DE19918967A1 - Fibre-reactive UV absorbers such as alpha, omega-bis(2-cyano-3,3-diphenylacryloylamide), can be applied to fabrics during washing to protect human skin against UV, or applied to colored fabrics to reduce fading - Google Patents

Abstract

Fibre-reactive UV absorbers containing a structural unit of formula (I). Use of compounds (A) with at least one structural unit of formula (I) as UV absorber which has affinity to textile fibres. X = -CR<1>=CR<2>- or carbonyl C=O; R<1> and R<2> = independently, H; 1-8C alkyl; 1-8C alkoxy; 1-8C alkoxycarbonyl; 1-8C acyloxy; carboxyl; cyano; nitro; F; Cl; Br; sulfonyl; 1-8C alkylsulfonyl; or phenyl which may be substituted by up to 3 groups selected from 1-8C alkyl, 1-8C alkoxy, 1-8C alkoxycarbonyl, 1-8C acyloxy, carboxyl, cyano, nitro, Cl, Br, sulfonyl and 1-8C alkylsulfonyl; or R<1> may also = -NQ-CO- linked to the ortho position of the neighboring phenyl nucleus by way of its carbonyl C atom to form a benzopyrrolidone system and in which Q = H or 1-8C alkyl; Z = substituents selected from 1-8C alkyl; 1-8C alkoxy; 1-8C alkoxycarbonyl; 1-8C acyloxy; carboxy; cyano; nitro; F; Cl; Br; sulfonyl; 1-8C alkylsulfonyl; amino; mono- or di-C1-C8-alkylamino; carboxamido which may carry one or two 1-8C alkyl groups on the amido N atom; hydroxy; or saturated or unsaturated 5- or 6-membered heterocyclic residue which may be condensed on; or any two neighboring substituents Z may together form a saturated or unsaturated 5- or 6-membered ring, and when p = 0, a carboxyl group in the ortho position and the carbonyl group already present may, together with N atoms bound to these carbonyl groups, form a cyclic imide; n = 0, 1, 2 or 3; p = 0, 1, 2, 3, 4 or 5.

Description

The present invention relates to the use of Compounds with a certain responsibility for UV absorption literal structural unit as a fiber-affine UV absorber, furthermore a method of protecting human skin from damaging UV radiation and a process for protecting dyed textile Material before the color fades, a process continues Increase in the UV protection factor UPF of textile material, further Towards a textile detergent and a textile pre-wash and Tex wash-after-treatment formulation, which these fiber affine UV absorbers included, as part of this fiber affinity UV absorber represents new substances - these new substances zen itself and a process for its manufacture and beyond textile material which ent this fiber-affine UV absorber holds.

The harmful effects of UV radiation from sunlight on human skin are not limited to just one premature skin aging and the formation of skin erythema (skin red sung, sunburn). If the skin becomes too long and too intense Exposed to UV radiation, the risk increases To develop skin cancer. Mainly responsible for the house redness and the increased risk of skin cancer is the UV-B portion of the UV radiation, d. H. the range from 280 to 320 nm. The maximum the erythema effect is 308 nm.

Textiles absorb UV radiation and thus protect as physi calic barrier the skin from the damaging influences of Sunlight ("textile skin protection"). However, the skin protective effect of textiles from many factors such as fiber type, fabric construction, fabric weight, color, moisture content or type of equipment or finishing. So just offers Summer clothes in the form of light and light cotton textiles only weak and therefore inadequate protection against UV rays lung.

So far, mainly conventional optical brighteners have been used processing and protecting the textiles themselves and also for textiles Skin protection used, especially those on stilbene and Triazine base, such as in EP-A 682 145, GB-A 2 313 375 or EP-A 728 749. The means are  but still need improvement in their effect and have one Series of disadvantages.

The object of the present invention was to ver in their effect to provide improved fiber-affine UV absorbers, which the No longer have disadvantages of the prior art.

Accordingly, the use of compounds (A) with at least one structural unit, in many cases preferably with at least two structural units, of the general formula (I)

in the
X represents groupings of the formula -CR ¹ = CR ² - or a carbonyl group C = O, where R ¹ and R ^{2 are} each independently of the other hydrogen, C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy , C ₁ - to C ₈ -alkoxycarbonyl, C ₁ - to C ₈ -acyloxy, carboxyl, cyano, nitro, fluorine, chlorine, bromine, sulfonyl, C ₁ - to C ₈ -alkylsulfonyl or phenyl, which consists of up to 3 radicals from the group C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy, C ₁ - to C ₈ -alkoxycarbonyl, C ₁ - to C ₈ -acyloxy, carboxyl, cyano, nitro, chlorine, bromine, sulfonyl and C ₁ - to C ₈ -alkylsulfonyl may be substituted,
Z substituents from the group C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy, C ₁ - to C ₈ -alkoxycarbonyl, C ₁ - to C ₈ -acyloxy, carboxyl, cyano, nitro, fluorine, chlorine , Bromine, sulfonyl, C ₁ - to C ₈ -alkylsulfonyl, amino, mono- or di-C ₁ - to C ₈ -alkylamino, carboxamido, which can carry one or two C ₁ - to C ₈ -alkyl groups on the amide nitrogen, hydroxy and saturated or unsaturated five- and six-membered heterocyclic radicals, which can be benzanellated, where two adjacent substituents Z can also form a saturated or unsaturated five- or six-membered ring, and in the case of p = 0 an ortho-stationary carboxyl group can form a cyclic imide together with the existing carbonyl group, including an N atom bonded directly to this carbonyl group,
n denotes the number 0, 1, 2 or 3, preferably the number 0 or 1, and
p denotes the number 0, 1, 2, 3, 4 or 5, preferably the number 0, 1, 2 or 3,
found as textile fiber affine UV absorber.

The compounds (A) with at least one structural unit (I) are preferably - in the sense of the task of the lying invention - in the form applied to textile material to protect human skin from damaging UV radiation. In addition, they also protect the textile material itself UV radiation, in particular they protect dyed textiles Material before the color fades.

In a preferred embodiment, compounds (A) which have the general formula (II)

have in which
Y represents the remainder of an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic group with an average molecular weight (M _W ) up to 100,000,000, which has at least m 'primary and / or secondary amino groups or m' hydroxyl groups or together at least m 'has primary and / or secondary amino groups and hydroxyl groups which are capable of forming amide or ester bonds with the structural unit (I), said grouping also on tertiary and / or free primary compounds present in the compounds (II) and / or secondary N atoms can be quaternized,
m 'denotes a number from 1 to 200, the number m of structural units (I) making up 10 to 100% of m', with the proviso that at least one structural unit (I) is present in the compounds (II),
and the variables X, Z, n and p have the meaning given above,
used.

The number m of structural units (I) in the compounds (II) is especially - depending on the size and structure of the grouping Y - 1 to 50, preferably 1 to 10, especially 1 to 5, or 2nd to 50, preferably 2 to 10, especially 2 to 5. In most In cases m denotes the number 1, 2 or 3. The number m 'of the Linking to the structural units (I) capable of amino or Hydroxyl groups in the group on which Y is based can be a Multiples of m; in particular, m 'denotes a number from 1 to 100, especially from 1 to 50, or a number from 2 to 200, preferably from 2 to 100, especially from 2 to 50. Preferred wise, m makes up 20 to 100%, in particular 30 to 100% of m '.

The compounds on which Y is based are, in particular, monomeric and polymeric amino alcohols, oligo- and polyamines, polyalkylene polyamines, polyamidoamines, polyvinylamines and polyalkylene polyamines grafted with (poly) ethylene imine, the amines and amino alcohols mentioned also being present on tertiary and / or in the compounds (II) or free primary and / or secondary N atoms still present can be guated. In the quaternized form, such N atoms generally carry a C ₁ - to C ₄ -alkyl group, usually a methyl or ethyl group, or a benzyl group, which has been introduced by customary methods, as the fourth organic radical.

In a particularly preferred embodiment, Y represents the residue of an aliphatic or cycloaliphatic oligoamine with 2 to 6 N atoms and a total of 2 to 30 C atoms, which can also carry 1 to 3 hydroxyl groups, the oligoamine mentioned also being present in the compounds ( II) existing tertiary and / or still existing free primary and / or secondary N atoms can be quaternized. Typical examples of such oligoamines are 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine, N- (2-aminoethyl) -1,3-propanediamine, N, N-dimethylethanolamine, diethanolamine, triethanol amine, 3-dimethylamino-1-propanol, N- (2-aminoethyl) ethanolamine, 3- (dimethylamino) propylamine, N, N'-bis (3-aminopropyl) -1.2 -ethylenediamine, N, N, N ', N'-tetrakis (3-aminopropyl) -1,2-ethylenediamine, N, N, N', N'-tetrakis [3- (C ₁ - to C ₄ -alkylamino ) propyl] -1,2-ethylenediamine, N, N'-bis (3-aminopropyl) piperazine and N, N'-bis [3- (C ₁ - to C ₄ -alkylamino) propyl] -piperazine. Suitable C ₁ -C ₄ -alkyl radicals in the oligoamines listed above are in each case methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

In a further particularly preferred embodiment, Y represents the remainder of a polyethyleneimine of the general formula (III)

with an average molecular weight (M _W ) of 200 to 1,000,000, in which the radicals R ³ to R ⁵ independently of one another are hydrogen, linear or branched C ₁ -C ₂₀ -alkyl-, -alkoxy-, -polyoxy ethylene- , -Hydroxyalkyl-, - (Alkyl) carboxy-, -Phosphonoalkyl-, -Alkylaminoreste, C ₂ - to C ₂₀ -Alkenylreste or C ₆ - to C ₂₀ -Aryl-, -Aryloxy-, -Hydroxyaryl-, -Arylcarboxy-, or arylamino radicals, which are optionally further substituted, and R ⁴ and R ⁵ also mean further polyethyleneimine polymer chains and x, y and z each independently denote 0 or an integer, said polyethyleneimine also being present in the compounds (II) existing tertiary and / or still existing free primary and / or secondary N atoms can be quaternized.

The sum of x, y and z should be chosen so that the average molar mass is in the specified range. Preferred ranges for the average molecular weight ( _MW ) of the polyethyleneimines (III) are 250 to 100,000, in particular 300 to 25,000.

Preferred radicals R ³ to R ⁸ are hydrogen, methyl, ethyl, carboxymethyl, carboxyethyl, phosphonomethyl, 2-hydroxyethyl, 2- (2'-hydroxyethoxy) ethyl and 2- [2 '- (2 "-hydroxyethoxy) ethoxy] ethyl.

In a further particularly preferred embodiment, Y represents the remainder of a polyamidoamine with an average molecular weight (M _W ) of 500 to 100,000,000, which is obtained by reacting C ₄ - to C ₁₀ -dicarboxylic acids with poly (C ₂ - to C ₄ - alkylene) polyamines with 3 to 20 basic nitrogen atoms in the molecule is available and which has at least m 'primary and / or secondary amino groups which are capable of forming amide or ester bonds with the structural unit (I), said poly amidoamine also may be quaternized on tertiary and / or free primary and / or secondary N atoms present in the compounds (II).

Preferred ranges for the average molar mass (M _W) of the polyamido amine 800 to 1,000,000, particularly 1,200 to 200,000.

In a further particularly preferred embodiment, Y represents the residue of a polyamine of the general formula (IV)

R ⁹ R ¹⁰ N- [C _q H _2q -NR ¹¹ -] _r -C _q H _2q -NR ⁹ R ¹⁰ (IV)

with an average molecular weight (M _W ) of 100 to 100,000,000, in which the radicals R ⁹ to R ¹¹ independently of one another are hydrogen, linear or branched C ₁ - to C ₂₀ -alkyl-, -alkoxy-, -polyoxy ethylene- , -Hydroxyalkyl-, - (Alkyl) carboxy-, -Phosphonoalkyl-, -Alkylaminoreste, C ₂ - to C ₂₀ -Alkenylreste or C ₆ - to C ₂₀ -Aryl-, -Aryloxy-, -Hydroxyaryl-, -Arylcarboxy-, or arylamino residues, which are optionally further substituted, q denotes an integer from 2 to 6 and r denotes an integer, where the alkylamino residues mentioned can also be continued in the manner of denimers in the alkyl moiety and wherein the polyamine mentioned can also be quaternized on the tertiary and / or free primary and / or secondary N atoms present in the compounds (II).

The number r should be chosen so that the average molecular weight is in the specified range. Preferred ranges for the average molecular weight ( _MW ) of the polyamines (IV) are 100 to 1,000,000, in particular 100 to 100,000. Q preferably denotes the number 2.

Preferred meanings for the radicals R ⁹ to R ¹¹ are also those given above for R ³ to R ⁸ .

Are dendrimers or dendrimer-like amines or their precursors N, N, N ', N'-tetraaminopropylethylenediamine, also as N6-amine records, as well as the producible therefrom by aminopropylation, dendrimeric amines designated by the number of their N atoms, such as N14, N30, N62 and N128 amine. These amines have an ethylene diamine backbone, whose hydrogen atoms on nitrogen are substituted by amino (n-propyl) radicals. The end permanent amino groups can in turn by appropriate amino be substituted propyl groups (N14-amine), etc. Manufacturing Processes for these amines are described in WO 96/15097 starting from ethylenediamine. Also preferred examples of these Amines are corresponding N-amines, as described in WO 93/14147 are written, starting from butylenediamine instead of as before hend ethylenediamine.  

In a further particularly preferred embodiment, Y represents the residue of a polyvinylamine of the general formula (V)

with an average molecular weight ( _MW ) of 300 to 100,000,000, in which the radicals R ¹² to R ¹⁶ independently of one another are hydrogen, linear or branched C ₁ - to C ₂₀ -alkyl-, -alkoxy-, -polyoxyethylene- , -Hydroxyalkyl-, - (Alkyl) carboxy-, -Phosphonoalkyl-, -Alkylaminoreste, C ₂ - to C ₂₀ -Alkenylreste or C ₆ - to C ₂₀ -Aryl-, -Aryloxy-, -Hydroxyaryl-, -Arylcarboxy-, or arylamino radicals, which are optionally further substituted, and R ^{15 also} mean a formamidyl, pyrrolidonyl or imidazolyl radical, s denotes an integer and t stands for 0 or an integer, the polyvinylamine mentioned also being in the compounds (II) existing tertiary and / or still existing free primary and / or secondary N atoms can be quaternized.

The sum of s and t should be chosen so that the average molar mass is in the specified range. Preferred ranges for the mitt sized molecular weight (M _W) of the polyvinylamines (V) are 500 to 500,000, in particular from 800 to 50,000.

Preferred meanings for the radicals R ¹² to R ¹⁶ are also those given above for R ³ to R ⁸ .

Furthermore, preference is given to using compounds (A) which have one or more structural units (I) in which X represents a group of the formula -CR ¹ = CR ² -, where R ¹ and R ^{2 are} each, independently of one another, hydrogen, cyano or is unsubstituted phenyl and n denotes the number 1.

Furthermore, preference is given to using compounds (A) which have one or more structural units (I) in which Z is a substituent from the group C ₁ - to C ₈ -alkoxy, amino, mono- or di-C ₁ - to C ₈ - denotes alkylamino and hydroxy and p denotes the number 1.

In connection with the variables R ¹ , R ² and Z above, C ₁ - to C ₈ -alkyl, -alkoxy and -acyloxy, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, iso- Butyl, sec.-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl or the corresponding alkoxy or acyloxy radicals.

As saturated or unsaturated five- and six-membered hetero cyclic residues for the variable Z, which are benzanellated can come, for example, the imidazolyl or benzimidazo lylrest into consideration.

As an unsaturated six-membered ring, the two neighboring ones Can form substituents Z, comes especially a benz anellant into consideration.

Individual particularly preferred structural units (I) for the compounds (A) are:

• P-aminobenzoyl
• - p- (Mono-C ₁ to C ₈ alkylamino) benzoyl
• - p- (Di-C ₁ to C ₈ alkylamino) benzoyl
• P-hydroxycinnamoyl (derived from p-hydroxycinnamic acid)
• pC ₁ to C ₈ alkoxycinnamoyl (derived from pC ₁ to C ₈ alkoxy cinnamic acid)
• O-hydroxybenzoyl
• - phthalimidoyl
• O-carboxamidobenzoyl
• - o- (C ₁ to C ₈ alkoxycarbonyl) benzoyl
• O-aminobenzoyl
• - o- (Mono-C ₁ to C ₈ alkylamino) benzoyl
• - o- (Di-C ₁ to C ₈ alkylamino) benzoyl
• - 2-cyano-3,3-diphenylacryloyl
• - m-benzimidazolyl-p-hydroxybenzoyl

Individual particularly preferred compounds (A) themselves are:

• - α, ω-bis [(p-dimethylamino) benzoylamide] from N, N'-bis (3-amino propyl) -1,2-ethylenediamine
• - α, ω-bis [(p-dimethylamino) benzoylamide] from triethylene tetramine
• - α, ω-bis [(p-dimethylamino) benzoylamide] from pentaethylene hexamine
• - α, ω-bis [p-methoxycinnamoylamide] from N, N'-bis (3-amino propyl) -1,2-ethylenediamine, on the two central ones secondary amino groups each with two methyl groups quaternized
• - α- (p-Methoxycinnamoylamid) from N, N'-bis (3-amino propyl) -1,2-ethylenediamine.
• - α, ω-bis [p-methoxycinnamoylamide] from pentaethylene hexamine
• - α- (p-Dimethylamino) benzoylamide from N, N'-bis (3-amino propyl) -1,2-ethylenediamine  
• - Reaction product of a polyethyleneimine of the formula (III) with M _W = 700 with p-methoxycinnamic acid methyl ester in a molar ratio of 1: 3
• - Reaction product of a polyethyleneimine of formula (III) with M _W = 700 with 2-cyano-3,3-diphenylacrylate in a molar ratio of 1: 3.

Textile material, on which the compounds (A) of the present Wind up invention and can develop its protective effect there, particularly includes clothing items, e.g. H. Textiles on of human skin, but also domestic 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 here clothing textiles made of cotton or cotton-polyester Mixtures of interest.

The present invention also relates to a method to protect human skin from damaging UV radiation, which is characterized in that compounds (A) with Structural units of the general formula (I) on textile mate rial in textile equipment, i.e. in the manufacture of Textiles.

The present invention also relates to a Ver drive to protect human skin from damaging UV Radiation, which is characterized in that Compounds (A) with structural units of the general formula (I) on textile material in textile washing and / or textile pre-wash or post-wash laundry.

The present invention also relates to a Ver drive to protect dyed textile material from fading the color, which is characterized in that one Compounds (A) with structural units of the general formula (I) on textile material in the textile equipment, i.e. in the manufacture position of the textiles.

The present invention also relates to a Ver drive to protect dyed textile material from fading the color, which is characterized in that one Compounds (A) with structural units of the general formula (I) on textile material in textile washing and / or textile pre-wash or post-wash laundry.  

The present invention also relates to a Process for increasing the UV protection factor UPF of textile Material which is characterized in that Ver bonds (A) with structural units of the general formula (I) on textile material in textile equipment, i.e. in the Manufacture of textiles.

The present invention also relates to a Ver drive to increase the UV protection factor UPF of textile mate rial, which is characterized in that connections (A) with structural units of the general formula (I) on textiles Material for textile washing and / or textile washing pre- or Applying textile laundry aftertreatment.

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

in which
S _λ = spectral radiation of the sun in the UV range at the wavelength λ
E _λ = spectral erythema effectiveness of UV radiation at the wavelength λ
T _λ = spectral transmission of the textile object at the wavelength λ

The fiber-affine UV absorber (A) according to the invention with at least a structural unit (I) can be used to equip the textile Materials, i.e. in the manufacture of textiles, or in the Care of the finished textile object, i.e. the textile  laundry and / or pretreatment or post-treatment of laundry lung, are applied.

Under textile equipment ("textile finishing") one understands the Work processes in the manufacture of textiles in which the Use value of the textiles is increased and by a before partial design of their external properties the textiles be embellished. Typical processes for increasing utility value are the easy care equipment, the anti-crease and the Shrink fencing equipment. Typical processes for designing the external properties are dyeing, bleaching, loading print and mercerize. When it comes to equipment in particular of piece goods, finishes are generally used, which contain the finishing agents and preferably also those Compounds (A) added in the sense of the present invention become.

The present invention also relates to a textile detergent formulation, which 0.01 to 20 wt .-%, in particular 0.1 to 10 wt .-%, especially 0.1 to 5 wt .-%, at least one Compound (A) with structural units of the general formula (I) contains in addition to the other usual ingredients.

The textile detergent formulation according to the invention generally contains other usual constituents

• A) 1 to 60 wt .-% inorganic builders based on crystalline NEN or amorphous aluminosilicates, crystalline or amorphous Silicates, carbonates or phosphates,
• B) 0.5 to 40 wt .-% anionic surfactants and
• C) 0.5 to 40% by weight of nonionic surfactants.

Suitable inorganic builders (B) are mainly crystalline ones or amorphous aluminosilicates with ion-exchanging properties like especially zeolites. Different types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially against others Cations such as Li, K, Ca, Mg or ammonium are exchanged. Suitable zeolites are described, for example, in EP-A 038591, EP-A 021491, EP-A 087035, US-A 4604224, GB-A 2013259, EP-A 522726, EP-A 384070 and WO-A 94/24251.

Suitable crystalline silicates (B) are, for example, disilicates or layered silicates, e.g. B. δ-Na ₂ Si ₂ O ₅ or β-Na ₂ Si ₂ O ₅ (SKS 6 or SKS 7, manufacturer: Hoechst). 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, which has a polymeric structure, or amorphous disilicate (Britesil® H 20 manufacturer: Akzo) can also be used.

Suitable inorganic builders (B) based on carbonate are carbonates and bicarbonates. These can take the form of their Alkali metal, alkaline earth metal or ammonium salts used become. Na, Li and Mg carbonates or -Hydrogen carbonates, especially sodium carbonate and / or Sodium bicarbonate used.

Common phosphates as inorganic builders (B) are polyphosphates such as B. pentasodium triphosphate.

The components (B) mentioned can be used individually or in mixtures can be used with each other.

Component (B) is in the textile detergent according to the invention tel formulation preferably in an amount of 5 to 50 wt .-%, in particular 10 to 45% by weight.

In a preferred embodiment, the invention contains Textile detergent formulation no phosphate-based builders or such only up to a maximum of 5% by weight, in particular only up to maximum 2% by weight.

Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols with 8 to 22, preferably 10 to 18 carbon atoms, e.g. B. C ₉ - to C ₁₁ alcohol sulfates, C ₁₂ - to C ₁₄ alcohol _sulfates , C ₁₂ -C ₁₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated C ₈ -C ₂₂ -alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by first using a C ₈ - to C ₂₂ -, preferably a C ₁₀ - to C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfa tiert. Ethylene oxide is preferably used for the alkoxylation, 1 to 50, preferably 1 to 20, mol of ethylene oxide being used per mol of alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Also suitable are those alkoxylated C ₈ - to C ₂₂ alcohols, the ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide. The alkoxylated C ₈ - to C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution. Depending on the type of alkoxylation catalyst, alkyl ether sulfates with a broad or narrow alkylene oxide homolog distribution can be obtained.

Other suitable anionic surfactants are alkane sulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkane sulfonates and soaps such as the Na and K salts of C ₈ to C ₂₄ carboxylic acids.

Other suitable anionic surfactants are linear C ₈ to C ₂₀ alkylbenzenesulfonates ("LAS"), preferably linear C ₉ to C ₁₃ alkylbenzenesulfonates and alkyltoluenesulfonates.

Still further suitable anionic surfactants (C) C ₈ - to C ₂₄ olefin sulfonates and disulfonates, which may also be mixtures of alkene and hydroxyalkane sulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerinsulfonate, fatty acid glycerol polyglycol ether, alkylphenol, Paraffin sulfonates with approx. 20 to approx. 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acylisethio nates, acyl taurates, acyl methyl taurates, alkyl succinic acids, alkenyl succinic acids or their half esters or half amides, alkyl sulfosuccinic acids or their amides, mono- and Diesters of sulfosuccinic acids, acyl sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are preferably in the detergent Form of salts added. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and Ammonium salts such as B. hydroxyethylammonium, di (hydroxy ethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Component (C) is preferably present in the textile detergent formulation according to the invention in an amount of 1 to 30% by weight, especially 3 to 25% by weight, in particular 5 to 15% by weight. If C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS) are also used, these are usually used in an amount of up to 10% by weight, in particular up to 8% by weight.

One can use single anionic surfactants or a combination use different anionic surfactants. It can be anionic Only one class of surfactants are used, for example only fatty alcohol sulfates or only alkyl benzene sulfonates, you can but also use surfactant mixtures from different classes, e.g. B. a mixture of fatty alcohol sulfates and alkylbenzene sulfonates.

Suitable nonionic surfactants (D) are, for example, alkoxylated C ₈ to C ₂₂ alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as surfactants. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol. The alkylene oxide used is preferably ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst, alkoxylates with a broad or narrow alkylene oxide homolog distribution can be obtained.

Another class of suitable nonionic surfactants are alkyl phenol alkoxylates such as alkyl phenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 moles of alkylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the Alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 glucoside units.

Another class of nonionic surfactants are N-alkyl glucamides of the general structures

wherein B _{1 is} a C ₆ to C ₂₂ alkyl, B ^{2 is} hydrogen or C ₁ to C ₄ alkyl and D is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. B ¹ is preferably C ₁₀ to C ₁₈ alkyl, B ^{2 is} CH ₃ and D is a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ to C ₁₈ carboxylic acids.

Other suitable nonionic surfactants are the end-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225

R ¹ -CO-NH- (CH ₂ ) _y -O- (A ¹ O) _x -R ²

in the
R ¹ denotes a C ₅ to C ₂₁ alkyl or alkenyl radical,
R ^{2 represents} a C ₁ to C ₄ alkyl group,
A ^{1 represents} C ₂ to C ₄ alkylene,
y denotes the number 2 or 3 and
x has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with methyl dodecane or the reaction products of ethyl tetraglycol amine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to C ₁₈ -fatty acid methyl esters.

Also suitable as nonionic surfactants (D) are blocks copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic® and Tetronic® brands from BASF), polyhydroxy or Polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxy fatty acid amides, fatty acid amide ethoxylates, especially end group capped, and Fatty acid alkanolamide alkoxylates.

Component (D) is in the laundry detergent according to the invention tel formulation preferably in an amount of 1 to 30 wt .-%, in particular 3 to 25% by weight, especially 5 to 20% by weight.

Individual nonionic surfactants or a combination of different nonionic surfactants can be used. Non-ionic surfactants from only one class can be used, in particular only alkoxylated C ₈ to C ₂₂ alcohols, but surfactant mixtures from different classes can also be used.

In a preferred embodiment, the invention contains Textile detergent formulation in addition to the inorganic Builders (B) 0.05 to 20% by weight, in particular 1 to 10% by weight organic cobuilders in the form of low molecular weight, oligomeric  or polymeric carboxylic acids, especially polycarboxylic acids, or Phosphonic acids or their salts, in particular Na or K salts.

Examples of low molecular weight carboxylic acids or phosphonic acids suitable as organic cobuilders are:
Phosphonic acids such as B. 1-hydroxyethane-1,1-diphosphonic acid, aminotris (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexamethylenediamine tetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid);
C ₄ - to C ₂₀ di, tri and tetracarboxylic acids such as. B. succinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ - to C ₁₆ alkyl or alkenyl radicals;
C ₄ - to C ₂₀ hydroxycarboxylic acids such. B. malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
Aminopolycarboxylic acids such as. B. Nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, alkylethylenediaminetriacetate, N, N-bis (carboxy methyl) glutamic acid, ethylenediaminedisuccinic acid and N- (2-hydroxyethyl) iminodiacetic acid, methyl- and acetic acid, methyl- and acetic acid.

Examples of suitable oligomeric or polymeric carboxylic acids as organic cobuilders are:
Oligomaleic acids, as described for example in EP-A 451508 and EP-A 396303;
Copolymers and terpolymers of unsaturated C ₄ -C ₈ dicarboxylic acids, with monoethylenically unsaturated monomers as comonomers
from group (i) in amounts of up to 95% by weight,
from group (ii) in amounts of up to 60% by weight and
from group (iii) in amounts of up to 20% by weight
can be polymerized.

Examples of suitable unsaturated C ₄ -C ₈ dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C ₂ -C ₂₂ olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, styrene, vinyl esters of C ₁ -C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ olefins, vinyl alkyl ethers having C ₁ -C ₄ alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) includes (meth) acrylic esters of C ₁ to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ -C ₈ amines, N-vinyl form amide and N-vinyl imidazole.

If the polymers of group (ii) polymerize vinyl esters contain, they can also partially or completely to vinyl alcohol structural units are hydrolyzed. Suitable co- and terpolymers are known, for example, from US-A 3887806 and DE-A 43 13 909 known.

Suitable copolymers of dicarboxylic acids as organic cobuilders are preferably:
Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 1000 to 150,000;
Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid to the vinyl ester can vary in the range from 30:70 to 70:30;
Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 44 15 623 and DE-A 43 13 909 are also suitable as organic cobuilder.  

Suitable unsaturated carboxylic acids are, for example Maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, Methacrylic acid, crotonic acid and vinyl acetic acid and mixtures from acrylic acid and maleic acid, in amounts of 40 to 95% by weight, based on the component to be grafted, grafted on become.

For modification, up to 30% by weight, based on the component to be grafted, further monoethylenically unsung saturated monomers are present in copolymerized form. Suitable modifi decorative monomers are the above-mentioned monomers of the groups (ii) and (iii).

Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolyzates and reduced (hydrogenated or hydrated aminated) degraded polysaccharides such as. B. mannitol, sorbitol, aminosorbitol and N-alkylglucamine suitable as well as polyalkylene glycols with molecular weights up to M _W = 5000 such as. B. polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyvalent C ₁ -C ₂₂ alcohols, cf. US-A 5756456.

Polyglyoxylic acids suitable as organic cobuilders are described for example in EP-B 001004, US-A 5399286, DE-A 41 06 355 and EP-A 656914. The end groups of the polyglyoxyl acids can have different structures.

Polyamidocarboxylic acids and. Suitable as organic cobuilders modified polyamidocarboxylic acids are known, for example from EP-A 454126, EP-B 511037, WO-A 94/01486 and EP-A 581452.

The organic cobuilders used include, in particular, polyaspartic acids or cocondensates of aspartic acid with further amino acids, C ₄ -C ₂₅ mono- or dicarboxylic acids and / or C ₄ -C ₂₅ mono- or diamines. Are particularly preferred in phosphorus-containing acids used prepared with C ₆ -C ₂₂ -mono- or -dicarboxylic acids or with C ₆ -C ₂₂ -mono- or -diamines.

Iminodibernstein is also suitable as an organic cobuilder acid, oxydisuccinic acid, aminopolycarboxylates, alkyl polyamino carboxylates, aminopolyalkylene phosphonates, polyglutamates, Hydrophobically modified citric acid such as B. agaricinic acid, Poly-α-hydroxyacrylic acid, N-acylethylenediamine triacetates such as  Lauroylethylenediamine triacetate and alkylamides of ethylenediamine tetraacetic acid such as EDTA tallow amide.

Oxidized starches can also be used as organic cobuilders be used.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally, especially in addition to the inorganic builders (B), the anionic surfactants (C) and / or the nonionic surfactants (D) 0.5 to 20% by weight, in particular 1 to 10% by weight, glycine-N, N- diacetic acid derivatives, as described in WO 97/19159 are.

In a further preferred embodiment, the Textile detergent formulation according to the invention additionally 0.5 up to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23% by weight bleach in the form of percarboxylic acids, e.g. B. Diper oxododecanedicarboxylic acid, phthalimidopercaproic acid or monoper oxophthalic acid or terephthalic acid, adducts of hydrogen peroxide to inorganic salts, e.g. B. sodium perborate monohydrate, Sodium perborate tetrahydrate, sodium carbonate perhydrate or Sodium phosphate perhydrate, adducts of hydrogen peroxide organic compounds, e.g. B. urea perhydrate, or from organic peroxo salts, e.g. B. alkali metal persulfates, or -peroxodisulfates, optionally in combination with 0 to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8% by weight, bleach activators. With color detergents it will Bleach (if present) usually without a bleach activator otherwise bleach activators are usually used available.

Suitable bleach activators are:

• - polyacylated sugars, e.g. B. Pentaacetylglucose;
• - Acyloxybenzenesulfonic acids and their alkali and alkaline earths metal salts, e.g. B. sodium p-nonanoyloxybenzenesulfonate or Sodium p-benzoyloxybenzenesulfonate;
• - N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. B. N, N, N ', N'-tetraacetylmethylene diamine and ethylene diamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethyl hydantoin;  
• - N-alkyl-N-sulfonylcarbonamides, e.g. B. N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide;
• - N-acylated cyclic hydrazides, acylated triazoles or Urazole, e.g. B. monoacetyl maleic acid hydrazide;
• - O, N, N-trisubstituted hydroxylamines, e.g. B. O-Benzoyl-N, N- succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, N-triacetylhydroxylamine;
• - N, N'-diacylsulfurylamides, e.g. B. N, N'-Dimethyl-N, N'-diacetyl sulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide;
• Acylated lactams such as acetylcaprolactam, Octanoylcaprolactam, benzoylcaprolactam or carbonylbisca prolactam;
• - Anthranil derivatives such as B. 2-methylanthranil or 2-phenyl anthranil;
• - Triacylcyanurate, e.g. B. triacetyl cyanurate or Tribenzoylcya nurat;
• - Oxime esters and bisoxime esters such as. B. O-acetylacetone oxime or Bisisopropyliminocarbonate;
• - Carboxylic anhydrides, e.g. B. acetic anhydride, benzoic acid anhydride, m-chlorobenzoic anhydride or phthalic acid anhydride;
• - enol esters such as B. isopropenyl acetate;
• - 1,3-diacyl-4,5-diacyloxy imidazolines, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline;
• - tetraacetylglycoluril and tetrapropionylglycoluril;
• - Diacylated 2,5-diketopiperazines, e.g. B. 1,4-diacetyl-2,5-di ketopiperazine;
• - Ammonium substituted nitriles such as. B. N-methylmorpholinium acetonitrile methyl sulfate;
• - acylation products of propylene diurea and 2,2-dimethyl propylene diurea, e.g. B. tetraacetylpropylene diurea;  
• - a-Acyloxypolyacylmalonamide, e.g. B. α-acetoxy-N, N'-diacetyl malonamide;
• - Diacyl-dioxohexahydro-1,3,5-triazines, e.g. B. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
• - Benz- (4H) 1,3-oxazin-4-one with alkyl radicals, e.g. B. methyl, or aromatic residues z. B. phenyl, in the 2-position.

The described bleaching system consisting of bleaching agents and bleaching stock vatoren can optionally also contain bleaching catalysts. Suitable bleaching catalysts are, for example, quaternized ones Imines and sulfonimines, which are described for example in US-A 5 360 569 and EP-A 453 003. Particularly effective bleaching Catalysts are manganese complexes that are used, for example, in the WO-A 94/21777 are described. Such connections are in If used in the detergent formulations, the maximum least in amounts up to 1.5% by weight, in particular up to 0.5% by weight, in In the case of very active manganese complexes in amounts up to 0.1% by weight.

In addition to the bleaching system described from bleaching agents, bleach activators and optionally bleaching catalysts is for the textile detergent formulation according to the invention also the Use of systems with enzymatic peroxide release or photo-activated bleaching systems possible.

In a further preferred embodiment, the Textile detergent formulation according to the invention additionally 0.05 up to 4% by weight of enzymes. Preferably used in detergents Enzymes are proteases, amylases, lipases and cellulases. Of the Enzymes are preferably amounts of 0.1 to 1.5 wt .-%, ins particularly preferably 0.2 to 1.0% by weight of the compound Enzyme added. Suitable proteases are e.g. B. Savinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is e.g. B. Lipolase (manufacturer: Novo Nordisk). A suitable cellu lase is e.g. B. Celluzym (manufacturer: Novo Nordisk). Also the Use of peroxidases to activate the bleaching system possible. One can use single enzymes or a combination different enzymes. If necessary, the Textile detergent formulation according to the invention still enzyme stabilizer lisators, e.g. As calcium propionate, sodium formate or boric acids or their salts, and / or contain antioxidants.  

The textile detergent formulation according to the invention can contain, in addition to the main components mentioned above, the following further customary additives in the amounts customary for this:

• - Cationic surfactants, usually in an amount of up to 25% by weight, preferably 3 to 15% by weight, for example C ₈ to C ₁₆ dialkyldimethylammonium halides, dialkoxydimethylam monium halides or imidazolinium salts with a long-chain alkyl radical;
• - Amphoteric surfactants, usually in an amount up to 15 wt .-%, preferably 2 to 10 wt .-%, for example derivatives of secondary or tertiary amines such as. B. C ₁₂ -C ₁₈ alkyl betaines or C ₁₂ -C ₁₈ alkyl sulfobetaines or amine oxides such as alkyldimethylamine oxides;
• - Graying inhibitors and soil release polymers (han is it z. B. to polyester from polyethylene oxides Ethylene glycol and / or propylene glycol and aromatic Dicarboxylic acids or aromatic and aliphatic dicarbon acids or polyester from one end group-capped Polyethylene oxides with di- and / or polyhydric alcohols and dicarboxylic acids. Such polyesters are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US-A-5 142 020. Other suitable Soil-Re lease polymers are amphiphilic graft or copolymers of Vinyl and / or acrylic esters on polyalkylene oxides, cf. US-A-4 746 456, US-A-4 846 995, DE-A-37 11 299, US-A-4 904 408, US-A-4 846 994 and US-A-4 849 126, or modified celluloses such as B. methyl cellulose, hydroxyl propyl cellulose or carboxymethyl cellulose. Graying inhi Bitterns and soil release polymers are in the detergent formulations of 0.1 to 2.5 wt .-%, preferably 0.2 to Contain 1.5% by weight, particularly preferably 0.3 to 1.2% by weight Soil-release polymers used with preference are those of U.S. Patent 4,746,456 to graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500-8000 in weight ratio 1, 2: 1 to 3.0: 1, as well as commercially available polyethylene terephthalate / polyoxyethylene terephthalate with a molecular weight of 3000 up to 25000 from polyethylene oxides with a molecular weight of 750 to 5000 Terephthalic acid and ethylene oxide and a molar ratio of 8: 1 polyethylene terephthalate to polyoxyethylene terephthalate up to 1: 1 and the block poly known from DE-A-44 03 866 condensates, the blocks of (a) ester units made of poly alkylene glycols with a molecular weight of 500 to 7500 and aliphati Dicarboxylic acids and / or monohydroxymonocarboxylic acids and  (b) Ester units from aromatic dicarboxylic acids and contain polyhydric alcohols. These amphiphiles Block copolymers have molecular weights from 1500 to 25000.);
• - Color transfer inhibitors, for example homo- and copoly merisates of N-vinylpyrrolidone, N-vinylimidazole, N- With vinyl oxazolidone or 4-vinyl pyridine-N-oxide Molar masses from 15,000 to 100,000 and cross-linked fine-particle Polymers based on these monomers with a particle size from 0.1 to 500, preferably 0.1 to 250 µm;
• - non-surfactant foam dampers or foam inhibitors, for example organopolysiloxanes and mixtures thereof microfine, optionally silanized silica and Paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica;
• - complexing agents (also in the function of organic Cobuilders);
• - optical brighteners;
• - polyethylene glycols;
• - perfumes or fragrances;
• - fillers;
• - inorganic adjusting agents, e.g. B. sodium sulfate;
• - assembly aids;
• - solubility enhancer;
• - opacifying and pearlescent agents;
• - dyes;
• - corrosion inhibitors;
• - peroxide stabilizers;
• - electrolytes.

A solid textile detergent formulation according to the invention lies usually in powder or granular form or in extrudate or Tablet form.

Powder or granular detergents according to the invention can contain up to 60% by weight of inorganic adjusting agents. More common Sodium sulfate is used for this. Preferably, the detergents according to the invention but low in adjusting agents and ent hold only up to 20% by weight, particularly preferably only up to 8 % By weight of adjusting agents, in particular in the case of compact or ultracom compact detergents. The solid detergents according to the invention can different bulk densities in the range from 300 to 1300 g / l, in particular from 550 to 1200 g / l. Modern compact detergents generally have high bulk densities and show a granulate structure. For the desired compression of the detergent the methods customary in technology can be used.

The textile detergent formulation according to the invention is after Manufactured customary methods and assembled if necessary.

The present invention also relates to a textile wash pretreatment and textile aftertreatment formulation which is 0.01 up to 40 wt .-%, in particular 0.5 to 20 wt .-%, at least one Compound (A) with structural units of the general formula (I) contains in addition to the other usual ingredients.

Pre-wash and pre-wash are preferred aftertreatment formulation, which further 1 to 50 wt .-%, in particular 3 to 30 wt .-%, one or more cationic Surfactants from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamido ammonium salts, the amidoamino ester and the imidazolinium salts contains.

Quaternary diester ammonium salts are in particular those which have two C ₁₁ -C ₂₂ -alk (en) ylcarbonyloxy (mono- to pentamethylene) radicals and two C ₁ -C ₃ -alkyl or hydroxyalkyl radicals on the quaternary N atom have and as a counter ion, for example, carry chloride, bromide, methosulfate or sulfate.

Quaternary diesterammonium further include in particular those having a C ₁₁ - to C ₂₂ -alk (en) ylcarbonyl-oxy-trimethylene radical, on the central carbon atom of the tri-methylene moiety is a C ₁₁ - to C ₂₂ -alk ( en) bears ylcarbonyloxy residue, and has three C ₁ - to C ₃ -alkyl or -hydroxyalkyl residues on the quaternary N atom and, for example, chloride, bromide, methosulfate or sulfate as counterion.

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

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

Amidoamino esters are, in particular, tertiary amines which, as substituents on the N atom, have a C ₁₁ to C ₂₂ alk (en) ylcarbonyl amino (mono- to trimethylene) radical, a C ₁₁ to C ₂₂ alk (en) yl carbonyl -oxy- (mono- to trimethylene) residue and a methyl group.

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

In the textile laundry after-treatment formulations come into play special fabric softener and fabric care products.

Other usual ingredients for such a textile laundry and fabric wash after-treatment formulation are non-ionic Surfactants, fragrances and colorants, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, Corrosion protection additives, bactericides, preservatives and Water in the usual amounts for this.

Some of the compounds (A) are new substances. The present invention therefore also relates to compounds (A ') which have the general formula (IIa)

have in which
Y 'represents the rest of an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic group with an average molecular weight (M _W ) up to 100,000,000, which has at least m' primary and / or secondary amino groups or together at least m 'primary and / or has secondary amino groups and hydroxyl groups which are capable of forming amide or ester bonds with the structural unit (I), said grouping also being present on the tertiary and / or free primary present in the compounds (IIa) and / or secondary N atoms can be quatered,
m 'denotes a number from 1 to 200, the number m of structural units (I) making up 10 to 100% of m', with the proviso that at least one structural unit (I) is present in the compounds (II),
and the variables X, Z, n and p have the meaning given above.

The compounds (A ') as well as the compounds (A) are expediently prepared in that carboxylic acid derivatives of the general formula (Ia)

in the Y "represents an alkyl group having 1 to 4 carbon atoms, for example methyl or ethyl, a halogen atom, for example chlorine or bromine, an amino group which may carry one or two C ₁ - to C ₄ -alkyl groups or a hydroxyl group and the other variables have the meaning given above,
with the compounds on which Y 'is based to form the corresponding carboxamide and / or carboxylic ester structures and, if appropriate, then partially or completely quaternized any tertiary and / or primary and / or secondary N atoms present in the compounds (IIa).

The textile-affinity UV absorbers according to the invention are suitable in an excellent way, both on textile material brought form, to protect human skin from damaging UV radiation as well as to protect dyed textile material before the color fades. Textile material, which at least a connection (A) with at least one structural unit of the general formula (I), is therefore also an object of the present invention.

The following examples are intended to illustrate the present invention refine without restricting them.

example 1 Production of α, ω-bis [p-methoxycinnamoylamid] from N, N'-bis (3-aminopropyl) -1,2-ethylenediamine

The following manufacturing instructions are a typical example for the preparation of compounds (A): 28.8 g (0.15 mol) p-Methoxycinnamic acid methyl ester was added together with 1.5 g (0.008 mol) of a 30% by weight solution of sodium methylate in Methanol and 13.2 g (0.075 mol) of N, N'-bis (3-aminopropyl) -1,2- ethylenediamine heated to 100 ° C for 4 hours, then was the methanol distilled off. After usual work-up received a light beige product in a yield of 78%.

Example 2 Quaternization of the product from Example 1

The product from Example 1 was obtained by reaction with dimethyl sulfate as a methylating agent in a molar ratio of 1: 4 after a usual method on the two central secondary amino groups methylated. A light beige product was obtained in one Yield 98%.

Application studies Example 3 Use in textile washing in the main wash cycle

White cotton fabric with a weight per unit area of 100 g / m ² and a UV protection factor UPF = 4.50 was washed at a water hardness of 3 mmol / l for 30 minutes at 60 ° C. A commercially available formulation (Persil © Megaperls Color) in a dosage of 4500 ppm, based on the wash liquor, was used as the detergent. Either no UV-absorber with a textile fiber affinity or 400 ppm, based on the wash liquor, of the UV absorber A1, A2 or A3 according to the invention had been added to the formulation before washing. After washing, rinsing, spinning and drying the cotton fabric, the UV protection factor UPF was determined.

Structures of the UV absorbers used:
A1 = α, ω-bis [p-methoxycinnamoylamide] from pentaethylene hexamine
A2 = reaction product of a commercially available polyethyleneimine of the formula (III) with M _W = 700 (Polymin G 10 from BASF Aktiengesellschaft) with methyl p-methoxycinnamate in a molar ratio of 1: 3
A3 = α, ω-bis [p-methoxycinnamoylamid] from N, N'-bis (3-amino propyl) -1,2-ethylenediamine, quaternized on the two central secondary amino groups with two methyl groups each (product from Example 2)

Table 1 shows the results of the tests:

Table 1

The results show that the use of UV absorbers A1 to A3 in the main wash in the textile wash as defined in the present Invention for a significant increase in textile UV protection leads.

Example 4 Application in textile laundry treatment in Fabric softener

White cotton fabric with a basis weight of 100 g / m ² and a UV protection factor UPF = 4.50 was washed five times in succession. A wash cycle consisted of a main wash at 40 ° C with a commercial detergent formulation (Persil® Megaperls Color) and a subsequent fabric softener. A commercial formulation (Lenor® ultra) was used as a fabric softener in a dosage of 1000 ppm, based on the liquor. The fabric softener formulation either had no textile fiber-affine UV absorber or 100 ppm, based on the liquor, of the UV absorber A1, A2 or A3 (see Example 3) according to the invention had been added before the fabric softener. A fabric sample was taken after each softener cycle and its UV protection factor UPF was determined in the dried state.

Table 2 shows the results of the tests:

Table 2

It can be clearly seen that when using the UV Absorbers A1 to A3 the UV protection factor UPF of the cotton fabric increases with an increase in the number of washing cycles. Already after the 5th Washing cycle gives you protection factors that are good to very good ensure good skin protection against UV radiation. The results further show that the textile without the addition of UV absorbers Protection from UV radiation is not improved.

Claims (25)

1. Use of compounds (A) with at least one structural unit of the general formula (I)
in the
X represents groups of the formula -CR ¹ = CR ² - or a carbonyl group C = O, where R ¹ and R ^{2 are} each independently hydrogen, C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy, C ₁ - to C ₈ -alkoxycarbonyl, C ₁ - to C ₈ -acyloxy, carboxyl, cyano, nitro, fluorine, chlorine, bromine, sulfonyl, C ₁ - to C ₈ -alkylsulfonyl or phenyl, which consists of up to 3 radicals the group C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy, C ₁ - to Ce-alkoxycarbonyl, C ₁ - to C ₈ -acyloxy, carboxyl, cyano, nitro, chlorine, bromine, sulfonyl and C ₁ - to C ₈ alkylsulfonyl may be substituted,
Z substituents from the group C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy, C ₁ - to C ₈ -alkoxycarbonyl, C ₁ - to C ₈ -acyloxy, carboxyl, cyano, nitro, fluorine, chlorine , Bromine, sulfonyl, C ₁ - to C ₈ -alkylsulfonyl, amino, mono- or di-C ₁ - to C ₈ -alkylamino, carboxamido, which can carry one or two C ₁ - to C ₈ -alkyl groups on the amide nitrogen, hydroxy and saturated or unsaturated five- and six-membered heterocyclic radicals, which may be benzanellated, where in each case two adjacent substituents Z can also form a saturated or unsaturated five- or six-membered ring, and where in the case p = 0 an ortho-standing carboxyl group together can form a cyclic imide with the carbonyl group present, including an N atom bonded directly to this carbonyl group,
n represents the number 0, 1, 2 or 3 and
p denotes the number 0, 1, 2, 3, 4 or 5,
as textile fiber-affine UV absorber. 2. Use of compounds (A) with at least one Structural unit (I) according to claim 1 in on textile material applied form to protect human skin from schä digging UV radiation. 3. Use of compounds (A) with at least one Structural unit (I) according to claim 1 for the protection of colored textile material before the color fades. 4. Use of compounds (A) which have the general formula (II)
have in which
Y stands for the remainder of an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic group with an average molecular weight (M _W ) up to 100,000,000, which has at least m 'primary and / or secondary amino groups or m' hydroxyl groups or together at least m 'Primary and / or secondary amino groups and hydroxyl groups which are capable of forming amide or ester bonds with the structural unit (I), said grouping also on the tertiary and / or free radicals present in the compounds (II) primary and / or secondary N atoms can be quaternized,
m 'denotes a number from 1 to 200, the number m of structural units (I) making up 10 to 100% of m', with the proviso that at least one structural unit (I) is present in the compounds (II),
and the variables X, Z, n and p have the meaning given in claim 1,
according to claims 1 to 3. 5. Use of compounds (A) which are general Have formula (II) according to claim 4, wherein the number m of the structural units (I) in the compounds (II) 1, 2 or 3 is. 6. Use of compounds (A) which are general Have formula (II) according to claim 4 or 5, wherein Y is the rest of an aliphatic or cycloaliphatic oligo amines with 2 to 6 N atoms and a total of 2 to 30 C atoms, which can still carry 1 to 3 hydroxyl groups, is where in the said oligoamine also in the compounds (II) existing tertiary and / or free primary available ren and / or secondary N atoms can be quaternized. 7. Use of compounds (A) which have the general formula (II) according to claim 4 or 5, wherein Y for the remainder of a polyethyleneimine of the general formula (III)
with an average molecular weight (M _W ) of 200 to 1,000,000, in which the radicals R ³ to R ⁸ independently of one another are hydrogen, linear or branched C ₁ -C ₂₀ -alkyl-, -alkoxy-, -polyoxyethylene-, Hydroxyalkyl, (alkyl) carboxy, phosphonoalkyl, alkylamino residues, C ₂ to C ₂₀ alkenyl residues or C ₆ to C ₂₀ aryl, aryloxy, hydroxyaryl, aryl carboxy, or arylamino radicals, which are optionally further substituted, and R ⁴ and R ⁵ also mean further polyethyleneimine polymer chains and x, y and z independently of one another each denote 0 or an integer, the polyethyleneimine also mentioned in the compounds (II) existing tertiary and / or existing free primary and / or secondary N atoms can be quatered. 8. Use of compounds (A) which have the general formula (II) according to claim 4 or 5, wherein Y represents the remainder of a polyamidoamine with an average molecular weight (M _W ) of 500 to 100,000,000, which by reaction of C ₄ - to C ₁₀ -dicarboxylic acids with poly (C ₂ - to C ₄ -alkylene) polyamines with 3 to 20 basic nitrogen atoms in the molecule and which has at least m 'primary and / or secondary amino groups which are used to form amide - or ester bonds with the structural unit (I) are capable, said polyamidoamine also being able to be quaternized on tertiary and / or still existing free primary and / or secondary N atoms present in the compounds (II). 9. Use of compounds (A) which have the general formula (II) according to claim 4 or 5, wherein Y represents the remainder of a polyamine of the general formula (IV)
R ⁹ R ¹⁰ N- [C _q H _2q -NR ¹¹ -] _r -C _q H _2q -NR ⁹ R ¹⁰ (IV)
with an average molecular weight (M _W ) of 100 to 100,000,000 in which the radicals R ⁹ to R ¹¹ independently of one another are hydrogen, linear or branched C ₁ -C ₂₀ -alkyl-, -alkoxy-, -polyoxyethylene-, -Hydroxyalkyl-, - (alkyl) carboxy-, -phosphonoalkyl-, -alkylamino residues, C ₂ - to C ₂₀ -alkenyl residues or C ₆ - to C ₂₀ -aryl, -Aryloxy-, -Hydroxyaryl-, -Arylcar boxy-, or arylamino residues, which are optionally further substituted, mean q denotes an integer from 2 to 6 and r denotes an integer, where the alkylamino residues mentioned can also be continued in the manner of dendrimers in the alkyl part and said polyamine can also be quaternized on tertiary and / or free primary and / or secondary N atoms present in the compounds (II). 10. Use of compounds (A) which have the general formula (II) according to claim 4 or 5, wherein Y represents the remainder of a polyvinylamine of the general formula (V)
with an average molecular weight (M _W ) of 300 to 100,000,000, in which the radicals R ¹² to R ¹⁶ independently of one another are hydrogen, linear or branched C ₁ -C ₂₀ -alkyl-, -alkoxy-, -polyoxyethylene-, -Hydroxyalkyl-, - (alkyl) carboxy-, -phosphonoalkyl-, -alkylamino residues, C ₂ - to C ₂₀ -alkenyl residues or C ₆ - to C ₂₀ -aryl, -Aryloxy-, -Hydroxyaryl-, -Arylcar boxy-, or arylamino radicals, which are optionally further substituted, and R ¹⁵ also mean a formamidyl, pyrrolidonyl or imidazolyl radical, s denotes an integer and t stands for 0 or an integer, the polyvinylamine mentioned also being in the Compounds (II) can be quaternized in front of existing tertiary and / or free primary and / or secondary N atoms still present. 11. Use of compounds (A) with at least one structural unit (I) according to claims 1 to 10, in which X represents a group of the formula -CR ¹ = CR ² -, where R ¹ and R ^{2 are} each independently hydrogen , Cyano or unsubstituted phenyl and n denotes the number 1 be. 12. Use of compounds (A) with at least one structural unit (I) according to claims 1 to 11, in which Z is a substituent from the group C ₁ - to C ₈ alkoxy, amino, mono- or di-C ₁ - bis C ₈ alkylamino and hydroxy and p denotes the number 1. 13. Use of compounds (A) with at least one Structural unit (I) according to claims 1 to 12 as a textile fiber-affine UV absorber for textile material made from Cellu is loose or contains cellulose. 14. Process for protecting human skin from damaging UV radiation, characterized in that compounds (A) with structural units of the general formula (I) according to claims 1 and 4 to 12 on textile material in the Applying textile equipment. 15. Process for protecting human skin from damaging UV radiation, characterized in that compounds (A) with structural units of the general formula (I) according to claims 1 and 4 to 12 on textile material in the Textile laundry and / or prewash or textile laundry applies aftertreatment. 16. Process for protecting dyed textile material from ver pale color, characterized in that one Compounds (A) with structural units of the general formula (I) according to claims 1 and 4 to 12 on textile material with the textile equipment. 17. Process for protecting dyed textile material from Ver pale color, characterized in that one Compounds (A) with structural units of the general  Formula (I) according to claims 1 and 4 to 12 on textiles Material for textile washing and / or textile washing pre- or textile laundry after-treatment. 18. Process for increasing the UV protection factor UPF of textile Material, characterized in that compounds (A) with structural units of the general formula (I) according to Claims 1 and 4 to 12 on textile material at the Applying textile equipment. 19. Process for increasing the UV protection factor UPF of textile Material, characterized in that compounds (A) with structural units of the general formula (I) according to Claims 1 and 4 to 12 on textile material at the Textile laundry and / or prewash or textile laundry applies aftertreatment. 20. Textile detergent formulation containing 0.01 to 20% by weight at least one compound (A) with structural units of general formula (I) according to claims 1 and 4 to 12 in addition to the other usual components. 21. Pre-wash and post-wash textile formulation tion containing 0.01 to 40 wt .-% of at least one ver bond (A) with structural units of the general formula (I) according to claims 1 and 4 to 12 in addition to the others usual components. 22. Textile laundry pretreatment and textile laundry after-treatment formulation according to claim 20, further comprising 1 to 50 wt .-% of one or more cationic surfactants from the group of the quaternary ren diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamidoammonium salts, the amidoamino ester and the imidazolinium salts. 23. Compounds (A ') which have the general formula (IIa)
have in which
Y 'represents the remainder of an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic group with an average molecular weight (M _W ) of up to 100,000,000, which has at least m' primary and / or secondary amino groups or together at least m 'primary and / or has secondary amino groups and hydroxyl groups which are capable of forming amide or ester bonds with the structural unit (I), where the said grouping also contains tertiary and / or free primary and / or free primary compounds present in the compounds (IIa) / or secondary N atoms can be quaternized,
m 'denotes a number from 1 to 200, the number m of structural units (I) making up 10 to 100% of m', with the proviso that at least one structural unit (I) is present in the compounds (II),
and the variables X, Z, n and p have the meaning given in claim 1. 24. A process for the preparation of compounds (A ') which have the general formula (IIa) according to claim 22, characterized in that carboxylic acid derivatives of the general formula (Ia)
in which Y "stands for an alkyl group with 1 to 4 C atoms, a halogen atom, an amino group optionally carrying one or two C ₁ to C ₄ alkyl groups or a hydroxyl group and the other variables have the meaning given above,
with the compounds on which Y 'is based to form the corresponding carboxamide and / or carboxylic acid ester structures and, if appropriate, then partially or completely quaternized tertiary and / or primary and / or secondary N atoms present in the compounds (IIa). 25. Textile material containing at least one compound (A) with at least one structural unit of the general Formula (I) according to claims 1 and 4 to 12.