural or synthetic derivatives such as acetyl- ⁇ -tocopherol,
  • Ascorbic acid and ascorbic acid derivatives in particular esterification products with long-chain fatty acids such as ascorbyl palmitate,
  • Diazabicyclooctane (DABCO) Chroman derivatives such as long-chain esters of 2,5,7,8-tetramethyl-6-hydroxychroman-2-acid,
  • aromatic amines such as ethoxyquin
  • organic sulfides such as 3,3'-thiodipropionic acid and dilaurylthiodipropionate
  • sterically hindered amines e.g. of the tetramethylpiperidine type such as Uvinul® 4049H, Uvinul® 4050H and Uvinul® 5050H from BASF AG,
  • Hydroxylamines such as those of dialkylamines and hydroxylamine ether derivatives of the tetramethylpiperidine compounds,
  • the inorganic pigments A and organic UV absorber B work together excellently as textile fiber-affine UV absorbers and reinforce each other in their effect. On the one hand, they protect human skin from damaging UV radiation when applied to textile material. On the other hand, they protect dyed textile material from color fading. Both protective effects preferably occur simultaneously.
  • Textile materials on which components A and B mount and develop their protective effect there, include in particular items of clothing, i.e. Textiles that are worn on human skin, but also house and garden items made of or with colored textiles such as awnings and parasols that are exposed to intense sunlight.
  • This textile material to be protected preferably consists of cellulose (cotton) or contains cellulose, for example clothing textiles made of cotton or of cotton-polyester mixtures.
  • 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 from color fading.
  • the mixture comprising components A and B is usually applied to the textile material, for example by spraying or dipping and pressing, in the form of an aqueous liquor which contains components A and B and may also contain further ingredients.
  • Components A and B can be applied to the textile material during textile finishing during the production of the textile material, during textile washing, during textile laundry pretreatment and / or after-textile treatment.
  • the UV protection factor UPF of the textile material is increased by the UV protective equipment.
  • the UN 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:
  • ⁇ ⁇ is the spectral erythema effectiveness of UV radiation at the wavelength ⁇
  • ⁇ ⁇ is the spectral transmission of the textile object at the wavelength ⁇ .
  • the present invention also relates to a textile detergent formulation which comprises 0.01 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.1 to 5 % By weight of components A and B in addition to other customary constituents.
  • 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 separately in the formulation or the pre-made mixture of A and B can be incorporated into the formulation.
  • 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
  • component F 0 to 60% by weight of other customary ingredients such as cationic surfactants, bulking agents, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, dye transfer inhibitors, graying inhibitors, soil release polyesters, dyes, dissolution improvers and / or disintegrant as component F,
  • customary ingredients such as cationic surfactants, bulking agents, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, dye transfer inhibitors, graying inhibitors, soil release polyesters, dyes, dissolution improvers and / or disintegrant as component F,
  • 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
  • component C 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant as component C, (d) 0 to 20% by weight of one or more inorganic builders as component D,
  • customary ingredients such as cationic surfactants, soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes, non-aqueous Solvents hydrotropes, thickeners and / or alkanolamines as component F and
  • Suitable anionic surfactants are in particular:
  • alkoxylated C to C 22 alcohols alkyl ether sulfates
  • Compounds of this type are prepared, for example, by first alkoxylating a C 8 to C 22 , preferably a C 10 to C 8 alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product.
  • Ethylene oxide is preferably used for the alkoxylation;
  • linear C 8 to C 20 alkyl benzosulfonates LAS
  • LAS alkyl benzosulfonates
  • alkyl toluenesulfonates preferably 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 ⁇ -, preferably C 10 - to C 18 -alkanesulfonates,
  • Soaps such as the Na and K salts of C 8 to C 2 carboxylic acids.
  • the anionic surfactants mentioned are preferably added to the detergent in the form of 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.
  • surfactants here come block polymers of ethylene oxide,
  • Propylene oxide and / or butylene oxide or adducts 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.
  • the type of alkoxylation catalyst used in the preparation has a broad or narrow alkylene oxide homolog distribution
  • Alkylphenol alkoxylates such as alkylphenol ethoxylates with C 6 - to C 4 alkyl chains and 5 to 30 alkylene oxide units;
  • Alkyl polyglucosides having 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;
  • 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:
  • 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 partly replaced by other cations such as Li, K, Ca, Mg or ammonium; crystalline silicates such as, in particular, disilicates or layered silicates, for example ⁇ -Na 2 Si 2 O 5 or ⁇ -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 can be used in the form of their alkali metal, alkaline earth metal or ammonium salts.
  • Na, Li and Mg carbonates or bicarbonates are preferred, in particular sodium carbonate and / or sodium bicarbonate;
  • Polyphosphates such as pentasodium triphosphate.
  • Suitable organic cobuilders are in particular low molecular weight, oligomeric or polymeric carboxylic acids.
  • Suitable low molecular weight 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, propa ⁇ tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids such as e.g.
  • Nitrilotriacetic acid ß-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediaminedisuccinic 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 isobutene or long-chain ⁇ -olefins, vinyl alkyl ethers with C 1 -C 8 alkyl groups, vinyl acetate, vinyl propionate, (Meth) acrylic esters of C Cs alcohols and styrene. It is preferred to use the
  • Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts such as sodium perborate monohydrate, sodium perborate tetrahydrate or sodium carbonate perhydrate or percarboxylic acids such as phthalimidopercaproic acid.
  • Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylethylene diamine (TAED), sodium p-nonanoyloxybenzenesulfonate or N-methylmorpholinium acetonitrile-methyl sulfate.
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • sodium p-nonanoyloxybenzenesulfonate sodium p-nonanoyloxybenzenesulfonate or N-methylmorpholinium acetonitrile-methyl sulfate.
  • Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases or peroxidases.
  • Suitable color transfer inhibitors are, for example, homopolymers and copolymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine-N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.
  • the present invention furthermore relates to laundry aftertreatment and laundry care compositions which, in addition to 0.01 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.1 to 5% by weight, of components A and B. contain other common ingredients.
  • 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, in particular from 3: 1 to 1: 1.
  • the addition of components A and B separately in the formulation or the pre-made mixture of A and B can be incorporated into the formulation.
  • the laundry aftertreatment and laundry care compositions according to the invention generally contain further customary constituents
  • 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 solvents, hydrotropes and / or alkanolamines as component E,
  • cationic polymers which contain amino and / or ammonium groups and are water-soluble or water-dispersible can be used as cationic polymers (component F).
  • cationic polymers are polyethyleneimines, amidated, alkoxylated and / or alkylated polyethyleneimines, crosslinked polyethyleneimines, polyamidoamines, alkoxylated and / or alkylated polyamidoamines, crosslinked polyamidoamines, crosslinked polyamidoamines grafted with ethyleneimine, amine-epichlorohydrin polycondensates, polyvinylamines, alkoxylated Polyvinylformamides, polyallylamines,
  • Polydimethyldiallylammonium chlorides polymers containing 1-vinylimidazole units such as poly-1-vinylimidazole or poly- (l-vinylimidazole-co-l-vinylpyrrolidone), polymers containing quaternary vinylimidazole units, condensates of imidazole and epichlorohydrin, basic (meth) acrylamide or (meth) acrylamide units containing polymers, basic quaternary (meth) acrylamide or (meth) acrylic ester units containing polymers and / or lysine condensates.
  • 1-vinylimidazole units such as poly-1-vinylimidazole or poly- (l-vinylimidazole-co-l-vinylpyrrolidone
  • polymers containing quaternary vinylimidazole units condensates of imidazole and epichlorohydrin
  • Cationic polymers are also understood to mean amphoteric polymers which have a net cationic charge, i.e. the polymers contain both anionic and cationic monomers in copolymerized form, but the molar proportion of the cationic units contained in the polymer is greater than that of the anionic units.
  • Preferred cationic surfactants 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 ⁇ to C 22 alk (en) yl carbonyloxy (mono- to pentamethylene) residues and two C to C 3 alkyl or hydroxyalkyl residues on the quaternary N atom and as a counter ion for example, wear chloride, bromide, methyl sulfate or sulfate.
  • Quaternary diesterammonium further include in particular those corresponding to the trimethylene group carries a C ⁇ - to C 22 -alk (en) ylcarbonyloxytrimethylen radical, on the central carbon atom form a C ⁇ - to C 22 -alk (en) ylcarbonyloxy radical, and have three C 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 -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 sulfate as counterion wear.
  • Quaternary diamidoammonium are in particular those which have two C 8 - a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene having up to 5 oxyethylene units and as fourth radical a methyl group on the quaternary nitrogen alk (en) ylcarbonylaminoethylene radicals, - to C 2 -Atom and have as counterion, for example, chloride, bromide, methyl sulfate or sulfate.
  • Amidoamino esters are, in particular, tertiary amines which, as substituents on the N atom, have a C ⁇ to C 22 alk (en) ylcarbonylamino (mono- to trimethylene) radical, a C ⁇ 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 1 -alk (en) yl radical, the neutral N-atom form a C 14 - to C 18 - Alk (en) ylcarbonyl (oxy or amino) 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 aftertreatment and laundry care products.
  • the present invention also relates to finishing agents for UV protective finishing of textile materials, comprising components A and B.
  • finishing agents according to the invention can be used, for example, as finishing agents in the narrower sense in the manufacture of the textiles or in the form of an aqueous one
  • Wash liquor or as a liquid textile treatment agent For example possible to treat the textiles with the finishing agent in connection with the textile production. Textiles that have not yet been treated or have been treated insufficiently with finishing agents can be treated, for example, in the home area before or after washing with a textile treatment agent which contains the inorganic pigments A and the organic UV absorbers B. However, it is also possible to treat the textiles with components (A) and (B) in the main wash cycle or after the main wash cycle in the care or fabric softener cycle, in some cases using the formulations described above.
  • Example 1 Use of the UV protection agents in the textile laundry aftertreatment in the fabric softener bath and determination of the UV protection factor UPF
  • the fabric was then checked for light stability tissue sample was placed in a table exposure apparatus SUNTEST ® CPS (Fa. Heraeus, Hanau) exposed for 4 and 24 hours (with out-door conditions with filter WG 295) at maximum radiation power of the device. After 4 and 24 hours of exposure was again the UV- Protection factor determined.
  • SUNTEST ® CPS Fe. Heraeus, Hanau
  • A 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester (Uvinul® N-539 T)
  • B 2-hydroxy-4- (n-octyloxy) benzophenone (Uvinul® 3008)
  • Example 2 Use in textile laundry aftertreatment in fabric softener and conditioner and determination of the light stability of the dyed cotton fabric used
  • Cotton fabric dyed with Reoxid Schwarz 5 (1/3 directional depth type) was rinsed in the fabric softener with a commercially available formulation (Downy from Lenor®, 1000 ppm based on the liquor) with the addition of a UV absorber combination according to the invention (each 200 ppm based on the liquor) treated in a liquor ratio of 1: 12.5.
  • the colored fabrics were removed and checked for light stability in the dried state.
  • 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.
  • K Absorption coefficient
  • S scattering coefficient
  • the photo stabilities were evaluated 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 larger the value in% given in Table 2, the greater the photostability.
  • Z-COTE® from BASF AG was used as the inorganic pigment.

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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

Verfahren zur UV-Schutzausrüstung von textilem Material Process for UV protective equipment of textile material
Die Erfindung betrifft ein Verfahren zur UV-Schutzausrüstung von textilem Material, Textilwaschmittel-, Wäschenachbehandlungs- und Wäschepflegemittel-Formulierungen, Ausrüstungsmittel zur UV-Schutzausrüstung von textilem Material, das so ausgerüstete textile Material selbst sowie die Verwendung von Zinkoxid und/oder Titandioxid zusammen mit organischen UV- Absorbern.The invention relates to a method for UV protective finishing of textile material, textile detergent, laundry treatment and laundry care formulations, finishing agent for UV protective finishing of textile material, the finished textile material itself and the use of zinc oxide and / or titanium dioxide together with organic UV absorbers.
Die schädigenden Auswirkungen der UV-Strahlung des Sonnenlichtes auf die menschliche Haut beschränken sich nicht nur auf eine vorzeitige Hautalterung und die Bildung von Hauterythemen (Hautrötungen, Sonnenbrand). Wird die Haut zu lange und zu intensiv der UV-Strahlung ausgesetzt, so erhöht sich zusätzlich die Gefahr, an Hautkrebs zu erkranken. Vornehmlich verantwortlich für die Hautrötung und das erhöhte Hautkrebsrisiko ist der UV-B-Anteil der UV-Strahlung, d.h. der Bereich von ca. 280 bis ca. 315 nm. Das Maximum der Erythemen- Wirkung liegt bei 308 nm.The damaging effects of UV radiation from sunlight on human skin are not limited to premature skin aging and the formation of skin erythema (reddening of the skin, sunburn). Exposing the skin to UV radiation for too long and too intensely increases the risk of developing skin cancer. Primarily responsible for the reddening of the skin and the increased risk of skin cancer is the UV-B portion of the UV radiation, i.e. the range from approx. 280 to approx. 315 nm. The maximum erythema effect is 308 nm.
Textilien streuen bzw. absorbieren UV-Strahlung und schützen somit als physikalische Barriere die Haut vor den schädigenden Einflüssen des Sonnenlichtes ("textiler Hautschutz"). Allerdings ist die hautschützende Wirkung der Textilien von vielen Faktoren wie Faserart, Gewebekonstruktion, Stoffgewicht, Farbe, Feuchtigkeitsgehalt oder Art der Ausrüstung bzw. Veredelung abhängig. So bietet gerade Sommerkleidung in Form von leichten und hellen Baumwolltextilien nur einen schwachen und damit unzulänglichen Schutz vor UV-Strahlung.Textiles scatter or absorb UV radiation and thus protect the skin as a physical barrier against the damaging effects of sunlight ("textile skin protection"). However, the skin-protecting effect of the textiles depends on many factors such as the type of fiber, fabric construction, fabric weight, color, moisture content or type of finishing or finishing. For example, summer clothing in the form of light and light cotton textiles offers only weak and therefore inadequate protection against UV radiation.
Eine zu hohe Dosis an UV-Strahlung kann nicht nur Hautschäden verursachen, sie ist auch maßgeblich verantwortlich für die durch Sonnenlicht induzierte Verblassung von farbigen Textilien. Deshalb besteht ein hohes Interesse daran, sowohl farbige Textilien als auch die menschliche Haut vor den schädigenden Einwirkungen der UV-Strahlung zu schützen.Too high a dose of UV radiation can not only cause skin damage, it is also largely responsible for the fading of colored textiles caused by sunlight. There is therefore a great interest in protecting both colored textiles and human skin from the damaging effects of UV radiation.
Bislang werden hauptsächlich übliche optische Aufheller zur Veredelung und zum Schutz der Textilien selbst und auch zum textilen Hautschutz eingesetzt, insbesondere solche aufSo far, conventional optical brighteners have mainly been used for finishing and protecting the textiles themselves and also for textile skin protection, especially those based on
Stilben- und Triazin-Basis, wie in EP-A 682 145, GB-A 2 313 375 oder EP-A 728 749 beschrieben. Die Mittel sind aber in ihrer Wirkung noch verbesserungsbedürftig und weisen eine Reihe von Nachteilen auf. Wesentliche Nachteile sind ihre schlechte Formulierbarkeit und ihre mangelnde Löslichkeit im jeweiligen Anwendungsmedium.Stilbene and triazine bases, as described in EP-A 682 145, GB-A 2 313 375 or EP-A 728 749. However, the effectiveness of the agents is still in need of improvement have a number of disadvantages. Significant disadvantages are their poor formulability and their poor solubility in the respective application medium.
Aus der WO 97/44422 ist bekannt, daß Sonnenschutzmittel insbesondere aus der Gruppe der Phenylbenzotriazole, Dibenzoylmethane, p-Aminobenzoesäureester, Zimtsäureester, Salicylsäureester, stickstofffreien 2-Hydroxybenzophenone, Phenylbenzimidazole und 2- Cyano-3,3-diphenylacrylsäureester sowie Mischungen hieraus - allerdings ohne Hinweise auf die jeweiligen Mischungsverhältnisse - gefärbtes textiles Material vor dem Verblassen der Farbe schützen. In der WO 96/03486 werden im wesentlichen die gleichen Sonnenschutzmittel, wie sie in der WO 97/44422 genannt werden, gleichermaßen als Mittel zum Schutz von gefärbtem textilem Material vor dem Verblassen der Farbe beschrieben. Diese Mittel sind aber in ihrer Wirkung ebenfalls noch verbesserungsbedürfltig und weisen eine Reihe von Nachteilen auf. Ein wesentlicher Nachteil ist die häufig zu geringe UV-Stabilität der oben genannten Mittel.From WO 97/44422 it is known that sunscreens, in particular from the group of 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, but also without mixtures here Notes on the respective mixing ratios - protect dyed textile material from fading of the color. WO 96/03486 describes essentially the same sunscreens as they are mentioned in WO 97/44422 as means for protecting dyed textile material from color fading. However, the effectiveness of these agents is also in need of improvement and has a number of disadvantages. A major disadvantage is the often too low UV stability of the above-mentioned agents.
Die Einlagerung von Pigmenten wie Titandioxid oder Zinkoxid in Fasern ist ein probates Mittel, Textilien aus diesen Fasern mit einem UN-Schutz auszustatten. Vor allem Kunstfasern aus Polyamid, Polyester oder Polyacrylnitril eignen sich für diese Art der UV- Schutzausrüstung. Cellulosefasern sind hierfür wenig geeignet.The incorporation of pigments such as titanium dioxide or zinc oxide in fibers is a tried and tested means of providing textiles made from these fibers with UN protection. Synthetic fibers made of polyamide, polyester or polyacrylonitrile are particularly suitable for this type of UV protective equipment. Cellulose fibers are not very suitable for this.
JP 03/277699 beschreibt feste Detergentien, speziell Seifen, mit einem Gehalt an Zinkoxid von 0,1 bis 15 Gew. %. Die Seifen zeigen eine gute UV- Absorption und besitzen eine desodorierende Wirkung.JP 03/277699 describes solid detergents, especially soaps, with a zinc oxide content of 0.1 to 15% by weight. The soaps show good UV absorption and have a deodorising effect.
WO 98/42909 beschreibt die UV-Schutzausrüstung von textilem Gewebe durch Behandlung mit anorganischen Partikeln, die UV-Strahlung absorbieren, reflektieren oder streuen können, in Kombination mit einem Binder. Die Anwendung dieser Partikel kann auch während des Waschens von Textilien erfolgen.WO 98/42909 describes the UV protective finish of textile fabrics by treatment with inorganic particles which can absorb, reflect or scatter UV radiation, in combination with a binder. These particles can also be used during the washing of textiles.
Aufgabe der vorliegenden Erfindung ist es, in ihrer Wirkung verbesserte und photostabilere UV- Absorber-Systeme bereitzustellen.The object of the present invention is to provide improved and more photostable UV absorber systems in their effect.
Gelöst wird die Aufgabe durch ein Verfahren zur UV-Schutzausrüstung von textilem Material, bei dem manThe task is solved by a process for UV protection of textile material, in which one
(a) Zinkoxid und/oder Titanoxid als Komponente A und (b) einen oder mehrere organische UV-Absorber als Komponente B auf das textile Material aufbringt.(a) Zinc oxide and / or titanium oxide as component A and (b) applying one or more organic UV absorbers as component B to the textile material.
Überraschend wurde gefunden, daß der kombinierte Einsatz von organischen UV- Absorbern und anorganischen Pigmenten aus Zinkoxid und/oder Titandioxid in Textilausrüstungsmitteln, Waschmitteln oder Wäschepflegemitteln zu einem wirksameren UV-Schutz der mit diesen Mitteln behandelten Textilien führt als die alleinige Verwendung der organischen UV-Absorber oder anorganischen Pigmente. Man erzielt sowohl einen höheren und stabileren Schutz der Haut vor schädigender UV-Strahlung, als auch bei farbigem Gewebe einen verstärkten Schutz gegen UV induzierte Farbverblassung.Surprisingly, it was found that the combined use of organic UV absorbers and inorganic pigments made of zinc oxide and / or titanium dioxide in textile finishing agents, detergents or laundry care agents leads to more effective UV protection of the textiles treated with these agents than the sole use of the organic UV absorbers or inorganic pigments. Both a higher and more stable protection of the skin from damaging UV radiation is achieved, as is increased protection against UV-induced color fading in the case of colored tissue.
Als Komponente A werden Zinkoxid und/oder Titandioxid als UV-Strahlung absorbierende anorganische Pigmente eingesetzt. Komponente A kann aus Zinkoxid oder Titandioxid jeweils alleine oder aus Gemischen beider Pigmente bestehen.Zinc oxide and / or titanium dioxide are used as component A as inorganic pigments absorbing UV radiation. Component A can consist of zinc oxide or titanium dioxide either alone or from mixtures of the two pigments.
Titandioxid kann in seinen drei Modifikationen Rutil, Anatas oder Brookit eingesetzt werden, bevorzugt wird es als Rutil eingesetzt. Die Partikelgröße beträgt im allgemeinen von 0,01 bis 100 μ , bevorzugt von 0,02 bis 0,25 μm.Titanium dioxide can be used in its three modifications rutile, anatase or brookite; it is preferably used as rutile. The particle size is generally from 0.01 to 100 μm, preferably from 0.02 to 0.25 μm.
Zinkoxid wird im allgemeinen mit einer Partikelgröße von 0,01 bis 100 μm eingesetzt. Vorzugsweise liegt die Teilchengröße im Bereich von 0,02 bis 2 μm, besonders bevorzugt im Bereich von 0,08 bis 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 from 0.08 to 0.25 μm.
Die Titandioxid- und Zinkoxid-Pigmentpartikel können eine Passivierungsschicht aus anorganischen Oxiden, insbesondere aus Siliziumdioxid oder Aluminiumoxid, aufweisen. Die Pigmentoberfläche kann ferner durch Behandlung mit organischen Verbindungen oder Silikonen gezielt hydrophiliert oder hydrophobiert werden. Zur Oberflächenmodifizierung ^ eingesetzt werden beispielsweise Amine, kationische Polymere wie Aminogruppen enthaltende Polymere, Polyole, Organophosphate, Alkylphthalate, Stearinsäure, Laurinsäure oder Silikonöle.The titanium dioxide and zinc oxide pigment particles can have a passivation layer made of inorganic oxides, in particular of silicon dioxide or aluminum oxide. The pigment surface can also be specifically hydrophilized or hydrophobized by treatment with organic compounds or silicones. Be used for surface modification ^ for example, amines, cationic polymers such as amino-containing polymers, polyols, organophosphates, alkyl phthalates, stearic acid, lauric acid or silicone oils.
Gut geeignet sind beispielsweise: Uvinul® TiO2 (der BASF AG), Z-COTE® (der BASF AG) und Z-COTE HP1® (der BASF AG). Als Komponente B können handelsübliche Sonnenschutzmittel eingesetzt werden, welche mindestens ein UV-Absorptionsmaximum im Bereich von 280 bis 450 nm aufweisen. In einer bevorzugten Ausfuhrungsform enthält die Komponente B solche Verbindungen, die mindestens ein UV- Absorptionsmaximum im Bereich von 290 bis 375 nm aufweisen. In einer weiteren bevorzugten Ausfuhrungsform enthält die Komponente B Verbindungen, die mindestens ein UV- Absorptionsmaximum im Bereich von 280 bis 315 nm (UV-B- Bereich) mit einem EVWert von mindestens 200, insbesondere von mindestens 250, und mindestens ein UV- Absorptionsmaximum im Bereich von 315 bis 400 nm (UV-A- Bereich) mit einem E^-Wert von mindestens 200, insbesondere von mindestens 250, aufweisen.Are well suited, for example: Uvinul ® TiO 2 (BASF AG), Z-COTE ® (BASF AG) and Z-COTE HP1 ® (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 EV value of at least 200, in particular at least 250, and at least one UV absorption maximum Range from 315 to 400 nm (UV-A range) with an E ^ value of at least 200, in particular at least 250.
Organische UV-Absorber B weisen im UV-Absorptionsspektrum eine oder mehrere Banden auf. Unter UV-Absorptionsmaxima sind hier die zu den entsprechenden lokalen oder absoluten Maxima im UV-Spektrum der jeweiligen Verbindung gehörigen Banden, gemessen in üblichen organischen Lösungsmitteln wie Dichlormethan oder Methanol bei Raumtemperatur, zu verstehen.Organic UV absorbers B have one or more bands in the UV absorption spectrum. UV absorption maxima are to be understood here as the bands belonging to the corresponding local or absolute maxima in the UV spectrum of the respective compound, measured in conventional organic solvents such as dichloromethane or methanol at room temperature.
Der E^-Wert bezeichnet die Extinktion der organischen UV-Absorber B, welche in Lösung bei einer Konzentration von 1 Gew.-% und einer Schichtdicke von 1 cm gemessen wird. Als Lösungsmittel wird hierbei üblicherweise Dichlormethan eingesetzt, die Verwendung anderer für derartige UV-Messungen üblicher Lösungsmittel erbringt keine grundsätzlich verschiedenen Werte.The E ^ 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 einer weiteren bevorzugten Ausfuhrungsform enthält die erfindungsgemäße Mischung solche organischen UV-Absorber als Komponente B, die einen n-Octanol/Wasser-In a further preferred embodiment, the mixture according to the invention contains, as component B, those organic UV absorbers which contain an n-octanol / water
Verteilungskoeffizienten log P von mindestens 1,9, insbesondere von mindestens 2,5, vor allem von mindestens 3,3 aufweisen. Log P kann experimentell bestimmt oder berechnet werden. Beide Verfahren werden in Chemical Reviews Volume 71, No. 5, Seiten 52-5-616Have distribution coefficients log P of at least 1.9, in particular at least 2.5, especially at least 3.3. Log P can be determined or calculated experimentally. Both procedures are described in Chemical Reviews Volume 71, No. 5, pages 52-5-616
(1971) beschrieben.(1971).
Vorzugsweise werden organische UV-Absorber B eingesetzt, die aus der Gruppe bestehend ausOrganic UV absorbers B, which are selected from the group consisting of
(I) Phenylbenzotriazolen, (II) Dibenzoylmethanen,(I) phenylbenzotriazoles, (II) dibenzoylmethanes,
(III) Estern der p-Aminobenzoesäure, (IV) Estern der Zimtsäure,(III) esters of p-aminobenzoic acid, (IV) esters of cinnamic acid,
(V) Estern der Salicylsäure,(V) esters of salicylic acid,
(VI) stickstofffreien 2-Hydroxybenzophenonen,(VI) nitrogen-free 2-hydroxybenzophenones,
(VII) Phenylbenzimidazolen, (VIII)Acrylaten,(VII) phenylbenzimidazoles, (VIII) acrylates,
(IX) Diarylbutadienen,(IX) diarylbutadienes,
(X) aminosubstituierten Hydroxybenzophenonen und(X) amino substituted hydroxybenzophenones and
(XI) Triazinen ausgewählt sind.(XI) triazines are selected.
Typische UV-absorbierende Phenylbenzotriazole (I) sind:Typical UV-absorbing phenylbenzotriazoles (I) are:
2,2 ' -Hydroxy-5 -methylphenylbenzotriazol,2,2'-hydroxy-5-methylphenylbenzotriazole,
2,2 ' -Hydroxy-5 -tert. -octylphenylbenzotriazol, 2-Hydroxy-3-sec.-butyl-5-tert.-butylbenzotriazol (Tinuvin® 350),2,2'-Hydroxy-5-tert. octylphenylbenzotriazole, 2-hydroxy-3-sec-butyl-5-tert-butylbenzotriazole (Tinuvin® 350),
2-Hydroxy-3-dodecyl-5-methylphenylbenzotriazol (Tinuvin® 571),2-hydroxy-3-dodecyl-5-methylphenylbenzotriazole (Tinuvin® 571),
2-(2H-Benzotriazol-2-yl)-4-methylphenol (Tinuvin® P),2- (2H-benzotriazol-2-yl) -4-methylphenol (Tinuvin® P),
2-(2H-Benzotriazol-2-yl)-4-n-octylρhenyl (Tinuvin® 329),2- (2H-benzotriazol-2-yl) -4-n-octylρhenyl (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)ρhenol (Tinuvin® 320),2- (2H-benzotriazol-2-yl) -4,6-di (2'-phenylisopropyl) phenol (Tinuvin® 234), 2- (2H-benzotriazol-2-yl) -4,6-di (tert. -butyl) ρhenol (Tinuvin® 320),
2-(6-Chlor-2H-benzotriazol-2-yl)-4-methyl-6-tert.-butylρhenol (Tinuvin® 326),2- (6-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol (Tinuvin® 326),
2-(6-Chlor-2H-benzotriazol-2-yl)-2,6-di-tert.-butylphenol (Tinuvin® 327),2- (6-chloro-2H-benzotriazol-2-yl) -2,6-di-tert-butylphenol (Tinuvin® 327),
2-(2'-Hydroxy-3'35'-di-tert.-amylρhenyl)-2H-benzotriazol (Tinuvin® 328),2- (2'-hydroxy-3 ' 3 5'-di-tert.-amylρhenyl) -2H-benzotriazole (Tinuvin® 328),
Mischung aus ß-[3-(2H-Benzotriazol-2-yl)-5-tert.-butyl-4-hydroxyphenyl]propionsäure- polyoxyethylenglykolester und Polyoxyethylenglykol-bis-ß-[3-(2H-Benzotriazol-2-yl)-5- tert.-butyl-4-hydroxyphenyl]propionat mit einem durchschnittlichen MolekulargewichtMixture of β- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid polyoxyethylene glycol ester and polyoxyethylene glycol bis-β- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate with an average molecular weight
>600 (Tinuvin® 1130),> 600 (Tinuvin® 1130),
Cocoyl-2- [2 ' -Hydroxy-3 ' -(cocoyldimethylbutanoat)-5 ' -methylphenyljbenzotriazol,Cocoyl-2- [2 '-hydroxy-3' - (cocoyldimethylbutanoate) -5 '-methylphenyljbenzotriazole,
Cocoyl-3 - [3 ' -(2H-benzotriazol-2 ' -yl)-5-tert.-butyl-4 ' -hydroxyphenyljpropionat, 2,2'-Methylen-bis-[6-(2H-benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)]phenolCocoyl-3 - [3 '- (2H-benzotriazol-2' -yl) -5-tert-butyl-4 '-hydroxyphenylpropionate, 2,2'-methylene-bis- [6- (2H-benzotriazole-2- yl) -4- (l, l, 3,3-tetramethylbutyl)] phenol
(Tinuvin® 360),(Tinuvin® 360),
2-(2H-l,2,3-Benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-{l,3,3,3-tetramethyl-l-2- (2H-l, 2,3-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- {l, 3,3,3-tetramethyl-l-
[(trimethylsilyl)oxy]disiloxanyl}propyl)phenol.[(Trimethylsilyl) oxy] disiloxanyl} propyl) phenol.
Typische UV-absorbierende Dibenzoylmethane (II) sind: 3-(4-Isopropylphenyl)-3-phenylpropan-l,3-dion (Eusolex® 8020), l-(4-tert.-Butylphenyl)-3-(4-methoxyphenyl)propan-l,3-dion (Uvinul® BMBM), 1 ,3 -Bis(4-methoxyphenyl)propan- 1 ,3-dion.Typical UV-absorbing dibenzoylmethanes (II) are: 3- (4-isopropylphenyl) -3-phenylpropane-1,3-dione (Eusolex® 8020), l- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (Uvinul ® BMBM), 1, 3-bis (4-methoxyphenyl) propane-1, 3-dione.
Typische UV-absorbierende Ester der p-Aminobenzoesäure (III) sind:Typical UV-absorbing esters of p-aminobenzoic acid (III) are:
Ethyl-4-bis(hydroxypropyl)aminobenzoat (Amerscheen® P),Ethyl 4-bis (hydroxypropyl) aminobenzoate (Amerscheen® P),
2,3-Dihydroxypropyl-4-aminobenzoat (Nipa® GMPA),2,3-dihydroxypropyl-4-aminobenzoate (Nipa® GMPA),
Menthyl-2-aminobenzoat (Sunarome® UVA), 2-Emylhexyl-4-dimethylaminobenzoat (Escalol® 507),Menthyl 2-aminobenzoate (Sunarome® UVA), 2-emylhexyl 4-dimethylaminobenzoate (Escalol® 507),
Amyl-4-dimethylaminobenzoat,Amyl 4-dimethylaminobenzoate,
Ethyl-4-dimethylaminobenzoat,Ethyl 4-dimethylaminobenzoate,
Butyl-4-dimethylaminobenzoat,Butyl 4-dimethylaminobenzoate,
Octyl-4-dimethylaminobenzoat, Lauryl-4-dimethylaminobenzoat,Octyl-4-dimethylaminobenzoate, lauryl-4-dimethylaminobenzoate,
Oleyl-4-dimethylaminobenzoat,Oleyl 4-dimethylaminobenzoate,
4-Bis-(polyethoxy)-4-aminobenzoesäurepolyethoxyethylester (Uvinul® P-25),4-bis- (polyethoxy) -4-aminobenzoic acid polyethoxyethyl ester (Uvinul® P-25),
N-propoxyliertes Ethyl-4-aminobenzoat.N-propoxylated ethyl 4-aminobenzoate.
Typische UV-absorbierende Ester der Zimtsäure (IN) sind:Typical UV-absorbing esters of cinnamic acid (IN) are:
2-Ethylhexyl-4-methoxycinnamat (Uvinul® MC80, Parsol® MCX),2-ethylhexyl-4-methoxycinnamate (Uvinul® MC80, Parsol® MCX),
2-Ethoxyethyl-4-methoxycinnamat,2-ethoxyethyl 4-methoxycinnamate,
Propyl-4-methoxycinnamat, iso-Amyl-4-methoxycinnamat,Propyl 4-methoxycinnamate, iso-amyl 4-methoxycinnamate,
Cyclohexyl-4-methoxycinnamat, iso-Propyl-4-methoxycinnamat,Cyclohexyl-4-methoxycinnamate, iso-propyl-4-methoxycinnamate,
Octylcinnamat,octyl,
Ethyl-4-isopropylcinnamat, Ethyl-α-cyano-ß-phenylcinnamat,Ethyl 4-isopropylcinnamate, ethyl α-cyano-β-phenylcinnamate,
2-Ethylhexyl-α-cyano-ß-phenylcinnamat.2-ethylhexyl α-cyano-ß-phenylcinnamate.
Typische UV-absorbierende Ester der Salicylsäure (V) sind:Typical UV-absorbing esters of salicylic acid (V) are:
2-Ethylhexylsalicylat (Sunarome® WMO), 3 ,3 ,5-Trimethylcyclohexyl-2-hydroxybenzoat, 3 ,3 ,5 -Trimethylcyclohexyl-2-acetamidobenzoat,2-ethylhexyl salicylate (Sunarome® WMO), 3, 3, 5-trimethylcyclohexyl-2-hydroxybenzoate, 3, 3, 5 -trimethylcyclohexyl-2-acetamidobenzoate,
2-Ethylhexyl-2-(4-phenylbenzoyl)benzoat,2-Ethylhexyl-2- (4-phenylbenzoyl) benzoate,
4-Isopropylbenzylsalicylat,4-isopropylbenzyl,
Amylsalicylat,amyl salicylate,
Menthylsalicylat,menthyl,
Homomethylsalicylat,homomethyl salicylate,
Phenylsalicylat,phenyl salicylate,
Benzylsalicylat, iso-Decylsalicylat.Benzyl salicylate, iso-decyl salicylate.
Typische UN-absorbierende stickstofffreie 2-Hydroxybenzophenone (VI) sind:Typical UN-absorbing nitrogen-free 2-hydroxybenzophenones (VI) are:
2-Hydroxy-4-methoxybenzophenon (Uvinul® M40),2-hydroxy-4-methoxybenzophenone (Uvinul® M40),
2,2'-Dihydroxy-4-methoxybenzophenon (Spectra-Sorb® UV-24), 2,4-Dihydroxybenzophenon (Uvinul® 3000),2,2'-dihydroxy-4-methoxybenzophenone (Spectra-Sorb® UV-24), 2,4-dihydroxybenzophenone (Uvinul® 3000),
2,2',4,4'-Tetrahydroxybenzophenon (Uvinul® D-50),2,2 ', 4,4'-tetrahydroxybenzophenone (Uvinul® D-50),
2,2'-Dihydroxy-4,4'-dimethoxybenzophenon (Uvinul® D-49),2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinul® D-49),
2,2-Dihydroxy-4,4-dimethoxybenzophenon (Uvinul® 3049),2,2-dihydroxy-4,4-dimethoxybenzophenone (Uvinul® 3049),
2-Hydroxy-4-(2-ethylhexyloxy)benzophenon, 2-Hydroxy-4-(n-octyloxy)benzophenon (Uvinul® 3008),2-hydroxy-4- (2-ethylhexyloxy) benzophenone, 2-hydroxy-4- (n-octyloxy) benzophenone (Uvinul® 3008),
2-Hydroxy-4-methoxy-4 ' -methylbenzophenon (Mexenone®),2-hydroxy-4-methoxy-4'-methylbenzophenone (Mexenone®),
2-Ethylhexyl-4 ' -phenylbenzophenon-2-carboxylat,2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate,
2-Hydroxy-3 -carboxybenzophenon,2-hydroxy-3-carboxybenzophenone,
Benzophenon-3 -cocoylacetatether, 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure (Uvinul® MS 40) und derenBenzophenone-3-cocoyl acetate ether, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (Uvinul® MS 40) and their
Νatriumsalz,Νatriumsalz,
2,2'-Dihydroxy-4,4'-dimethoxybenzophenon-5,5'-bissulfonsäure und deren Νatriumsalz2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bissulfonic acid and its sodium salt
(Uvinul® DS 49).(Uvinul® DS 49).
Typische UV-absorbierende Phenylbenzimidazole (VII) sind:Typical UV-absorbing phenylbenzimidazoles (VII) are:
2-Phenylbenzimidazol-5-sulfonsäure (Eusolex® 232) und deren Kalium-, Natrium- und2-phenylbenzimidazole-5-sulfonic acid (Eusolex® 232) and its potassium, sodium and
Triethanolaminsalze,triethanolamine,
2- [5 ,6-Disulfo( 1 H-benzimidazol-2-yl)phenyl] - 1 H-benzimidazol-5 ,6-disulfonsäure.2- [5,6-Disulfo (1H-benzimidazol-2-yl) phenyl] -1H-benzimidazol-5,6-disulfonic acid.
Typische UV-absorbierende Acrylate (VIII) sind: 3 -Imidazol-4-yl-acrylsäure, 3-Imidazol-4-yl-acrylsäureethylester, 2-Cyano-3-(4-methoxyphenyl)acrylsäure, 2-Cyano-3-(4-methoxyphenyl)acrylsäurehexylester.Typical UV-absorbing 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) acrylic acid hexyl ester.
Bevorzugte Acrylate sind C6- bis C18-Alkylesters oder C5- bis C8-Cycloalkylesters der 2- Cyano-3,3-diphenylacrylsäure. Der C6- bis C18-Alkoholrest in den Cyano-3,3- diphenylacrylsäureestern kann linear oder ein- oder mehrfach verzweigt sein, er kann natürlichen oder synthetischen Ursprungs ein. Derartige Alkohole können beispielsweise Fettalkohole, Oxo- Alkohole, Ziegler- Alkohole oder Guerbet- Alkohole sein. Typische Beispiele für derartige Verbindungen sind der 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 oder Eicosylester. Es können auch ungesättigte Alkoholreste wie der Oleyl-, Linolyl- oder der Linolenyl-Rest auftreten. Es können auch Mischungen derartiger Ester vorliegen.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.
Als C5- bis C8-Cycloalkanolreste in den Cyano-3,3-diphenylacrylsäureestern kommen beispielsweise Cyclopentyl-, 2- oder 3-Methylcyclopentyl-, Cyclohexyl-, 2-, 3- oder 4- Methylcyclohexyl-, Dimethylcyclohexyl-, Cycloheptyl- oder Cyclooctyl-Reste in Betracht.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.
Bevorzugt werden lineare oder ein- oder mehrfach verzweigte C8- bis C13-Alkylesters der 2-Cyano-3,3-diphenylacrylsäure. Der entsprechende 2-Ethylhexylester ist als Uvinul® N- 539 T der BASF Aktiengesellschaft im Handel.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.
Typische UV-absorbierende Diarylbutadiene (IX) sind insbesondere 4,4-Diarylbutadiene der Formel (1), wie sie in der DE-A 198 28 463 für kosmetische und pharmazeutische Zubereitungen beschrieben sind: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 der das Diensystem in der Z,Z-; Z,E-; E,Z- oder E,E-Konfiguration oder einer Mischung davon vorliegt und in der die Variablen unabhängig voneinander folgende Bedeutung haben: 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:
R1 und R2 R 1 and R 2
Wasserstoff, Cι-C2o-Alkyl, C2-C10-Alkenyl, C3-C10-Cycloalkyl, C3-Cι0-Cycloalkenyl, C C^-Alkoxy, C1-C2o-Alkoxycarbonyl, Cι-Cι2-Alkylamino, CrCπ-Dialkylamino, Aryl, Heteroaryl, gegebenenfalls substituiert, sowie wasserlöslich machende Substituenten, ausgewählt aus der Gruppe bestehend ausAre hydrogen, C 2 -alkyl, C 2 -C 10 alkenyl, C 3 -C 10 cycloalkyl, C 3 -Cι 0 cycloalkenyl, CC ^ alkoxy, C 1 -C 2 o-alkoxycarbonyl, Cι- C 2 alkylamino, CrCπ dialkylamino, aryl, heteroaryl, optionally substituted, and water-solubilizing substituents selected from the group consisting of
Carboxylat-, Sulfonat- oder Ammoniumresten;Carboxylate, sulfonate or ammonium residues;
R3 Wasserstoff, COOR5, COR5, CONR5R6, CN;R 3 is hydrogen, COOR 5 , COR 5 , CONR 5 R 6 , CN;
R4 COOR6, COR6, CONR5R6;R 4 COOR 6 , COR 6 , CONR 5 R 6 ;
R5 Wasserstoff, [X]0-R7, Cj- -Alkylen-SOsY, Cι-C6-Alkylen-PO3Y, C C6-Alkylen- N(R8)3 + A";R 5 is hydrogen, [X] 0 -R 7 , Cj- -alkylene-SOsY, -C-C 6 -alkylene-PO 3 Y, CC 6 -alkylene- N (R 8 ) 3 + A " ;
R6 [X]0-R7, Cι-C6-Alkylen-SO3Y, C1-C6-Alkylen-PO3Y, Cι-C6-Alkylen-N(R8)3 + A";R 6 [X] 0 -R 7 , -CC 6 alkylene-SO 3 Y, C 1 -C 6 -alkylene-PO 3 Y, -C 6 -alkylene-N (R 8 ) 3 + A " ;
X -CH2-CH2-Z-, -CH2-CH2-CH2-Z-, -CH(CH3)-CH2-Z-, -CH2-CH2-CH2-CH2-Z-, -CH2- CH(CH2-CH3)-Z-;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, SO4R9;A Cl, Br, J, SO 4 R 9 ;
Y Wasserstoff, Na+, K+, Mg2+, Ca2+, Li+, Al3+, N(R8)4 +;Y is hydrogen, Na + , K + , Mg 2+ , Ca 2+ , Li + , Al 3+ , N (R 8 ) 4 + ;
Z O, NH;Z O, NH;
R7 und R8 R 7 and R 8
Wasserstoff, Ci-Cβ-Alk l, C2-C6-Alkenyl, Cι-C6-Acyl;Hydrogen, Ci-Cβ-Alk l, C 2 -C 6 alkenyl, -CC 6 -acyl;
R9 Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl; n 1 bis 3;R 9 is hydrogen, -CC 6 alkyl, C 2 -C 6 alkenyl; n 1 to 3;
o 1 bis 150.o 1 to 150.
Bezüglich der näheren Spezifizierung der Strukturen der 4,4-Diarylbutadiene der Formel (1) und Beispiele für solche Verbindungen (1) wird ausdrücklich auf die Offenbarung der DE-A 198 28 463 verwiesen. Als ein typisches Beispiel für einen Vertreter einer solchen Verbindung (IX) wird l,l-Bis(neopentyloxycarbonyl)-4,4-diphenyl-l,3-butadien genannt.With regard to the more detailed specification of the structures of the 4,4-diarylbutadienes of the formula (1) and examples of such compounds (1), reference is expressly made to the disclosure of DE-A 198 28 463. A typical example of a representative of such a compound (IX) is 1,1-bis (neopentyloxycarbonyl) -4,4-diphenyl-1,3-butadiene.
Typische UV-absorbierende aminosubstituierte Hydroxybenzophenone (X) sind insbesondere solche der Formel (2), wie sie in der deutschen Patentanmeldung Az. 199 17 906.9 für kosmetische und pharmazeutische Zubereitungen beschrieben sind: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 der die Variablen unabhängig voneinander folgende Bedeutung haben:in which the variables have the following meaning independently of one another:
R^d R2 Wasserstoff, C1-C20-Alkyl, C2-C10-Alkenyl, C3-C10-Cycloalkyl, C3-C10- Cycloalkenyl, wobei die Substituenten R1 und R2 gemeinsam mit dem Stickstoffatom, an dem sie gebunden sind, einen 5- oder 6-Ring bilden können;R ^ d R 2 is 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;
R3 und R4 Ci- jo-Al yl, C -Cι0-Alkenyl, C3-C10-Cycloalkyl, C3-C10-Cycloalkenyl, d- C12-Alkoxy, C1-C2o-Alkoxycarbonyl, Ci-Cπ-Alkylamino, Ci-C^- Dialkylamino, Aryl, Heteroaryl, gegebenenfalls substituiert, sowie wasserlöslich machende Substituenten, ausgewählt aus der Gruppe bestehend aus einer Nitrilgruppe, Carboxylat-, Sulfonat- oder Arnmoniumresten;R 3 and R 4 Ci- jo-Al yl, C -Cι 0 alkenyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkenyl, d- C 12 alkoxy, C 1 -C 2 o-alkoxycarbonyl , Ci-Cπ-alkylamino, Ci-C ^ - dialkylamino, aryl, heteroaryl, optionally substituted, and water-solubilizing substituents selected from the group consisting of a nitrile group, carboxylate, sulfonate or ammonium residues;
X Wasserstoff, COOR5, CONR6R7; R5 bis R7 Wasserstoff, C1-C20-Alkyl, C2-C10-Alkenyl, C3-Cιo-Cycloalkyl, C3-C10- Cycloalkenyl, -(Y-O)0-Z, Aryl;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 -Cιo cycloalkyl, C 3 -C 10 cycloalkenyl, - (YO) 0 -Z, aryl;
Y -(CH2)2- -(CH2)3-, -(CH2)4- -CH(CH3)-CH2-;Y - (CH 2 ) 2 - - (CH 2 ) 3 -, - (CH 2 ) 4 - -CH (CH 3 ) -CH2-;
Z -CH2-CH3, -CH2-CH2-CH3, -CH2-CH2-CH2-CH3, -CH(CH3)-CH3;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 bis 3;m 0 to 3;
n 0 bis 4;n 0 to 4;
o 1 bis 20.o 1 to 20.
Bezüglich der näheren Spezifizierung der Strukturen der ammosubstituierten Hydroxybenzophenone der Formel II und Beispiele für solche Verbindungen II wird in diesem Zusammenhang ausdrücklich auf die Offenbarung der deutschen Patentanmeldung Az. 199 17 906.9 verwiesen. Als ein typisches Beispiel für einen Vertreter einer solchen Verbindung (X) wird 2-(4'-Diethylamino-2'-hydroxybenzoyl)benzoesäure-n-hexylester genannt.With regard to the more detailed specification of the structures of the amino-substituted hydroxybenzophenones of the formula II and examples of such compounds II, reference is expressly made in this connection to the disclosure of the German patent application Az. 199 17 906.9. 2- (4'-Diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester is mentioned as a typical example of a representative of such a compound (X).
Typische UV-absorbierende Triazine (XI) sind:Typical UV-absorbing triazines (XI) are:
2,4,6-Trianilino-4-(carbo-2 ' -ethylhexyl- 1 ' -oxy)- 1 ,3 ,5-triazin (Uvinul® T- 150), 2-Ethylhexyl-4-{[4-{4-[tert.-butylamino]carbonyl]anilino}-6-(4-{[2- ethylhexyl)oxy]carbonyl}anilino)-l,3,5-triazin-2-yl]amino}benzoat,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) -l, 3,5-triazin-2-yl] amino} benzoate,
2-(4-Methoxyphenyl)-4,6-di[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-l,3,5-triazin.2- (4-methoxyphenyl) -4,6-di [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -l, 3,5-triazine.
Vertreter der Verbindungen B des Typs (I) bis (VIII) und (XI) sind im übrigen in der WO 97/44422 und der WO 96/03486 beschrieben.Representatives of compounds B of types (I) to (VIII) and (XI) are also described in WO 97/44422 and WO 96/03486.
Neben den Verbindungen des Typs (I) bis (XI) können als organische UV-Absorber B weiterhin beispielsweise auch noch die folgenden verwendet werden:In addition to the compounds of types (I) to (XI), the following can also be used as organic UV absorbers B:
3-(4-Methylbenzyliden)bornan-2-on (Eusolex® 6300), 5 -(3 ,3 -Dimethyl-2-norbornyliden)-3 -penten-2-on, 3 -Benzylidenbornan-2-on, Digalloyltrioleat,3- (4-methylbenzylidene) bornan-2-one (Eusolex® 6300), 5 - (3, 3-dimethyl-2-norbornylidene) -3-penten-2-one, 3-benzylidene bornan-2-one, digalloyltrioleate,
2-Hydroxy- 1 ,4-naphthalendion,2-hydroxy-1,4-naphthalenedione,
5-Methyl-2-phenylbenzoxazol,5-Methyl-2-phenylbenzoxazole,
Dibenzaldehydamin, Dianisoylmethan,Dibenzaldehydamine, dianisoylmethane,
Methyleugenol,methyl eugenol,
2-Amino-6-hydroxypurin,2-amino-6-hydroxypurine,
N-(4-Ethoxycarbonylphenyl)-N' -methyl-N' -phenylformamidin (Givosorb® UV 1 ),N- (4-ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidin (Givosorb® UV 1),
N-(4-Ethoxycarbonylphenyl)-N' -ethyl-N' -phenylformamidin (Givosorb® UV2), 3-(4'-Methylbenzyliden)campher (Uvinul® MBC95),N- (4-ethoxycarbonylphenyl) -N'-ethyl-N'-phenylformamidine (Givosorb® UV2), 3- (4'-methylbenzylidene) camphor (Uvinul® MBC95),
N -(2-Ethoxyphenyl)-N -(2-ethylphenyl)ethandiamid,N - (2-ethoxyphenyl) -N - (2-ethylphenyl) ethanediamide,
N1-(2-Ethoxyphenyl)-N2-(4-dodecaphenyl)ethandiamid,N 1 - (2-ethoxyphenyl) -N 2 - (4-dodecaphenyl) ethanediamide,
2-Ethylhexyl-2-cyano-(3-oxo-2,3-dihydro-lH-isoindol-l-yliden)ethanoat,2-ethylhexyl-2-cyano- (3-oxo-2,3-dihydro-lH-isoindol-l-ylidene) ethanoate,
1 , 1 -Dicyano-2-(4-butyloxy)phenyl-2-phenyl-ethen.1, 1-Dicyano-2- (4-butyloxy) phenyl-2-phenyl-ethene.
Besonders bevorzugte organische UV-Absorber B, die gemeinsam mit Zinkoxid und/oderParticularly preferred organic UV absorbers B, which together with zinc oxide and / or
Titandioxid eingesetzt werden, sind die Verbindungen:The compounds used are titanium dioxide:
l-(4-tert.-Butylphenyl)-3-(4-methoxyphenyl)propan-l,3-dion (Uvinul® BMBM), 4-Bis-(polyethoxy)-4-aminobenzoesäurepolyethoxyethylester (Uvinul® P-25),l- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-l, 3-dione (Uvinul® BMBM), 4-bis- (polyethoxy) -4-aminobenzoic acid polyethoxyethyl ester (Uvinul® P-25),
2-Ethylhexyl-4-methoxycinnamat (Uvinul® MC80),2-ethylhexyl-4-methoxycinnamate (Uvinul® MC80),
2-Hydroxy-4-methoxybenzophenon (Uvinul® M40),2-hydroxy-4-methoxybenzophenone (Uvinul® M40),
2,4-Dihydroxybenzophenon (Uvinul® 3000),2,4-dihydroxybenzophenone (Uvinul® 3000),
2,2',4,4'-Tetrahydroxybenzophenon (Uvinul® D-50), 2,2'-Dihydroxy-4,4'-dimethoxybenzophenon (Uvinul® D-49),2,2 ', 4,4'-tetrahydroxybenzophenone (Uvinul® D-50), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinul® D-49),
2,2-Dihydroxy-4,4-dimethoxybenzophenon (Uvinul® 3049),2,2-dihydroxy-4,4-dimethoxybenzophenone (Uvinul® 3049),
2-Hydroxy-4-(2-ethylhexyloxy)benzophenon,2-hydroxy-4- (2-ethylhexyloxy) benzophenone,
2-Hydroxy-4-(n-octyloxy)benzophenon (Uvinul® 3008),2-hydroxy-4- (n-octyloxy) benzophenone (Uvinul® 3008),
2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure (Uvinul® MS 40) und deren Salze, 2,2'-Dihydroxy-4,4'-dimethoxybenzophenon-5,5'-bissulfonsäure und deren Salze2-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),(Uvinul® DS49),
2-Cyano-3,3-diphenylacrylsäure-2'-ethylhexylester (Uvinul® N 539 T),2'-ethyl-2-cyano-3,3-diphenylacrylic acid (Uvinul® N 539 T),
2-Cyano-3,3-diphenylacrylsäureethylester (Uvinul® 3035),Ethyl 2-cyano-3,3-diphenylacrylate (Uvinul® 3035),
1 , 1 -Bis(neopentyloxycarbonyl)-4,4-diphenyl- 1 ,3 -butadien, 2-(4 ' -Diethylamino-2 ' -hydroxybenzoyl)benzoesäure-n-hexylester,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-l '-oxy)-l,3,5-triazin (Uvinul® T-150), 3-(4'-Methylbenzyliden)campher (Uvinul® MBC95).2,4,6-trianilino-4- (carbo-2'-ethylhexyl-l'-oxy) -l, 3,5-triazine (Uvinul® T-150), 3- (4'-methylbenzylidene) camphor (Uvinul® MBC95).
Bisweilen kann es von Vorteil sein, wenn die Komponenten A und B zusammen mit Antioxidantien und/oder Radikalfänger eingesetzt werden. Zu den Antioxidantien und Radikalfängern, die hier zur Anwendung gelangen können, zählen alle Verbindungen, die üblicherweise zur Stabilisierung von Nahrungs- und Futtermittel aber auch zur Stabilisierung von Kunststoffen oder Schmierstoffen eingesetzt werden. Eine Liste solcher Verbindungen findet man z.B. in Kirk-Othmer, Encyclopedia of Chemical Technology, fourth edition, volume 3, p. 424-447 oder in Ullmann's Encyclopedia of Industrial Chemistry, sixth edition, 2000 Electronic Release, chapters antioxidants und food additives.Sometimes it can be advantageous if components A and B are used together with antioxidants and / or radical scavengers. The antioxidants and radical scavengers that can be used here include all compounds that are usually used to stabilize food and feed but also to stabilize plastics or lubricants. A list of such connections can be found e.g. 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 additives.
Es zählen jedoch insbesondere dazu:However, these include in particular:
- Substituierte Phenole, Hydrochinone, Brenzcatechine und Gallate wie 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'-Methylenbis(4-methyl-6-tert.-butylphenol), Propyl-, Octyl- und Dodecylgallat oder tert.-Butylhydrochinon (TBHQ), butyliertes Hydroxyanisol (BHA) und butyliertes Hydroxytoluol (BHT),- 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®- Antioxidantien (von Ciba-Geigy) wie Irganox® 1010Irganox® antioxidants (from Ciba-Geigy) such as Irganox® 1010
(Tetrakismethylen(3,5-di-tert-butyl-4-hydroxycinnamat))methan), Irganox® 1035(Tetrakis methylene (3,5-di-tert-butyl-4-hydroxycinnamate)) methane), Irganox® 1035
(Thiodiethylenbis(3,5-di-tert-butyl-4-hydroxycinnamat)) und Irganox® 1076 (Octadecylpropan(3-benzene-3',5'-di-tert-butyl-4'-hydroxybenzyl)phosphonat),(Thiodiethylenebis (3,5-di-tert-butyl-4-hydroxycinnamate)) and Irganox® 1076 (octadecylpropane (3-benzene-3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) phosphonate),
Trihydroxybutyrophenon (THBP),Trihydroxybutyrophenone (THBP),
α-Tocopherol und dessen natürliche oder synthetische Derivate wie Acetyl-α- Tocopherol,α-tocopherol and its natural or synthetic derivatives such as acetyl-α-tocopherol,
Ascorbinsäure und Ascorbinsäure-Derivate, insbesondere Veresterungsprodukte mit langkettigen Fettsäuren wie Ascorbylpalmitat,Ascorbic acid and ascorbic acid derivatives, in particular esterification products with long-chain fatty acids such as ascorbyl palmitate,
- Diazabicyclooctan (DABCO), Chroman-Derivate wie langkettige Ester der 2,5,7,8-Tetramethyl-6- hydroxychroman-2-säure,Diazabicyclooctane (DABCO), Chroman derivatives such as long-chain esters of 2,5,7,8-tetramethyl-6-hydroxychroman-2-acid,
aromatische Amine wie Ethoxyquin,aromatic amines such as ethoxyquin,
organische Sulfide wie 3,3'-Thiodipropionsäure und Dilaurylthiodipropionat,organic sulfides such as 3,3'-thiodipropionic acid and dilaurylthiodipropionate,
sterisch gehinderte Amine, z.B. vom Tetramethylpiperidin-Typ wie Uvinul® 4049H, Uvinul® 4050H und Uvinul® 5050H der BASF AG,sterically hindered amines, e.g. of the tetramethylpiperidine type such as Uvinul® 4049H, Uvinul® 4050H and Uvinul® 5050H from BASF AG,
freie Radikale vom N-Oxyl-Typ wie 4-Hydroxytetramethylpiperidin-N-oxid, deren Veresterungsprodukte mit Carbonsäuren und weitere Derivate,free radicals of the N-oxyl type, such as 4-hydroxytetramethylpiperidine-N-oxide, their esterification products with carboxylic acids and other derivatives,
Hydroxylamine wie diej enigen von Dialkylaminen und Hydroxylaminether- Derivate der Tetramethylpiperidin- Verbindungen,Hydroxylamines such as those of dialkylamines and hydroxylamine ether derivatives of the tetramethylpiperidine compounds,
Ascorbin-, Milch-, Citronen- und Weinsäure und deren Salze.Ascorbic, lactic, citric and tartaric acid and their salts.
Die anorganischen Pigmente A und organischen UV-Absorber B wirken in hervorragender Weise als textilfaseraffine UV-Absorber zusammen und verstärken sich gegenseitig in ihrer Wirkung. Zum einen schützen sie in auf textiles Material aufgebrachter Form die menschliche Haut vor schädigender UV-Strahlung. Zum anderen schützen sie gefärbtes textiles Material vor Verblassung der Farbe. Vorzugsweise treten beide Schutzeffekte gleichzeitig auf.The inorganic pigments A and organic UV absorber B work together excellently as textile fiber-affine UV absorbers and reinforce each other in their effect. On the one hand, they protect human skin from damaging UV radiation when applied to textile material. On the other hand, they protect dyed textile material from color fading. Both protective effects preferably occur simultaneously.
Textile Materialien, worauf die Komponenten A und B aufziehen und dort ihre Schutzwirkung entfalten, umfassen insbesondere Bekleidungsartikel, d.h. Textilien, die auf der menschlichen Haut getragen werden, aber auch Haus- und Gartenartikel aus oder mit gefärbten Textilien wie Markisen und Sonnenschirme, die intensiver Sonnenbestrahlung ausgesetzt sind. Vorzugsweise besteht dieses zu schützende textile Material aus Cellulose (Baumwolle) oder enthält Cellulose, beispielsweise Bekleidungstextilien aus Baumwolle oder aus Baumwoll-Polyester-Mischungen.Textile materials, on which components A and B mount and develop their protective effect there, include in particular items of clothing, i.e. Textiles that are worn on human skin, but also house and garden items made of or with colored textiles such as awnings and parasols that are exposed to intense sunlight. This textile material to be protected preferably consists of cellulose (cotton) or contains cellulose, for example clothing textiles made of cotton or of cotton-polyester mixtures.
Gegenstand der vorliegenden Erfindung ist auch die Verwendung von Zinkoxid und/oder Titandioxid zusammen mit organischen UV- Absorbern auf textilem Material zum Schutz der menschlichen Haut vor schädigender UV-Strahlung und/oder zum Schutz von gefärbtem textilem Material vor Verblassung der Farbe.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 from color fading.
Üblicherweise wird das Gemisch enthaltend die Komponenten A und B in Form einer wäßrigen Flotte, die die Komponenten A und B enthält und daneben weitere Inhaltsstoffe enthalten kann, auf das textile Material, beispielsweise durch Sprühen oder Eintauchen und Abpressen, aufgebracht. Die Komponenten A und B können bei der Textilausrüstung während der Herstellung des textilen Materials, bei der Textilwäsche, bei der Textilwäschevorbehandlung und/oder der Textilwäschenachbehandlung auf das textile Material aufgebracht werden.The mixture comprising components A and B is usually applied to the textile material, for example by spraying or dipping and pressing, in the form of an aqueous liquor which contains components A and B and may also contain further ingredients. Components A and B can be applied to the textile material during textile finishing during the production of the textile material, during textile washing, during textile laundry pretreatment and / or after-textile treatment.
Durch die UV-Schutzausrüstung wird der UV-Schutzfaktor UPF des textilen Materials erhöht.The UV protection factor UPF of the textile material is increased by the UV protective equipment.
Der UN-Schutzfaktor UPF ("Ultraviolet Radiation Protection Factor") von Textilien wird gemäß der australischen/neuseeländischen Norm AS/NZS 4399:1996 mittels einer in vitro- Methode gestimmt. Gemessen wird die UV-Durchlässigkeit des textilen Objektes. Aus der spektralen Transmission läßt sich anhand der nachfolgenden Gleichung der Schutzfaktor direkt ermitteln:The UN 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:
wobeiin which
sλ die Spektraleinstrahlung der Sonne im UV-Bereich bei der Wellenlänge λ,s λ the spectral radiation of the sun in the UV range at the wavelength λ,
Ελ die spektrale Erythemwirksamkeit der UV-Strahlung bei der Wellenlänge λ, und τλ die spektrale Durchlässigkeit des textilen Objektes bei der Wellenlänge λ ist.Ε λ is the spectral erythema effectiveness of UV radiation at the wavelength λ, and τ λ is the spectral transmission of the textile object at the wavelength λ.
Gegenstand der vorliegenden Erfindung ist auch eine Textilwaschmittel-Formulierung, welche 0,01 bis 20 Gew.-%, bevorzugt 0,1 bis 10 Gew.-%, besonders bevorzugt 0,1 bis 5 Gew.-% der Komponenten A und B neben weiteren üblichen Bestandteilen enthält. Vorzugsweise beträgt das Gewichtsverhältnis der Komponente A zu der Komponente B von 20 : 1 bis 1 : 10, besonders bevorzugt von 8 : 1 bis 1 : 5 und speziell bevorzugt von 3 : 1 bis 1 : 1. Dabei kann die Zugabe der Komponenten A und B separat in die Formulierung erfolgen oder es kann die vorgefertigte Mischung aus A und B in die Formulierung eingearbeitet werden.The present invention also relates to a textile detergent formulation which comprises 0.01 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.1 to 5 % By weight of components A and B in addition to other customary constituents. 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 separately in the formulation or the pre-made mixture of A and B can be incorporated into the formulation.
Erfindungsgemäße Textilwaschmittel-Formulierungen können feste oder flüssige Formulierungen sein.Textile detergent formulations according to the invention can be solid or liquid formulations.
Erfmdungsgemäße feste Waschmittelformulierungen enthalten in der Regel als weitere übliche BestandteileSolid detergent formulations according to the invention generally contain further customary constituents
(c) 0,1 bis 40 Gew.-% mindestens eines nichtionischen und/oder anionischen Tensids als Komponente C,(c) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant as component C,
(d) 0 bis 50 Gew.-% eines oder mehrerer anorganischer Builder als Komponente D,(d) 0 to 50% by weight of one or more inorganic builders as component D,
(e) 0 bis 20 Gew.-% eines oder mehrerer organischer Cόbuilder E,(e) 0 to 20% by weight of one or more organic builders E,
(f) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe wie kationische Tenside, Stellmittel, Enzyme, Parfüm, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, Vergrauungs- inhibitoren, Soil-Release-Polyester, Farbstoffe, Auflösungsverbesserer und/oder Sprengmittel als Komponente F,(f) 0 to 60% by weight of other customary ingredients such as cationic surfactants, bulking agents, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, dye transfer inhibitors, graying inhibitors, soil release polyesters, dyes, dissolution improvers and / or disintegrant as component F,
wobei die Summe der Komponenten A bis F 100 Gew.-% ergibt.the sum of components A to F being 100% by weight.
Die erfindungsgemäßen festen Waschmittelformulierungen liegen üblicherweise als Pulver, Granulat, Extrudat oder in Tablettenform vor.The solid detergent formulations according to the invention are usually in the form of powder, granules, extrudate or in tablet form.
Erfindungsgemäße flüssige Waschmittelformulierungen enthalten in der Regel als weitere übliche BestandteileLiquid detergent formulations according to the invention generally contain further customary constituents
(c) 0,1 bis 40 Gew.-% mindestens eines nichtionischen und/oder anionischen Tensids als Komponente C, (d) 0 bis 20 Gew.-% eines oder mehrerer anorganischer Builder als Komponente D,(c) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant as component C, (d) 0 to 20% by weight of one or more inorganic builders as component D,
(e) 0 bis 10 Gew.-% eines oder mehrerer organischer Cobuilder als Komponente E,(e) 0 to 10% by weight of one or more organic cobuilders as component E,
(f) 0 bis 40 Gew.-% anderer üblicher Inhaltsstoffe wie kationische Tenside, Soda, Enzyme, Parfüm, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, Vergrauungs- inhibitoren, Soil-Release-Polyester, Farbstoffe, nicht-wäßrige Lösemittel Hydrotrope, Verdicker und/oder Alkanolamine als Komponente F und(f) 0 to 40% by weight of other customary ingredients such as cationic surfactants, soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes, non-aqueous Solvents hydrotropes, thickeners and / or alkanolamines as component F and
(g) 0 bis 99,85 Gew.-% Wasser als Komponente G,(g) 0 to 99.85% by weight of water as component G,
wobei die Summe der Komponenten A bis G 100 Gew.-% ergibt.the sum of components A to G being 100% by weight.
Geeignete anionische Tenside sind insbesondere:Suitable anionic surfactants are in particular:
(Fett)alkoholsulfate von (Fett)alkoholen mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen, z.B. C9- bis Cπ- Alkoholsulfate, C12- bis C14-Alkoholsulfate, C12- Cis-Alkoholsulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat;(Fat) alcohol sulfates of (fatty) alcohols with 8 to 22, preferably 10 to 18 carbon atoms, for example C 9 to Cπ alcohol sulfates, C 12 to C 14 alcohol sulfates, C 12 cis alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate , Palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;
sulfatierte alkoxylierte C - bis C22- Alkohole (Alkylethersulfate). Verbindungen dieser Art werden beispielsweise dadurch hergestellt, dass man zunächst einen C8- bis C22-, vorzugsweise einen C10- bis Cι8-Alkohol, z.B. einen Fettalkohol, alkoxyliert und das Alkoxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid;sulfated alkoxylated C to C 22 alcohols (alkyl ether sulfates). Compounds of this type are prepared, for example, by first alkoxylating a C 8 to C 22 , preferably a C 10 to C 8 alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation;
lineare C8- bis C20-Alkylbenzosulfonate (LAS), vorzugsweise lineare C9- bis C13- Alkylbenzolsulfonate und -Alkyltoluolsulfonate,linear C 8 to C 20 alkyl benzosulfonates (LAS), preferably linear C 9 to C 13 alkyl benzene sulfonates and alkyl toluenesulfonates,
Alkansulfonate wie C8- bis C^-, vorzugsweise C10- bis C18-Alkansulfonate,Alkanesulfonates such as C 8 - to C ^ -, preferably C 10 - to C 18 -alkanesulfonates,
Seifen wie beispielsweise die Na- und K-Salze von C8- bis C2 -Carbonsäuren.Soaps such as the Na and K salts of C 8 to C 2 carboxylic acids.
Die genannten anionischen Tenside werden dem Waschmittel vorzugsweise in Form von Salzen zugegeben. Geeignete Kationen in diesen Salzen sind Alkalimetallionen wie Natrium, Kalium und Lithium und Ammoniumionen wie Hydroxyethylammonium, Di(hydroxyethyl)ammonium und Tri(hydroxyethyl)ammonium.The anionic surfactants mentioned are preferably added to the detergent in the form of 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.
Geeignete nichtionische Tenside sind insbesondere:Suitable nonionic surfactants are in particular:
alkoxylierte C8- bis C22-Alkohole wie Fettalkoholalkoxylate oder Oxoalkoholalkoxylate. Diese können mit Ethylenoxid, Propylenoxid und/oder Butylenoxid alkoxyliert sein. Als Tenside einsetzbar sind hierbei sämtliche alkoxylierten Alkohole, die mindestens zwei Moleküle eines der vorstehend genannten Alkylenoxide addiert enthalten. Hierbei kommen Blockpolymerisate von Ethylenoxid,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 come block polymers of ethylene oxide,
Propylenoxid und/oder Butylenoxid in Betracht oder Anlagerungsprodukte, die die genannten Alkylenoxide in statistischer Verteilung enthalten. Die nichtionischen Tenside enthalten pro Mol Alkohol im allgemeinen 2 bis 50, vorzugsweise 3 bis 20 Mol mindestens eines Alkylenoxids. Vorzugsweise enthalten diese als Alkylenoxid Ethylenoxid. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome. Je nachPropylene oxide and / or butylene oxide or adducts 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
Art des bei der Herstellung verwendeten Alkoxylierungskatalysators weisen die Alkoxylate eine breite oder enge Alkylenoxid-Homologenverteilung auf;The type of alkoxylation catalyst used in the preparation has a broad or narrow alkylene oxide homolog distribution;
Alkylphenolalkoxylate wie Alkylphenolethoxylate mit C6- bis Cι4-Alkylketten und 5 bis 30 Alkylenoxideinheiten;Alkylphenol alkoxylates such as alkylphenol ethoxylates with C 6 - to C 4 alkyl chains and 5 to 30 alkylene oxide units;
Alkylpolyglucoside mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen in der Alkylkette und im allgemeinen 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten;Alkyl polyglucosides having 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-Alkylglucamide, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate sowie Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid.- N-alkyl glucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.
Geeignete anorganische Builder sind insbesondere:Suitable inorganic builders are in particular:
- kristalline oder amorphe Alumosilicate mit ionenaustauschenden Eigenschaften wie insbesondere Zeolithe. Als Zeolithe geeignet sind insbesondere Zeolithe A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg oder Ammonium ausgetauscht ist; kristalline Silicate wie insbesondere Disilicate oder Schichtsilicate, z.B. δ-Na2Si2O5 oder ß-Na2Si2O5. Die Silicate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, vorzugsweise als Na-, Li- und Mg-Silicate;- Crystalline or amorphous aluminosilicates with ion-exchanging properties such as, in particular, 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 partly replaced by other cations such as Li, K, Ca, Mg or ammonium; crystalline silicates such as, in particular, disilicates or layered silicates, for example 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;
- amorphe Silicate wie Natriummetasilicat oder amorphes Disilicat;- amorphous silicates such as sodium metasilicate or amorphous disilicate;
Carbonate und Hydrogencarbonate. Diese können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden. Bevorzugt sind Na-, Li- und Mg-Carbonate bzw. -Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat;Carbonates and hydrogen carbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Na, Li and Mg carbonates or bicarbonates are preferred, in particular sodium carbonate and / or sodium bicarbonate;
Polyphosphate wie Pentanatriumtriphosphat.Polyphosphates such as pentasodium triphosphate.
Geeignete organische Cobuilder sind insbesondere niedermolekulare, oligomere oder polymere Carbonsäuren.Suitable organic cobuilders are in particular low molecular weight, oligomeric or polymeric carboxylic acids.
II
Geeignete niedermolekulare Carbonsäuren sind beispielsweise Citronensäure, hydrophob modifizierte Citronensäure wie z. B. Agaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Oxydibernsteinsäure, Propaήtricarbonsäure, Butantetracarbonsäure, Cyclopentantetra- carbonsäure, Alkyl- und Alkenylbernsteinsäuren und Aminopolycarbonsäuren wie z.B. Nitrilotriessigsäure, ß-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure;Suitable low molecular weight 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, propaήtricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids such as e.g. Nitrilotriacetic acid, ß-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediaminedisuccinic acid and methyl and ethylglycinediacetic acid;
Geeignete oligomere oder polymere Carbonsäuren sind beispielsweise Homopolymere der Acrylsäure, Oligomaleinsäuren, Copolymere der Maleinsäure mit Acrylsäure, Methacrylsäure, C2-C22-Olefine wie z.B. Isobuten oder langkettige α-Olefine, Vinylalkylether mit Cι-C8-Alkylgruppen, Vinylacetat, Vinylpropionat, (Meth)acrylester von C Cs- Alkoholen und Styrol. Bevorzugt verwendet man dieSuitable 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 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 Cs alcohols and styrene. It is preferred to use the
Homopolymeren der Acrylsäure sowie Copolymere von Acrylsäure mit Maleinsäure. Weiterhin eignen sich Polyasparaginsäuren als organische Cobuilder. Die oligomeren und polymeren Carbonsäuren werden in Säureform oder als Natriumsalz eingesetzt. Geeignete Bleichmittel sind beispielsweise Addukte von Wasserstoffperoxid an anorganische Salze wie z.B. Natriumperborat-Monohydrat, Natriumperborat-Tetrahydrat oder Natriumcarbonat-Perhydrat oder Percarbonsäuren wie Phthalimidopercapronsäure.Homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. 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 bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts such as sodium perborate monohydrate, sodium perborate tetrahydrate or sodium carbonate perhydrate or percarboxylic acids such as phthalimidopercaproic acid.
Als Bleichaktivatoren eignen sich beispielsweise N,N,N',N'-Tetraacetylethylendiamin (TAED), Natrium-p-nonanoyloxybenzolsulfonat oder N-Methylmorpholiniumacetonitril- methylsulfat.Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylethylene diamine (TAED), sodium p-nonanoyloxybenzenesulfonate or N-methylmorpholinium acetonitrile-methyl sulfate.
Vorzugsweise in Waschmitteln eingesetzte Enzyme sind Proteasen, Lipasen, Amylasen, Cellulasen, Oxidasen oder Peroxidasen.Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases or peroxidases.
Geeignete Farbübertragungsinhibitoren sind beispielsweise Homo- und Copolymere des 1- Vinylpyrrolidons, des 1-Vinylimidazols oder des 4-Vinylpyridin-N-oxids. Auch mit Chloressigsäure umgesetzte Homo- und Copolymere des 4-Vinylpyridins eignen sich als Farbübertragungsinhibitoren.Suitable color transfer inhibitors are, for example, homopolymers and copolymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine-N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.
Gegenstand der vorliegenden Erfindung sind ferner Wäschenachbehandlungs- und Wäschepflegemittel, welche 0,01 bis 20 Gew.-%, bevorzugt 0,1 bis 10 Gew.-%, besonders bevorzugt 0,1 bis 5 Gew.-% der Komponenten A und B neben weiteren üblichen Bestandteilen enthalten. Vorzugsweise beträgt das Gewichtsverhältnis der Komponente A zu der Komponente B von 20 : 1 bis 1 : 10, besonders bevorzugt von 8 : 1 bis 1 : 5, insbesondere von 3 : 1 bis 1 : 1. Dabei kann die Zugabe der Komponenten A und B separat in die Formulierung erfolgen oder es kann die vorgefertigte Mischung aus A und B in die Formulierung eingearbeitet werden.The present invention furthermore relates to laundry aftertreatment and laundry care compositions which, in addition to 0.01 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.1 to 5% by weight, of components A and B. contain other common ingredients. 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, in particular from 3: 1 to 1: 1. The addition of components A and B separately in the formulation or the pre-made mixture of A and B can be incorporated into the formulation.
Als weitere übliche Bestandteile enthalten die erfindungsgemäßen Wäschenachbehandlungs- und Wäschepflegemittel in der RegelThe laundry aftertreatment and laundry care compositions according to the invention generally contain further customary constituents
c) 0,1 bis 40 Gew.% mindestens eines kationischen Tensids als Komponente C,c) 0.1 to 40% by weight of at least one cationic surfactant as component C,
d) 0 bis 30 Gew.% eines oder mehrerer nichtionischer Tenside als Komponente D,d) 0 to 30% by weight of one or more nonionic surfactants as component D,
e) 0 bis 30 Gew.% weiterer üblicher Inhaltsstoffe wie Duft- und Farbstoffe,e) 0 to 30% by weight of other customary ingredients, such as fragrances and colorants,
Stabilisatoren, Faser- und Farbschutzadditive, Viskositätsmodifizierer, Soil- Release- Additive, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Komplexbildner, Korrosionsschutzadditive, Bakterizide, Konservierungsmittel, nicht wässriges Lösemittel, Hydrotrope und/oder Alkanolamine als Komponente E,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 solvents, hydrotropes and / or alkanolamines as component E,
f) 0 bis 25 Gew.% kationischer Polymere als Bindemittel als Komponente F, undf) 0 to 25% by weight of cationic polymers as binders as component F, and
g) Wasser zur Ergänzung auf 100 Gew.% als Komponente G.g) water to make up to 100% by weight as component G.
Als kationische Polymere (Komponente F) können alle natürlichen oder synthetischen kationischen Polymere verwendet werden, die Amino und/oder Ammoniumgruppen enthalten und wasserlöslich bzw. wasserdispergierbar sind. Beispiele für solche kationischen Polymere sind Polyethylenimine, amidierte, alkoxylierte und/oder alkylierte Polyethylenimine, vernetzte Polyethylemmine, Polyamidoamine, alkoxylierte und/oder alkylierte Polyamidoamine, vernetzte Polyamidoamine, mit Ethylenimin gepfropfte vernetzte Polyamidoamine, Amin-Epichlorhydrin-Polykondensate, Polyvinylamine, alkoxylierte Polyvinylamine, teilhydrolysierte Polyvinylformamide, Polyallylamine,All natural or synthetic cationic polymers which contain amino and / or ammonium groups and are water-soluble or water-dispersible can be used as cationic polymers (component F). Examples of such cationic polymers are polyethyleneimines, amidated, alkoxylated and / or alkylated polyethyleneimines, crosslinked polyethyleneimines, polyamidoamines, alkoxylated and / or alkylated polyamidoamines, crosslinked polyamidoamines, crosslinked polyamidoamines grafted with ethyleneimine, amine-epichlorohydrin polycondensates, polyvinylamines, alkoxylated Polyvinylformamides, polyallylamines,
Polydimethyldiallylammoniumchloride, 1-Vinylimidazoleinheiten enthaltende Polymere wie Poly-1-vinylimidazol oder Poly-(l-vinylimidazol-co-l-vinylpyrrolidon), quaternäre Vinylimidazoleinheiten enthaltende Polymere, Kondensate aus Imidazol und Epichlorhydrin, basische (Meth)acrylamid- oder (Meth)acrylestereinheiten enthaltende Polymere, basische quaternäre (Meth)acrylamid- oder (Meth)acrylestereinheiten enthaltende Polymere und/oder Lysinkondensate.Polydimethyldiallylammonium chlorides, polymers containing 1-vinylimidazole units such as poly-1-vinylimidazole or poly- (l-vinylimidazole-co-l-vinylpyrrolidone), polymers containing quaternary vinylimidazole units, condensates of imidazole and epichlorohydrin, basic (meth) acrylamide or (meth) acrylamide units containing polymers, basic quaternary (meth) acrylamide or (meth) acrylic ester units containing polymers and / or lysine condensates.
Unter kationischen Polymeren werden auch amphotere Polymerisate verstanden, die eine kationische Netto-Ladung aufweisen, d.h. die Polymere enthalten sowohl anionische als auch kationische Monomere in einpolymerisierter Form, jedoch ist der molare Anteil der im Polymeren enthaltenen kationischen Einheiten größer als der der anionischen Einheiten.Cationic polymers are also understood to mean amphoteric polymers which have a net cationic charge, i.e. the polymers contain both anionic and cationic monomers in copolymerized form, but the molar proportion of the cationic units contained in the polymer is greater than that of the anionic units.
Bevorzugte kationische Tenside (Komponente C) sind ausgewählt aus der Gruppe der quartären Diesterammoniumsalze, der quartären Tetraalkylammoniumsalze, der quartären Diamidoammoniumsalze, der Amidoaminester und Imidazoliumsalze. Diese sind vorzugweise in einer Menge von 3 bis 30 Gew.-% in den Wäschepflegespülmitteln enthalten. Beispiele sind quartäre Diesterammoniumsalze, die zwei Cπ- bis C22-Alk(en)yl- carbonyloxy(mono- bis pentamethylen)-Reste und zwei C bis C3-Alkyl- oder Hydroxy- alkylreste am quartären N-Atom aufweisen und als Gegenion beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat tragen. Quartäre Diesterammoniumsalze sind weiterhin insbesondere solche, die einen Cπ- bis C22-Alk(en)ylcarbonyloxytrimethylen-Rest, der am mittleren C-Atom der Trimethylen- Gruppierung einen Cπ- bis C22-Alk(en)ylcarbonyloxy-Rest trägt, und drei C bis C3- Alkyl- oder -Hydroxyalkylreste am quartären N-Atom aufweisen und als Gegenion beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat tragen.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 Cπ to C 22 alk (en) yl carbonyloxy (mono- to pentamethylene) residues and two C to C 3 alkyl or hydroxyalkyl residues on the quaternary N atom and as a counter ion for example, wear chloride, bromide, methyl sulfate or sulfate. Quaternary diesterammonium further include in particular those corresponding to the trimethylene group carries a Cπ- to C 22 -alk (en) ylcarbonyloxytrimethylen radical, on the central carbon atom form a Cπ- to C 22 -alk (en) ylcarbonyloxy radical, and have three C to C 3 alkyl or hydroxyalkyl radicals on the quaternary N atom and, for example, carry chloride, bromide, methyl sulfate or sulfate as counterion.
Quartäre Tettaalkylarnmoniumsalze sind insbesondere solche, die zwei Ci- bis C6-Alkyl- Reste und zwei C8- bis C24-Alk(en)yl-Reste am quartären N-Atom aufweisen und als Gegenion beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat tragen.Quaternary tetraalkylammonium salts are, in particular, those which have two C 1 -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 sulfate as counterion wear.
Quartäre Diamidoammoniumsalze sind insbesondere solche, die zwei C8- bis C2 - Alk(en)ylcarbonylaminoethylen-Reste, einen Substituenten ausgewählt aus Wasserstoff, Methyl, Ethyl und Polyoxyethylen mit bis zu 5 Oxyethylen-Einheiten und als vierten Rest eine Methylgruppe am quartären N-Atom aufweisen und als Gegenion beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat tragen.Quaternary diamidoammonium are in particular those which have two C 8 - a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene having up to 5 oxyethylene units and as fourth radical a methyl group on the quaternary nitrogen alk (en) ylcarbonylaminoethylene radicals, - to C 2 -Atom and have as counterion, for example, chloride, bromide, methyl sulfate or sulfate.
Amidoaminoester sind insbesondere tertiäre Amine, die als Substituenten am N-Atom einen Cπ- bis C22-Alk(en)ylcarbonylamino(mono- bis trimethylen)-Rest, einen Cπ- bis C22-Alk(en)ylcarbonyloxy(mono- bis trimethylen)-Rest und eine Methylgruppe tragen.Amidoamino esters are, in particular, tertiary amines which, as substituents on the N atom, have a Cπ to C 22 alk (en) ylcarbonylamino (mono- to trimethylene) radical, a Cπ to C 22 alk (en) ylcarbonyloxy (mono- to trimethylene) residue and a methyl group.
Imidazoliniumsalze sind insbesondere solche, die in der 2-Position des Heterocyclus einen C14- bis C1 -Alk(en)yl-Rest, am neutralen N-Atom einen C14- bis C18- Alk(en)ylcarbonyl(oxy oder amino)ethylen-Rest und am die positive Ladung tragenden N- Atom Wasserstoff, Methyl oder Ethyl tragen, Gegenionen sind hierbei beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat.Imidazolinium salts are in particular those in which the 2-position of the heterocycle, a C 14 - to C 1 -alk (en) yl radical, the neutral N-atom form a C 14 - to C 18 - Alk (en) ylcarbonyl (oxy or amino) 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.
Gegenstand der vorliegenden Erfindung ist auch die Verwendung von Zinkoxid und/oder Titandioxid zusammen mit organischen UV-Absorbern in Textilwaschmitteln, Wäschenachbehandlungs- und Wäschepflegemitteln.The present invention also relates to the use of zinc oxide and / or titanium dioxide together with organic UV absorbers in textile detergents, laundry aftertreatment and laundry care products.
Gegenstand der vorliegenden Erfindung sind ferner Ausrüstungsmittel zur UV- Schutzausrüstung textiler Materialien, enthaltend die Komponente A und B.The present invention also relates to finishing agents for UV protective finishing of textile materials, comprising components A and B.
Die erfindungsgemäßen Ausrüstungsmitteln können beispielsweise als Ausrüstungsmittel im engeren Sinne bei der Herstellung der Textilien oder in Form einer wäßrigenThe finishing agents according to the invention can be used, for example, as finishing agents in the narrower sense in the manufacture of the textiles or in the form of an aqueous one
Waschflotte oder als flüssiges Textilbehandlungsmittel vorliegen. So ist es beispielsweise möglich, im Zusammenhang mit der Textilherstellung die Textilien mit dem Ausrüstungsmittel zu behandeln. Textilien, die noch nicht oder nur unzureichend mit Ausrüstungsmittel behandelt worden sind, können beispielsweise im Heimbereich vor oder nach dem Waschen mit einem Textilbehandlungsmittel, das die anorganischen Pigmente A und die organischen UV-Absorber B enthält, behandelt werden. Es ist aber auch möglich, die Textilien im Hauptwaschgang oder nach dem Hauptwaschgang im Pflege- oder Weichspülgang der Waschmaschine mit den Komponenten (A) und (B) zu behandeln, teilweise unter Verwendung der oben beschriebenen Formulierungen.Wash liquor or as a liquid textile treatment agent. For example possible to treat the textiles with the finishing agent in connection with the textile production. Textiles that have not yet been treated or have been treated insufficiently with finishing agents can be treated, for example, in the home area before or after washing with a textile treatment agent which contains the inorganic pigments A and the organic UV absorbers B. However, it is also possible to treat the textiles with components (A) and (B) in the main wash cycle or after the main wash cycle in the care or fabric softener cycle, in some cases using the formulations described above.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung erläutern, ohne sie jedoch zu beschränken.The following examples are intended to illustrate the present invention without, however, restricting it.
Beispiel 1 - Anwendung der UV-Schutzmittel bei der Textilwäschenachbehandlung im Weichspülbad und Bestimmung des UV-Schutzfaktors UPFExample 1 - Use of the UV protection agents in the textile laundry aftertreatment in the fabric softener bath and determination of the UV protection factor UPF
Weißes Baumwollgewebe mit einem Flächengewicht von 100 g/m2 und einem UV- Schutzfaktor (UPF) von 4,1 wurde bei einer Wasserhärte von 3 mmol/1 gewaschen. Der Waschprozeß bestand aus einem Hauptwaschgang bei 40 °C (Ariel® Color als Waschmittel) und anschließendem Weichspülgang. Als Gewebeconditioner wurde eine handelsübliche Formulierung (Dbwny von Lenor") in einer Dosis von 1000 ppm, bezogen auf die Flotte, eingesetzt. Der Gewebeconditioner-Formulierung war entweder kein UV- Absorber oder jeweils 100 oder 200 ppm, bezogen auf die Flotte, einer erfindungsgemäßen UV-Absorberkombination vor dem Weich-/Pfiegespülen zugesetzt worden. Das Flottenverhältnis betrug 1:12,5. Nach dem Weich-/Pflegespülgang wurde das Gewebe entnommen und in getrocknetem Zustand sein UV-Schutzfaktor bestimmt. Anschließend wurde das Gewebe auf Lichtstabilität geprüft. Die Gewebeprobe wurde in einem Tischbelichtungsgerät SUNTEST® CPS (Fa. Heraeus, Hanau) für 4 und 24 Stunden (unter out-door-Bedingungen mit Filter WG 295) bei maximaler Strahlungsleistung des Geräts belichtet. Nach 4 und 24 Stunden Belichtung wurde erneut der UV-Schutzfaktor bestimmt.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 / 1. The washing process consisted of a main wash at 40 ° C (Ariel ® Color as a detergent) followed by a fabric softener. A commercial formulation (Dbwny von Lenor ") was used as the fabric conditioner in a dose of 1000 ppm, based on the liquor. The fabric conditioner formulation was either not a UV absorber or in each case 100 or 200 ppm, based on the liquor, of an inventive one The liquor ratio was 1: 12.5. After the fabric / conditioner rinse, the fabric was removed and its UV protection factor was determined in the dried state. The fabric was then checked for light stability tissue sample was placed in a table exposure apparatus SUNTEST ® CPS (Fa. Heraeus, Hanau) exposed for 4 and 24 hours (with out-door conditions with filter WG 295) at maximum radiation power of the device. After 4 and 24 hours of exposure was again the UV- Protection factor determined.
Als anorganische Pigmente wurden eingesetzt:The following were used as inorganic pigments:
- Z-COTE®, ein amphiphiles Zinkoxid der BASF AG- Z-COTE®, an amphiphilic zinc oxide from BASF AG
- Uvinul® TiO2 der BASF AG- Uvinul® TiO 2 from BASF AG
Als organische UV- Absorber wurden eingesetzt: A = 2-Cyano-3,3-diphenylacrylsäure-2-ethylhexylester (Uvinul® N-539 T) B = 2-Hydroxy-4-(n-octyloxy)benzophenon (Uvinul® 3008)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)
Die Ergebnisse sind in Tabelle 1 zusammengefasst.The results are summarized in Table 1.
Tabelle 1Table 1
Δ = UPF (mit Additiv) - UPF (ohne Additiv)Δ = UPF (with additive) - UPF (without additive)
Die Ergebnisse zeigen deutlich den synergistischen Effekt beim kombinierten Einsatz der UV-Absorber A bzw. B mit Zinkoxid bzw. Titandioxid. Ebenfalls klar ersichtlich ist der positive Einfluss der Pigmentoxide auf die Photostabilität der organischen UV-Absorber A und B. Zinkoxid und Titandioxid erhöhen den UV-Schutzfaktor des Baumwoll-Gewebes nur unwesentlich, wenn sie jeweils alleine eingesetzt werden.The results clearly show the synergistic effect when UV absorbers A and B are used in combination with zinc oxide and titanium dioxide. The positive influence of pigment oxides on the photostability of organic UV absorbers A and B is also clearly visible. Zinc oxide and titanium dioxide only increase the UV protection factor of the cotton fabric insignificantly if they are used alone.
Beispiel 2 - Anwendung bei der Textilwäschenachbehandlung im Weich-/Pflegespülbad und Bestimmung der Lichtstabilität des eingesetzten gefärbten Baumwollgewebes Mit Reaktiv Schwarz 5 gefärbtes Baumwollgewebe (1/3 Richttieftype) wurde im Weichspülgang mit einer handelsüblichen Formulierung (Downy von Lenor®, 1000 ppm bezogen auf die Flotte) unter Zusatz einer erfindungsgemäßen UV- Absorber-Kombination (jeweils 200 ppm bezogen auf die Flotte) im Flottenverhältnis 1:12,5 behandelt. Nach dem Weichspülgang wurden die Farbgewebe entnommen und in getrocknetem Zustand auf Lichtstabilität geprüft. Die Lichtstabilitäten (Photostabilitäten) wurden wie folgt gemessen:Example 2 - Use in textile laundry aftertreatment in fabric softener and 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 rinsed in the fabric softener with a commercially available formulation (Downy from Lenor®, 1000 ppm based on the liquor) with the addition of a UV absorber combination according to the invention (each 200 ppm based on the liquor) treated in a liquor ratio of 1: 12.5. After the fabric softener cycle, the colored fabrics were removed and checked for light stability in the dried state. The light stabilities (photostabilities) were measured as follows:
Die Proben wurden in einem Tischbelichtungsgerät SUNTEST® (Fa. Heraeus, Hanau) für 8 bzw. 24 Stunden (unter out-door-Bedingungen mit Filter WG 295) bei maximaler Strahlungsleistung des Geräts belichtet. Von den Färbungen wurde mittels eines Spektralphotometers mit Integrationskugel („Lambda 900" der Fa. Perkin Eimer) jeweils die Remissionsspektren vor und nach der Belichtung gemessen; diese Remissionsspektren wurden entsprechend der Kubelka-Munk-Theorie in K/S-Spektren umgerechnet ( K = Absorptionskoeffizient, S = Streukoeffizient). Die Photostabilitäten wurden anhand der nach 8 bzw. 24-stündiger Belichtung verbleibenden K/S- Werte bezogen auf die K/S- Werte vor Belichtung bewertet (K/S jeweils beim Maximum der K/S-Spektren). Je größer der in Tabelle 2 angegebene Wert in % ist, desto größer ist die Photostabilität.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 in accordance with the Kubelka-Munk theory (K = Absorption coefficient, S = scattering coefficient) The photo stabilities were evaluated 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 larger the value in% given in Table 2, the greater the photostability.
Als anorganisches Pigment wurde Z-COTE® der BASF AG eingesetzt.Z-COTE® from BASF AG was used as the inorganic pigment.
Als organische UV- Absorber wurden eingesetzt:The following were used as organic UV absorbers:
C = 2-(4 ' -Diethylamino-2 ' -hydroxybenzoyl)-benzoesäure-n-hexylester D = l-(4-tert.-Butylphenyl)-3-(4-methoxyphenyl)-propan-l,3-dion (Uvinul® BMBM)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)
Tabelle 2Table 2
Die Ergebnisse zeigen deutlich den synergistischen Effekt beim kombinierten Einsatz von C bzw. D mit Zinkoxid. The results clearly show the synergistic effect when C or D is combined with zinc oxide.

Claims

Patentansprüche claims
[ . Verfahren zur UV-Schutzausrüstung von textilem Material, bei dem man[. Process for the UV protective equipment of textile material, in which one
(a) Zinkoxid und/oder Titanoxid als Komponente A und(a) Zinc oxide and / or titanium oxide as component A and
(b) einen oder mehrere organischen UV-Absorber als Komponente B auf das textile Material aufbringt.(b) applying one or more organic UV absorbers as component B to the textile material.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß Komponente A UV- Absorber mit einem Absorptionsmaximum im Bereich von 280 bis 450 nm enthält.2. The method according to claim 1, characterized in that component A contains UV absorbers with an absorption maximum in the range from 280 to 450 nm.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass Komponente B eine oder mehrere Verbindungen, ausgewählt aus der Gruppe bestehend aus3. The method according to claim 1 or 2, characterized in that component B one or more compounds selected from the group consisting of
Phenylbenzotriazolen,phenylbenzotriazoles,
Dibenzoylmethanen,dibenzoylmethanes,
Estern der p-Aminobenzoesäure,Esters of p-aminobenzoic acid,
Estern der Zimtsäure, - Estern der Salicylsäure, stickstofffreien 2-Hydroxybenzophenonen,Esters of cinnamic acid, esters of salicylic acid, nitrogen-free 2-hydroxybenzophenones,
Phenylbenzimidazolen,Phenylbenzimidazolen,
Acrylaten,acrylates,
Diarylbutadienen, - ammosubstituierten Hydroxybenzophenonen,Diarylbutadienes, - amine-substituted hydroxybenzophenones,
Triazinen enthält.Contains triazines.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Gewichtsverhältnis der Komponente A zu der Komponente B von 20 : 1 bis 1 : 10 beträgt.4. The method according to any one of claims 1 to 3, characterized in that the weight ratio of component A to component B is from 20: 1 to 1:10.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Komponenten A und B in Form einer wäßrigen Flotte, die die Komponenten A und B enthält und daneben weitere Inhaltsstoffe enthalten kann, auf das textile Material aufbringt. 5. The method according to any one of claims 1 to 4, characterized in that components A and B are applied to the textile material in the form of an aqueous liquor which contains components A and B and may also contain further ingredients.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man die Komponenten A und B bei der Textilausrüstung während der Herstellung des textilen Materials, bei der Textilwäsche und/oder bei der Textilwäschenachbehandlung auf das textile Material aufbringt.6. The method according to any one of claims 1 to 5, characterized in that components A and B are applied to the textile material during textile finishing during the production of the textile material, during textile washing and / or during textile laundry treatment.
7. Textilwaschmittel-Formulierung, enthaltend 0,01 bis 20 Gew.-%, bezogen auf deren Summe, die Komponenten A und B wie in einem der Ansprüche 1 bis 4 definiert, neben weiteren üblichen Bestandteilen.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, in addition to other conventional ingredients.
8. Wäschenachbehandlungs- und Wäschepflegemittel-Formulierung, enthaltend 0,01 bis 20 Gew.-%, bezogen auf deren Summe, die Komponenten A und B wie in einem der Ansprüche 1 bis 4 definiert, neben weiteren üblichen Bestandteilen.8. laundry aftertreatment and laundry care 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 usual ingredients.
9. Wäschenachbehandlungs- und Wäschepflegemittel-Formulierung nach Anspruch 8, enthaltend 1 bis 50 Gew.-% eines oder mehrerer kationischer Tenside ausgewählt aus der Gruppe bestehend aus quartären Diesterammoniumsalzen, quartären Tetraalkylammoniumsalzen, quartären Diamidoammoniumsalzen,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,
Amidoaminoestern und Imidazolinen.Amido amino esters and imidazolines.
10. Ausrüstungsmittel zur UV-Schutzausrüstung von textilem Material, enthaltend ein Gemisch aus den Komponenten A und B, wie in einem der Ansprüche 1 bis 4 definiert.10. finishing agent for UV protective finishing of textile material, containing a mixture of components A and B, as defined in one of claims 1 to 4.
11. Textiles Material, enthaltend ein Gemisch aus den Komponenten A und B, wie in einem der Ansprüche 1 bis 4 definiert.11. Textile material containing a mixture of components A and B as defined in one of claims 1 to 4.
12. Verwendung von Zinkoxid und/oder Titandioxid zusammen mit organischen UV- Absorbern auf textilem Material zum Schutz der menschlichen Haut vor schädigender UV-Strahlung und/oder zum Schutz von gefärbtem textilem Material vor Verblassung der Farbe. 12. Use of zinc oxide and / or titanium dioxide together with organic UV absorbers on textile material to protect human skin from damaging UV radiation and / or to protect colored textile material from color fading.
EP02704685A 2001-02-06 2002-02-05 Method for providing textile material with uv protection Withdrawn EP1383952A2 (en)

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