EP1177342A1

EP1177342A1 - Uv-absorbers with an affinity for textile fibres

Info

Publication number: EP1177342A1
Application number: EP00926969A
Authority: EP
Inventors: Jürgen Detering; Werner Bertleff; Gerhard Wagenblast; Christian Ott; Elisabeth Kappes; Thorsten Habeck
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1999-04-27
Filing date: 2000-04-17
Publication date: 2002-02-06
Also published as: BR0010167A; AU4551300A; NZ515216A; AU771215B2; MXPA01011060A; US6916778B1; BR0010167B1; WO2000065142A1

Abstract

The invention relates to the use of compounds (A) with at least one structural unit of formula (I), wherein X represents groups of formula -CR<1>=CR<2>- or a carbonyl group C=O, R<1> and R<2> meaning hydrogen or essentially organic radicals, Z means essentially organic radicals, n means a number from 0 to 3 and p means a number from 0 to 5, as UV absorbers with an affinity for textile fibres, for protecting the human skin from harmful UV radiation and for protecting dyed textile materials from fading.

Description

Textile fiber affine UV absorber

description

The present invention relates to the use of compounds with a specific structural unit responsible for UV absorption as fiber-affine UV absorbers, further to a method for protecting human skin from damaging UV radiation and a method for protecting colored textile material from fading Color, furthermore a process for increasing the UV protection factor UPF of textile material, furthermore a textile detergent formulation and a textile washing pretreatment and textile washing after-treatment formulation which contain these fiber-affine UV absorbers, because part of this fiber-affine UV -Absorber represents new substances - these new substances themselves as well as a process for their production and also textile material which contains these fiber-affine UV absorbers.

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. The UV-B component of UV radiation is primarily responsible for the reddening of the skin and the increased risk of skin cancer. the range from 280 to 320 nm. The maximum erythema effect is 308 nm.

Textiles 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 is dependent 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.

So far, conventional optical brighteners have mainly been used for finishing and protecting the textiles themselves and also for textile skin protection, in particular those based on stilbene and Tπazm, for example in EP-A 682 145, GB-A 2 313 375 or EP-A A 728 749. The means are but still need improvement in their effect and have a number of disadvantages.

The object of the present invention was to dereitcellen m their effect ver improved fiber-affine UV absorbers, which no longer have the 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)

0

m the

X stands for groupings of the formula -CR ^{1 =} CR ² - or a carbonyl group C = 0, where R ¹ and R ^{2 are} each independently of one another the hydrogen, Cι ~ to Cs-alkyl, Cι ~ to Cg-alkoxy, Cι ~ to Cg-alkoxycarbonyl, Cι ~ to Cs-acyloxy, carboxyl, cyano, nitro, fluorine, chlorine, bromine, sulfonyl, Cι ~ to Cs-alkylsulfonyl or phenyl, which by up to 3 radicals from the group Cι ~ to C ₈ ~ Alkyl, -C ~ to Cs-alkoxy, Cι ~ to Cs-alkoxycarbonyl, C] _- to Cβ-acyloxy, carboxyl, cyano, nitro, chlorine, bromine, sulfonyl and Cι ~ to Cs-alkylsulfonyl may be substituted, wherein R ^{1 can} also stand for the grouping -NQ-CO-, which is bonded with its carbonyl carbon atom to the ortho position of the adjacent phenyl nucleus to form a benzopyrroli-don system and m the Q is hydrogen or a Ci to Cs Denotes alkyl radical,

Z substituents from the group Cι ~ to C _ß -alkyl, Cι ~ bis

Cg-alkoxy, Ci- to Cs-alkoxycarbonyl, Cι ~ to Cs-acyloxy, carboxyl, cyano, nitro, fluorine, chlorine, bromine, sulfonyl, C] _- to Cs-alkylsulfonyl, ammo, mono- or Dι-Cχ- to Cs-alkylammo, carboxamido, which can carry one or two Cι ~ to Cs-alkyl groups on the amide nitrogen, hydroxyl and saturated or unsaturated five- and six-membered heterocyclic radicals, which can be benzanellated, referred to, where two adjacent substituents Z also a saturated or can form an unsaturated five- or six-membered ring, and in the case where p = 0 an ortho-position carboxyl group together with the carbonyl group present an N atom bonded directly to this carbonyl group can form a cyclic imide,

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 suitable - in the sense of the object of the present invention - in the form applied to textile material for protecting the human skin from damaging UV radiation. In addition, they also protect the textile material itself from UV radiation, in particular they protect dyed textile material from fading of the color.

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

have m

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 being present on the tertiary and / or free primary compounds present on the compounds (II) and / or secondary N atoms can be quaternized, m 'denotes a number from 1 to 200, where the number m of structural units (I) makes up 10 to 100% of m', with the proviso that at least one structural unit (I) m is present in the compounds (II), 5 and the variables X, Z, n and p have the meaning given above,

used.

10

The number m of structural units (I) m of the compounds (II) is in particular - depending on the size and structure of the group Y - 1 to 50, preferably 1 to 10, especially 1 to 5, or 2 to 50, preferably 2 to 10 , especially 2 to 5. In most

15 cases m denotes the number 1, 2 or 3. The number m 'of the ammo- or hydroxyl groups m of the group on which Y is capable of linking to the structural units (I) can be a multiple of m; in particular, m 'denotes a number from 1 to 100, especially from 1 to 50, or a number from 2 to

20 200, preferably from 2 to 100, especially from 2 to 50. Preferably, 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 ammo alcohols, oligo- and polyamines, polyalkylene

25 polyamines, polyamidamines, polyvinylamines and polyalkylene polyamines grafted with (poly) ethylene - imm, the nurses and ammo alcohols mentioned also being quaternized on tertiary and / or free primary and / or secondary N atoms present in the compounds (II) . In the quaternized

Such N atoms generally have the fourth organic radical in the form of a C 1 -C 8 -alkyl group, usually a methyl or ethyl group, or a benzyl group which has been introduced by customary methods.

5 In a particularly preferred embodiment, Y stands for the remainder of an aliphatic or cycloaliphatic oligoamm 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 oligoammon also mentioned on the compounds (II) existing tertiary and / or 0 still existing free primary and / or secondary N atoms can be quaternized. Typical examples of such oligoams are 1,2-diammoethane, 1,3-diammopropane, 1,4-diammobutane, diethylammin, dipropylenetramm, tetramethylene tetramm, tetraethylene pentamm, pentaethylene hexam, N- (2-ammethyl) -1, 3 - 5 propanediamine, N, N-dimethylethanolamm, diethanolamm, triethanol - amm, 3 - dirnethylammo- 1-propanol, N- (2-ammethyl) ethanolamm, 3- (dimethylammo) propylamm, N, N'-bis (3-ammopropyl) -1, 2-ethylene diamm, N, N, N ', N' tetrakis (3-ammopropyl) -1, 2-ethylenediamm, N, N, N ', N'-tetrakis [3- (Ci to Ci-al ylamino) propyl] -1, 2-ethylenediamm, N, N 'bis (3-amopropyl) piperaz and N, N' bis [3- (Ci to C ₄ alkylammo) propyl] piperaz. As C 1 -C ₄ -alkyl radicals m the oligoams listed above are in each case methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl m.

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

R ³ - [CH ₂ CH ₂ -NR -] _X [CH ₂ CH ₂ -N-] _y - [CH ₂ CH ₂ -NR ⁷ R ⁸ ] _z

| ^" (III)

CH ₂ CH ₂ -NR ⁵ R ^δ

with an average molecular weight (M _w ) of 200 to 1,000,000, m of which the radicals R ³ to R ⁸ independently of one another are hydrogen, linear or branched C 1 ~ to C ₂ o-alkyl, alkoxy, polyoxyethylene -, -hydroxyalkyl-, - (alkyl) carboxy-, -phosphonoalkyl-,

-Alkylammoreste, C ₂ - to C ₂ o-alkenyl residues or Cg- to C ₂ o ~ aryl, -Aryloxy-, -Hydroxyaryl-, -Arylcarboxy- or -Arylammoreste, which are optionally further substituted, and R ⁴ and R ⁵ furthermore mean further polyethyleneimm polymer chains and x, y and z independently denote 0 or an integer, the said polyethyleneimm also on m the compounds (II) present tertiary and / or free primary and / or secondary present N atoms can be quaternized.

The sum of x, y and z should be chosen so that the average molecular weight is in the range given. Preferred ranges for the average molecular weight (M _w ) of the polyethylene block (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 stands for the remainder of a polyamidoamm with an average molecular weight (M _w ) of 500 to 100,000,000, which polyamines by reaction of C - to Cio-dicarboxylic acids with poly (C ₂ - to C -alkylene) is available with 3 to 20 basic nitrogen atoms in the molecule l and which has at least m 'primary and / or secondary amino groups which are used to form Am d or ester bonds the structural unit (I) are capable, said polyamidoamm also being quaternized on the tertiary and / or free primary and / or secondary N atoms present in the compounds (II).

Preferred ranges for the average molecular weight (M _w ) of the polyamido amme are 800 to 1,000,000, in particular 1200 to 200,000.

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

_R 9 _R 10 _N _ [ _CqH2q _ _NR ll_] _r -C _q H _2q -NR ⁹ R ¹⁰ (IV)

with an average molecular weight (M _w ) of 100 to 100,000,000, m of which the radicals R ⁹ to R ¹¹ independently of one another are hydrogen, linear or branched C 1 ~ to C ₂ o-alkyl, alkoxy, polyoxyethylene -, -Hydroxyalkyl-, - (Alkyl) carboxy-, -Phosphonoalkyl-, -Alkylammoreste, C - to C ₂ o ^_A lkenyl residues or Cς- to C ₂ o-aryl-, -Aryloxy-, -Hydroxyaryl-, -Arylcarboxy- , or arylammo radicals, which are optionally further substituted, q denotes an integer from 2 to 6 and r denotes an integer, the alkylammo radicals mentioned also being able to be continued in the alkyl part in the manner of denim dimers and the ge ^¬ mentioned polyamm 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 range specified. Preferred ranges for the average molar mass (M _w ) of the polyamene (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 .

Dendπmere or dendrimer nurse or their precursors are N, N, N ', N' -Tetraammopropylethylendiam, also referred to as Nβ-A-mm ^¬ be, as well as the therefrom produced by Ammopropylierung, according to the number of N atoms designated dendπmeren nurse as N14 -, N30, N62 and N128 Amm. These nurses have an ethylene diamm structure, the hydrogen atoms of which are substituted on the nitrogen by ammo (n-propyl) residues. In turn, the final thereby stan-ended amino groups by corresponding ammonium propyl substituted (N14-Amm), etc .. manufacturing methods for such nurse m are described in WO 96/15097, been ^¬ from Ethylendiamm. Likewise preferred examples of these nurses are corresponding N nurses, as described in WO 93/14147. are written, which are prepared from butylene diamine instead of ethylene diamine as above.

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

R ¹² - [CH ₂ -CH-] _S - [CH ₂ -CHR ¹⁵ -] _t -R ¹⁶ NR ¹³ R ¹⁴

with an average molecular weight (M _w ) of 300 to 100,000,000, m of which the radicals R ¹² to R ¹⁶ independently of one another are hydrogen, linear or branched C 1 ~ to C ₂ o-alkyl, alkoxy, polyoxyethylene -, -hydroxyalkyl-, - (alkyl) carboxy-, -phosphonoalkyl-,

-Alkylammoreste, C - to C ₂ o-alkenyl residues or Cg- to C ₂ o-aryl-, -Aryloxy-, -hydroxyaryl-, -Arylcarboxy- or -Arylammoreste, which are optionally further substituted, and R ¹⁵ above also mean a formamidyl, pyrrolidonyl or imidazolyl radical, s denotes an integer and t stands for 0 or an integer, the polyamine mentioned also being present on the tertiary and / or free primary and / or free primary and / still present compounds (II) 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 average molecular weight (M _w ) of the polyvinylammers (V) are 500 to 500,000, in particular 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 in} each case independently of one another hydrogen, cyano or are unsubstituted phenyl or where R ^{1 represents} the group -NH-CO, which is bonded with its carbonyl carbon atom to the ortho position of the adjacent phenyl nucleus to form a benzopyrrolidone system, and R ² also denotes cyano and n denotes the number 1 designated.

Furthermore, compounds (A) are preferably used which have one or more structural units (I) in which Z is a substituent from the group Ci _. - bs Cs-alkoxy, ammo, mono- or Dι-C_- to Cs-alkylam o and hydroxy and p denotes the number 1.

In connection with the variables R ¹ , R ² , Q and Z mentioned above, C ¹ -C 4 -alkyl, alkoxy and acyloxy mean in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl or the corresponding alkoxy or acyloxy radicals.

The saturated or unsaturated five- and six-membered heterocyclic radicals for the variable Z, which can be benzanellated, are, for example, the imidazolyl or benzimidazolyl radical m.

A benzanellant m is particularly suitable as the unsaturated six-membered ring which two adjacent substituents Z can form.

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

p-Ammobenzoyl p- (Mono-Ci to Cs-alkylammo) benzoyl p- (Di-Ci to Cs-alkylammo) benzoyl p-Hydroxycmnamoyl (derived from p-Hydroxyzimtsaure) p-Cι ~ to C ₈ -alkoxycmnamoyl (derived from p-Ci to

C ₈ ~ alkoxycinnamic acid) o-hydroxybenzoyl

Phthalimidoyl- o-carboxamidobenzoyl o- (Ci to Cs-alkoxycarbonyl) benzoyl o-ammobenzoyl o- (mono-Cχ to Cs-alkylammo) benzoyl o- (Dι-Cχ- to Cs-alkylammo) benzoyl

2-cyano-3, 3-dιphenylacryloyl m-benzimidazolyl-p-hydroxybenzoyl the structural unit of the formula

Individual particularly preferred compounds (A) themselves are:

• α, ω-bis [(p-dimethylam o) benzoylamide] from N, N 'bis (3-aιιno - propyl) -1, 2-ethylenediamine • α, ω-bis [(p-dimethylammo) benzoylamide] Methylene tetramm

• α, ω-Bιs [(p-dimethylammo) benzoylamide] from pentaethylene hexam

• α, ω-bis [p-methoxycmnamoylamid] from N, N 'bis (3-ammopropyl) -1, 2-ethylenediamine, quaternized on the two central secondary amino groups, each with two methyl groups

• - (p-Methoxycmnamoylamid) from N, N '-Bis (3-ammo - propyl) -1, 2-ethylenediamm

• α, ω-bis [p-methoxycmnamoylamid] from pentaethylene hexamm

• α- (p-Dimethylammo) benzoylamide from N, N 'bis (3-amopropyl) -1, 2-ethylenediamine

• reaction product of a polyethylene imine of the formula (III) with M _w = 700 with methyl p-methoxycinnamate in a molar ratio of 1: 3

• Reaction product of a polyethylene imine of the formula (III) with M _w = 700 with 2-cyano-3, 3 -diphenylacrylic acid ethyl ester in a molar ratio of 1: 3.

It can sometimes be advantageous if the fiber-affine UV absorbers (A) used in accordance with the invention with at least one structural unit (I) or the fiber-affine compounds (A) of general formula (II) used in accordance with the invention in combination with other UV absorbers, Antioxidants and / or radical scavengers are used.

Can enter or to the UV absorbers, the m combination with the compounds (A) for use in conjunction with these ingredients of application formulation be charged in principle, all übli ^¬ chen UV-A-absorber, UV-B absorbers, and broadband absorber, the are structurally different from the respective compounds (A). Examples of such UV absorbers are in particular:

• esters of p-ammobenzoic acid, such as 4-dimethylamobenzoate, methyl ester, 4-dimethylammobenzoate, 4-dimethyl-2-ethylhexyl ester or 4-bis (polyethoxy) on the above-polyethoxyethyl ester

• Alkyl esters of p-alkoxycinnamic acids such as methyl p-methoxycinnamate, ethyl p-methoxycinnamate, propyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate or n-octyl p-methoxycinnamate • Alkyl esters of 2-cyano-3, 3-dιphenylacrylsaure such as 2-cyano-3, 3-dιphenylacrylsauremethylester, 2-cyano-3, 3-dιphe nylacrylsaureethylester, 2-Cyano-3, 3-Dιphenylacrylsaure-r-oc tylester, 2nd -Cyano-3, 3-diphylacrylic acid 2'-ethylhexyl or 2-cyano-3, 3-diphylacrylic acid polyethoxymethyl ester

• esters of salicylic acid such as 2-ethylhexyl salicylate or phenyl salicylate

• 2-hydroxybenzophenones such as 2, 4-dihydroxybenzophenone, 2 - ^ - j droxy-4-methoxybenzophenone, 2, 2 ', 4, 4' -tetrahydroxybenzcpne non, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hy droxy-4-n-octoxybenzophenone, 2,2 '-Dιhydroxy-4, 4' -dimetnox benzophenone, 2,2 '-Dιhydroxy-4, 4' -dimethoxybenzophe non-5, 5 '-bissulfonic acid (sodium salt), 2-Hydroxy-4-all _/ loxy benzophenone, 2-Hydroxy-4- (2 '-ethylhexyloxy) benzophenone, 2-Hydroxy-3-carboxybenzophenone or 2- (4' -Dιethylammo-2 '-r / dro xybenzoyl) benzoic acid hexyl ester

• furthermore dibenzoylmethanes, phenylbenzotπazoles and phenylbenzimidazoles and 3- (4-methylbenzylidene) camphor and 2,4,6-trιanιlmo-p- (carbo-2 'ethylhexyl-1' oxy) -1,3,5-tπazm

The antioxidants and radical scavengers which are used in combination with the compounds (A) or which together can be components of the application formulation include all customary compounds of this type, in particular any compound.

• substituted phenols, hydrochmones and pyrocatechols such as 2, 6-Dι-tert. -butylphenol, 2, 4, 6-Tπ-tert -butylphenoi,

2, 4-dimethyl-6-tert-bulylphenol, 2, 6-dim-tert. -butyl-4- e thylphenol, 2, 6-Dι-tert. -butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-tert.-butyl phenol), propyl, octyl and dodecyl gallate or tert. -Butylhy drochmon

Ascorbic, lactic, citric and tartaric acid and their salts

Tocopherol (acetyl-α-tocopherol)

Diazobicyclo [2.2.2] octane

usual aromatic nurse

usual organic sulfides • usual sterically hindered wet nurse such as Uvmul®4049K, Uv ul 4050H and Uvmul 5050H (sold by BASF Aktiengesellschaft)

Textile material on which the compounds (A) of the present invention can absorb and develop their protective action there includes in particular articles 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 cotton-polyester mixtures are of interest.

The present invention also relates to a process for protecting human skin from damaging UV radiation, which is characterized in that compounds (A) having structural units of the general formula (I) are used on textile material in textile finishing, that is to say in Manufacture of textiles.

The present invention also relates to a method for protecting human skin from damaging UV radiation, which is characterized in that

Applies compounds (A) with structural units of the general formula (I) to textile material in textile washing and / or textile washing pretreatment or textile washing aftertreatment.

The present invention also ^relates to a process for protecting dyed textile material from fading of the color, which is characterized in that compounds (A) having structural units of the general formula (I) are used on textile material in textile finishing, ie oei the manufacture of textiles.

The present invention also relates to processes for protecting dyed textile material from fading of the color, which is characterized in that compounds (A) having structural units of the general formula (I) on textile material during textile washing and / or Applying textile washing or textile washing aftertreatment.

The present invention further provides a method for increasing the ultraviolet protection factor of UPF of a textile material, which is characterized in that Ver ^¬ compounds (A) having 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 method for increasing the UV protection factor UPF of textile material, which is characterized in that compounds (A) with structural units of the general formula (I) on textile material during textile washing and / or who applies pre-treatment or post-treatment of textile washing.

The UV protection factor UPF ("Ultraviolet Radiation Protection Factor") of textiles is tuned in accordance with the Australian / New Zealand standard AS / NZS 4399: 1996 using an m 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:

400 nm

S _/ , x E, x dλ λ = 280 nm

UPF =

400 nm

S) x E> x T> x dλ λ = 280 nm

in which

Sχ = spectral radiation of the sun in the UV range for long waves λ

Eχ = spectral erythema effectiveness of UV radiation at the wavelength λ

Tχ = spectral transmission of the textile object at the wavelength λ

The fiber-affine UV absorber (A) according to the invention with at least one structural unit (I) can be used in the finishing of the textile material, that is to say in the manufacture of the textiles, or in the care of the finished textile article, that is to say in the washing and / or washing of textiles - or textile washing aftertreatment. Textile finishing ("textile finishing") is understood to mean the work processes in the production of textiles, in which the geo-smoke value of the textiles is increased and the textiles are embellished by an advantageous design of their external properties. Typical processes for increasing the utility value are the easy care equipment, the anti-crease and the shrink resistant equipment. Typical processes for the design of the outer properties are coloring, bleaching, printing and mercury. When finishing, in particular stucco goods, finishes are generally used which contain the finishing agents and to which the compounds (A) in the sense of the present invention are preferably also added.

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

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

(B) 1 to 60% by weight of inorganic builders based on stable or amorphous aluminosilicates, crystalline or amorphous

Silicates, carbonates or phosphates,

(C) 0.5 to 40% by weight of anionic surfactants and

(D) 0.5 to 40% by weight of nonionic surfactants.

Suitable inorganic builders (B) are, above all, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as, in particular, zeolites. Different types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg or ammonium. 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, for example δ-Na ₂ Si ₂ 0 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 (Bπtesil® H 20 manufacturer: Akzo) can also be used.

Suitable inorganic builder substances (B) based on carbonate are 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 hydrogen carbonates, in particular sodium carbonate and / or sodium hydrogen carbonate, are preferably used.

Common phosphates as inorganic builders (B) are polyphosphates such as e.g. Pentasodium tphosphate.

The components (B) mentioned can be used individually or in mixtures with one another.

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

In a preferred embodiment, the textile detergent formulation according to the invention does not contain any phosphate-based builders or only up to a maximum of 5% by weight, in particular only up to a maximum of 2% by weight.

Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ to Cn alcohol sulfates, Cχ ₂ to C ₁₄ alcohol sulfates, Cχ-Ciβ alcohol sulfates, lauryl sulfa, cetyl sulfate, myπstyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated Cs "to C ₂₂ ~ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by first adding a CQ - to C ₂₂ "_', preferably a C ₁ -C ₁ - -Alcohol, for example a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. 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 with all propylene oxide and, if appropriate, butylene oxide. Also suitable are those alkoxylated CQ to C ₂₂ alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide. The alkoxylated Cs to C ₂₂ "alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or m random distribution. Depending on the type of alkoxylation catalyst, alkyl ether sulfates with broad or narrow alkylene oxide homolog distribution can be obtained.

Other suitable anionic surfactants are alkane sulfonates such as C "to C ₂₄ -, preferably Cι ₀ - to C _X8 alkanesulfonates, and soaps such as the Na and K salts of Cs to C ₂ -Carbonsauren.

Other suitable anionic surfactants are linear Cs to C ₂₀ "alkylbenzenesulfonates (" LAS "), preferably linear Cg - to -C ₃ alkylbenzenesulfonates and alkyltoluenesulfonates.

Also suitable as anionic surfactants (C), Cs to C ₂₄ -01efmsulfonate and -disulfonates, which may also be mixtures of alkene and hydroxyalkane sulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl - glycermsulfonate, Fettsaureglycermestersulfonate, alkyl phenol - polyglycol ether , Paraffin sulfonates with about 20 to about 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acylmethyl taurates, alkyl amber acid, alkenyl succinic acids or their half esters or half amides, alkyl sulfide amine acids or their monosides - and diesters of sulfosuccinic acids, acyl sarcosmates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosmates.

The anionic surfactants 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 salts such as e.g. Hydroxyethylammonium, di (hydroxyethyl) ammonium and Tπ (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 Cg - to C ₂₀ linear alkyl benzene sulfonates (LAS) are also used, these are usually used in an amount of up to 10% by weight, in particular up to 8% by weight.

Individual anionic surfactants or a combination of different anionic surfactants can be used. Anionic surfactants from only one class can be used, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but it is also possible to use surfactant mixtures from different classes, for example a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.

Suitable nonionic surfactants (D) are, for example, alkoxylated Cs 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 abovementioned alkylene oxide added 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. Ethylene oxide is preferably used as the alkylene 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 alkylphenol ethoxylates with C ₆ to Cχ alkyl chains and 5 to 30 mol alkylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms of 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

ßl CNDB ¹ NCD

OB ² B ² 0

wherein Bi is a Cζ - to C ₂ alkyl, B ² hydrogen or Ci- to C -alkyl and D is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. Preferably B ¹ stands for C ₁₀ - to Cis-alkyl, B ² for CH ₃ and D for a C ₅ - or C ₆ "est. For example, such compounds are obtained by acylation of reducing animated sugars with acid chlorides from Cio" to Cis -Carboxylic acids. Other nonionic surfactants that come into consideration are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225

R ¹ -CO NH- (CH ₂ ) _y -0- (A ¹ 0) _x -R ²

m the

R ¹ denotes a C ₅ -C ₂ -alkyl or alkenyl radical, R ² denotes a C ¹ -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-butyltriglycolamm of the formula H ₂ N- (CH ₂ -CH ₂ -0) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyl tetraglycol amine of the formula H ₂ N- ( CH ₂ -CH ₂ -0) ₄ -C ₂ H ₅ with a commercially available mixture of saturated Cs to Cis fatty acid methyl esters.

Also suitable as nonionic surfactants (D) are block 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 amide Fatty acid amide ethoxylates, in particular end group-capped, and fatty acid alkanolamide alkoxylates.

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

You can use individual nonionic surfactants or a combination un ^¬ terschiedlicher nonionic surfactants. Nonionic surfactants from only one class can be used, in particular only alkoxylated Cs to C ₂₂ alcohols, but it is also possible to use surfactant mixtures from different classes.

In a preferred embodiment, the textile detergent formulation according to the invention contains 0.05 to 20% by weight, in particular 1 to 10% by weight, organic cobuilder in the form of low molecular weight, oligomeric or polymeric carboxylic acids, in particular polycarboxylic acids, in addition to the inorganic builders (B). or phosphonic acids or their salts, in particular sodium or potassium salts. Examples of suitable low-molecular carboxylic acids or phosphonic acids as organic cobuilders are:

Phosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid, ammotris (methylenephosphonic acid), ethylenediammetetra (methylenephosphonic acid), hexamethylenediammetetra (methylenephosphonic acid) and diethylenetrammine penta (methylenephosphonic acid);

C ₄ - to C ₂ o -di-, tri- and tetracarboxylic acids such as, for example, succinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkenyl amber acid with C ₂ to C ₆ alkyl or alkenyl Leftovers;

C ₄ - to C o -hydroxycarboxylic acids such as malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tπcarboxylic acid;

Ammopolycarboxylic acids such as Nitπlotπessigsaure, ß-Alanmdi acetic acid, Ethylenediammtetraessigsaure, Sermdiessigsaure, Isosermermiesdigsigsaure, Alkylethylenediammtriacetate, N, N-bιs (Carboxy methyl) glutamic acid, Ethylenediammdibernstemsauredure and N- (2) Ethylsydic acid, N- (2)

Examples of suitable oligomeric or polymeric carboxylic acids as organic cobuilders are:

Oligomalem 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 monoethyl-unsaturated monomers as comonomers

from group (1) m amounts of up to 95% by weight, from group (11) m amounts of up to 60% by weight and from group (111) m amounts of up to 20% by weight

can be empolymeπsiert.

Examples of suitable unsaturated C ₄ -Cs dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred. Group (1) comprises monoethylenically unsaturated C ₈ -C ₈ "monocarboxylic acids such as, for example, acrylic acid, methacrylic acid, crotonic acid and methyl acetic acid. Acrylic acid and methacrylic acid are preferably used from group (1).

The group (s) includes monoethylenically unsaturated C ₂ -C -01ef e, methyl alkyl ethers with Ci Cs alkyl groups, styrene, methyl esters of Ci-Cs carboxylic acids, (meth) acrylamide and Vmyl - pyrrolidone. ₂ -C _ß -Olefme, Vmylalkylether with _Ci-C4 alkyl, V are preferably selected from the group (n) C ylacetate and Vmyl - propionate used.

Group (111) includes (meth) acrylic esters of Ci- to Cs alcohols, (meth) acrylonitrile, (meth) acrylamides of Ci-Cs amines, N-Vmylform amide and N-Vmylimidazole.

If the polymers of group (11) contain Vmylester empolymeπsiert, they can also be partially or completely hydrolyzed to Vmyl alcohol structural units. Suitable copolymers and terpolymers are known for example from US-A 3887806 and DE-A 4313909.

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 molar masses of 1000 to 150,000;

Terpolymers of maleic acid, acrylic acid and a methyl ester of a Cχ-C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + methyl ester) to 95 (maleic acid): 10 (acrylic acid + methyl ester), the weight ratio of acrylic acid to Vmyl ^¬ ester can vary in the range from 30:70 to 70:30;

Copolymers of maleic acid with C ₂ -Cs 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 4415623 and DE-A 4313909 are also suitable as organic cobuilders. Suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vylacetic acid as well as mixtures of acrylic acid and maleic acid, the amounts of 40 to 95% by weight, based on the component to be grafted on.

For modification, up to 30% by weight, based on the component to be grafted, of additional monoethylenically unsaturated monomers can also be present in polymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (n) and (m).

Degraded polysaccharides such as, for example, acidic or enzymatically degraded starches, inulms or cellulose, protein hydrolyzates and reduced (hydrogenated or hydrogenated ammylated) degraded polysaccharides such as, for example, mannitol, sorbitol, amosorbitol and N-alkylglucam are also suitable, as are polyalkylene glycols with molar masses with bismol 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 ₂₂ -C ₂₂ "alcohols, see. US-A 5756456.

Polyglyoxylic acids suitable as organic cobuilders are described, for example, in EP-B 001004, US-A 5399286, DE-A 4106355 and EP-A 656914. The end groups of the polyglyoxylic acids can have different structures.

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

Organic cobuilders used include, in particular, polyaspartic acids or cocondensates of aspartic acid with other amino acids, C ₄ -C ₂₅ mono- or dicarboxylic acids and / or C ₄ -C ₂₅ mono- or diamines. Polyaspartic acids modified with C ₆ -C ₂₂ "mono- or dicarboxylic acids or modified with Cg-C ₂₂ mono- or diamines are particularly preferably used.

Also suitable as organic cobuilders are immodibernic acid, oxydibernic acid, ammopolycarboxylates, alkyl polyammocarboxylates, ammopolyalkylene phosphonates, polyglutamates, hydrophobically modified citric acid such as, for example, agaic acid, poly-α-hydroxyacrylic acid, N-acyl ethylenediammate Lauroylethylene diamine triacetate and alkyl amides of ethylene diamine tetraacetic acid such as EDTA tallow amide.

Oxidized starches can also be used as organic cobuilders.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally contains, in particular in addition to the inorganic builders (B), the anionic surfactants (C) and / or the nonionic surfactants

(D), 0.5 to 20 wt .-%, in particular 1 to 10 wt .-%, Glycm-N, N-diacetic acid derivatives, as described in WO 97/19159.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally contains 0.5 to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23% by weight, of bleaching agent in the form of percarboxylic acids, e.g. Diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoper oxophthalic or terephthalic acid, adducts of hydrogen peroxide with inorganic salts, e.g. Sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide with organic compounds, e.g. Urea perhydrate, or of inorganic peroxo salts, e.g. 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, of bleach activators. In the case of color detergents, the bleach (if present) is generally used without a bleach activator, otherwise bleach activators are usually present.

Suitable bleach activators are:

polyacylated sugars, e.g. Pentaacetyl glucose;

Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, e.g. Sodium p-nonanoyloxybenzenesulfonate or sodium p -benzoyloxybenzenesulfonate;

N, N-diacylated and N, N, N ', N' - tetraacylated ames, for example N, N, N ', N' tetraacetylmethylene diamine and ethylenediamine (TAED), N, N-diacetylanilm, N, N-diacetyl -p toluidm or 1, 3 -diacylated hydantoms such as 1, 3 -diacetyl-5, 5 -dimethyl-hydantome; N-alkyl-N-sulfonylcarbonamides, for example N-methyl -N-mesylacetamide or N methyl -N-mesylbenzamide;

N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. Monoacetylmalemic acid hydrazide;

0, N, N-tπ-substituted hydroxylammes, e.g. O-benzoyl -N, N succmylhydroxylamm, O-acetyl -N, N-succmylhydroxylamm or 0, N, N-Tπacetylhydroxylamm;

N, N '-diacylsulfurylamides, e.g. N, N '-dimethyl -N, N' -diacetyl-sulfurylamide or N, '-diethyl -N, N' -dipropionylsulfurylamide;

acylated lactams such as, for example, acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam;

Anthramite derivatives such as 2-methylanthranil or 2-phenylanthranil;

Triacylcyanurates, e.g. Tπacetylcyanurat or Tπbenzoylcyanurat;

Oxime esters and bisoxime esters such as 0-acetylacetone oxime or bisisopropylimocarbonate;

Carboxylic acid anhydrides, e.g. Acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;

Enol esters such as Isopropenyl acetate;

1,3-diacyl -4,5 -diacyloxy imidazoles, e.g. 1,3-diacetyl -4,5 diacetoxyimidazole;

Tetraacetylglycoluril and tetrapropionylglycoluπl;

diacylated 2,5 -diketopiperazme, e.g. 1,4 -diacetyl -2,5 -di-ketopiperazm;

ammonium substituted nitπle such as e.g. N-methylmorpholmium acetonitπlmethylsulfat;

Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, for example tetraacetylpropylene diurea; α-acyloxypolyacylmalonamides, for example α-acetoxy N, '-diacetyl-malonamide;

Diacyl-dioxohexahydro- 1, 3, 5 tπazme, e.g. 1.5 diacetyl 2, 4 -dioxohexahydro 1,3,5-tπazιn;

Benz - (4H) 1, 3-oxazm-4 -one with alkyl radicals, e.g. Methyl, or aromatic residues e.g. Phenyl, m the 2 position.

The described bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleaching catalysts. Suitable bleaching catalysts are, for example, quaternized inks and sulfonimme, which are described, for example, in US Pat. No. 5,360,569 and EP-A 453,003. Particularly effective bleaching catalysts are manganese complexes, which are described, for example, in WO-A 94/21777. When used in detergent formulations, such compounds are used in a maximum of m amounts up to 1.5% by weight, in particular up to 0.5% by weight, and in the case of very active manganese complexes up to 0.1% by weight. -%, incorporated.

In addition to the bleaching system described, comprising bleaching agents, bleach activators and, if appropriate, bleaching catalysts, it is also possible to use systems with enzymatic peroxide release or photoactivated bleaching systems for the textile detergent formulation according to the invention.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally contains 0.05 to 4% by weight of enzymes. Enzymes preferably used in detergents are proteases, amylases, lipases and cellulases. Quantities of 0.1 to 1.5% by weight, particularly preferably 0.2 to 1.0% by weight, of the prepared enzyme are preferably added. Suitable proteases are, for example, Savmase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is e.g. B. Lipolase (manufacturer: Novo Nordisk). A suitable cellulase is eg Celluzym (manufacturer: Novo Nordisk). Peroxidases can also be used to activate the bleaching system. You can use single enzymes or a combination of different enzymes. If appropriate, the textile detergent formulation according to the invention may also contain enzyme stabilizers, for example calcium propionate, sodium formate or boric acids or their salts, and / or oxidation inhibitors. 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 usual amounts:

- Cationic surfactants, usually in an amount up to

25% by weight, preferably 3 to 15% by weight, for example Cg- to Ci ₆ -Dιalkyldιmethylammonιumhalogenιde, Dialkoxydimethylam monium halides or imidazolmium salts with long-chain alkyl radical;

amphoteric surfactants, usually in an amount of up to 15% by weight, preferably 2 to 10% by weight, for example derivatives of secondary or tertiary amines such as, for example, -C ₈ alkyl betame or C ₁ -Cis alkyl sulfobetame or ammoxides such as alkyldimethylammoxides;

Graying inhibitors and target release polymers (these are, for example, polyesters from polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids or polyesters from polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acids Polyesters are known, see 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 release 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-3 711 299, US-A 4 904 408, US-A-4 846 994 and US-A-4 849 126, or modified celluloses such as methyl cellulose, hydroxyl propyl cellulose or carboxymethyl cellulose. Graying mixers and target release polymers are 0.1 to 2.5% by weight of the detergent formulations, preferably 0.2 to 1.5% by weight, particularly preferably 0.3 to 1%. .. 2 wt -% contained ^¬ th preferred target -release polymers used are selected from the US-A-4746456 the known graft polymer of Vmylacetat on polyethylene oxide of molecular weight ratio 2500 8000 in 1.2: 1 to 3.0: 1 , as well as commercially available polyethylene terephthalate / polyoxyethylene terephthalates of molecular weight 3000 to 25000 made of polyethylene oxides of molecular weight 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and those known from DE-A-44 03 866 Block polycondensates, the blocks of (a) ester units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) contain ester units from aromatic dicarboxylic acids and polyhydric alcohols. These amphiphilic block copolymers have molecular weights from 1500 to 25000.);

Color transfer inhibitors, for example homo- and copolymerizates of N-Vmylpyrrolidone, N-Vmylimidazole, N-Vmyloxazolidone or 4-Vmylpyπdm-N-oxide with molecular weights from 15,000 to 100,000 and crosslinked fine-particle polymers based on these monomers with a particle size 0.1 to 500, preferably 0.1 to 250 μm;

non-surfactant-like foam steamers or foam inhibitors, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica;

Complexing agents (also in the function of organic cobuilders);

optical brighteners;

Polyethylene glycols;

- perfumes or fragrances;

Fillers;

inorganic leveling agents, e.g. 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 is usually in powder or granule form or in extrudate or tablet form.

Detergents in powder or granular form according to the invention can contain up to 60% by weight of inorganic fillers. Sodium sulfate is usually used for this. The detergents according to the invention are preferably low in leveling agents and contain only up to 20% by weight, particularly preferably only up to 8% by weight of leveling agents, particularly in the case of compact or ultra-compact detergents. The solid detergents according to the invention can have different rubble densities in the range from 300 to 1300 g / 1, in particular from 550 to 1200 g / 1. Modern compact laundry detergents generally have high debris densities and show a granular structure. The processes which are public in technology can be used for the desired compression of the detergents.

The textile detergent formulation according to the invention is produced by customary methods and, if appropriate, is made up.

The present invention also relates to a textile laundry pretreatment and textile laundry after-treatment formulation which comprises 0.01 to 40% by weight, in particular 0.5 to 20% by weight, of at least one compound (A) having structural units of the general formula (I) in addition to the other usual ingredients.

Preference is given to a textile pre-wash and post-treatment formulation which further comprises 1 to 50% by weight, in particular 3 to 30% by weight, of one or more cationic surfactants from the group of the quaternary diester ammonium salts, the quaternary tetraalkylammonium salts, the quaternaries Contains diamidoammonium salts, the amidoammoester and the imidazolmium salts.

Quaternary diester ammonium salts are in particular those which have two C i to C ₂₂ alk (en) ylcarbonyloxy (mono- to pentamethylene) radicals and two Ci _. have up to C ₃ alkyl or hydroxyalkyl residues on the quaternary N atom and, for example, carry chloride, bromide, methosulfate or sulfate as counterion

Quaternary diesterammonium further include in particular those which have a Cn to C ₂₂ ^_ alk (en) ylcarbonyl-oxy-tπmethylen radical, on the central carbon atom of the tri-methylene grouping a Cιχ- -C ₂ alk (en) ylcarbonyl-oxy residue carries, and three Ci _. - C ₃ alkyl or hydroxyalkyl radicals on the quaternary N atom and as Counterion, for example, wear chloride, bromide, methosulfate or sulfate.

Quaternary tetraalkylammonium salts are, in particular, those which have two Ci to C _e 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 are in particular those which have two Cβ- to C ₂₄ -alk (en) ylcarbonyl-ammo-ethylene radicals, a

Substituents selected from hydrogen, methyl, ethyl and poly oxyethylene with up to 5 oxyethylene units and as the fourth radicals have a methyl group on the quaternary N atom and, for example, carry chloride, bromide, methosulfate or sulfate as counterion.

Amidoammoesters are, in particular, tertiary amines which, as substituents on the N atom, have a Cn ~ to C ₂₂ alk (en) ylcarbonyl ammo- (mono- to trimethylene) residue, a Cιχ to C ₂₂ - lk (en) ylcarbonyl- oxy (mono to trimethylene) residue and a methyl group.

Imidazolmiumsalze are in particular those which m of 2-Posι- tion of the heterocycle a C ₁₄ - to cis-alk (en) yl radical new spectral N atom, are a C ₁₄ - to cis-alk (en) yl-carbonyl (oxy or ammo) -ethylene residue and on the N-atom carrying the positive charge carry hydrogen, methyl or ethyl, counterions are, for example, chloride, bromide, methosulfate or sulfate.

In the case of textile laundry after-treatment formulations, special fabric softeners and fabric care agents are considered.

Other common constituents for such a textile washing pretreatment and textile washing after-treatment formulation are nonionic surfactants, fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides, preservatives and water in the amounts customary for this.

Part of the compounds (A) represents new substances. Therefore, the present invention also relates to compounds (A ') which have the general formula (Ha)

have m

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 together at least m 'primary and / or has secondary amine 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 compounds (Ha) present in the tertiary and / or free 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) m 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 by reacting Carnonsauredeπvate of the general formula (Ia)

m the Y ″ for an alkoxyl group having 1 to 4 carbon atoms, for example methyl or ethyl, em halogen atom, for example chlorine or bromine, an am o group which may optionally carry em or two C] - to C ₄ -alkyl groups or a hydroxyl group stands and the other variables have the meaning given above, or precursors of carboxylic acid derivatives of the general formula (Ia), in which the structural unit responsible for UV absorption is formed only in a subsequent reaction step,

with the compounds on which Y 'is based to form the corresponding carboxylic acid amide and / or caronate ester structures and, if appropriate, then partially or completely quaternized any tertiary and / or primary and / or secondary N atoms present in the compounds (Ha) .

In the case of 2-cyano-3-diphenylacryloyl structural units for (A), it can be advantageous to use cyanoacetic acid esters as the precursor of (Ia), which are based on the Y '

React compounds and finally m t with the corresponding ketim such as a benzophenone or an acylphenon to convert to the desired compound (A ') or (A).

The textile fiber-affine UV absorbers according to the invention are outstandingly suitable both for the protection of human skin from harmful UV radiation and for the protection of colored textile material from fading of the color. Textile material which contains at least one compound (A) with at least one structural unit of the general formula (I) is thus also an object of the present invention.

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

Example 1 - Preparation of α, ω-bis [p-methoxycmnamoylamide] from N, N '-Bis (3-ammopropyl) -1, 2-ethylenediamine

The following preparation instructions represent a typical example for the preparation of the compounds ^ A): 28.8 g (0.15 mol) of methyl p-methoxycinnamate were combined with 1.5 g (0.008 mol) of a 30% by weight solution of Natπummethylat methanol and 13.2 g (0.075 mol) of N, N 'bis (3-ammopropyl) -1, 2-ethylenediamine for 4 hours at 100 ° C, then the methanol was distilled off. After the usual work-up, a light beige product was obtained with a yield of 78%. Example 2 - Quaternization of the Product from Example 1

The product from Example 1 was methylated by reaction with dimethyl sulfate as methylating agent in a molar ratio of 1: 4 using a conventional method on the two secondary amino groups in the middle. A light product was obtained with a yield of 98%.

Example 3 - Preparation of a, ω-bis [2 - cyano-3, 3 -diphenylacrylo-ylamide] from diethylene

396 g (4.0 mol) of methyl cyanoacetate were added dropwise to a solution of 206 g (2.0 mol) of diethylene ether in 1000 ml of methanol at 20 to 25 ° C. in the course of 30 minutes. The mixture was stirred at 20 ° C for 3 hours and left overnight. The precipitate was filtered off, washed with methanol and dried. 412 g of the corresponding diamide were obtained (88% yield).

400 g (2.2 mol) of benzophenone were added dropwise at 60 ° C. to a solution of 237 g (1.0 mol) of this diamide in 800 ml of methanol. The mixture was then stirred at 60 ° C for 6 hours. After cooling, the precipitate was filtered off and washed with methanol and petroleum ether. 474 g of the title compound were obtained (84% yield).

Application studies

Example 4 - Use in textile washing in the main wash cycle

White cotton fabric with a flake weight 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 low in textile fibers or 400 ppm, based on the wash liquor, of the UV absorber AI, A2, A3 or A4 according to the invention had been added to the formulation before the wash. After washing, rinsing, spinning and drying the cotton fabric, the UV protection factor UPF was determined.

Structures of the UV absorbers used:

I = α, ω-bis [p-methoxycmnamoylamid] from pentaethylene hexamm A2 = reaction product of a commercial polyethylene imine of formula (III) with M _w = 700 (Polymm G 10 from BASF Aktiengesellschaft) with methyl p-methoxycinnamate in a molar ratio of 1: 3

A3 = α, ω-bis [p-methoxycmnamoylamid] from N, N 'bis (3-ammo propyl) -1, 2-ethylenediamine, quaternized on the two secondary secondary amino groups with two methyl groups each (product from Example 2)

A4 = a, ω-Bιs [2 -cyano -3, 3 -diphenylacryloylamid] from Diethylenentπ amm (product from Example 3)

Table 1 shows the results of the tests:

Table 1

without UV absorber UPF = 4.60 with UV absorber AI UPF = 11.30 with UV absorber A2 UPF = 10.00 with UV absorber A3 UPF = 11.70 with UV absorber A4 UPF = 15.40

The results show that the use of the UV absorbers AI to A4 in the main wash cycle for washing textiles in the smn of the present invention leads to a significant increase in textile UV protection.

Example 5 - Application in textile washing aftertreatment in fabric softener bath

White cotton fabric with a basis weight of 100g / m2 and a UV protection factor UPF = 4.50 was washed five times in a row. Each wash cycle consisted of a main wash at 40 ° C with a commercial detergent formulation (Persil® Megaperls Color) followed by a fabric softener. A commercial formulation (Lenor® ultra) with a dosage of 1000 ppm, based on the liquor, was used as the softener. Either no UV-absorber with low textile fiber content or 100 ppm, based on the liquor, of the UV absorber AI, A2, A3 or A4 (see Example 4) according to the invention had been added to the softener formulation before softening. A tissue sample was taken from each soft rinse cycle and its UV protection factor UPF was determined in the dried state. Table 2 shows the results of the

Table 2

It can clearly be seen that when the UV absorbers AI to A4 are used, the UV protection factor UPF of the cotton fabric increases with an increase in the number of washing cycles. Protection factors that ensure good to very good skin protection against UV radiation are already obtained after the 5th wash cycle. The results further show that the textile protection against UV radiation is not improved without the addition of UV absorbers.

Claims

claims

1. Use of compounds (A) with at least one structural unit of the general formula (I)

m the

X represents groups of the formula ~ CR ^{1 =} CR ² - or a carbonyl group C = 0, where R ¹ and R ^{2 are} each independently hydrogen, Ci _. - to Cs-alkyl, Cι ~ to Cs-alkoxy, Cι ~ to Cs-alkoxycarbo 1, Cι ~ to C ₈ -acyloxy, carboxyl, cyano, nitro, fluorine, chlorine, bromine, sulfonyl, C _x - to Cs-alkylsulfonyl or phenyl, which contains up to 3 radicals from the group Cι ~ to Cs-alkyl, Cι ~ bis

Cs-alkoxy, Cι ~ to Cs-alkoxycarbonyl, Cι ~ to Cs-acyloxy, carboxyl, cyano, nitro, chlorine, bromine, sulfonyl and Cι ~ to Cs-alkylsulfonyl may be substituted, where R ^{1 is} also for the grouping - NQ-CO-, which is bonded with its carbonyl carbon atom to the ortho position of the adjacent phenyl nucleus to form a benzopyrrolidone system and m which Q denotes hydrogen or a Ci to Cs'alkyl radical,

Z substituents from the group C _λ to Cs alkyl, Ci _. - to

Cs-alkoxy, C _± - to Cs-alkoxycarbonyl, Cι ~ to Cs-acyloxy, carboxyl, cyano, nitro, fluorine, chlorine, bromine, sulfonyl, Cι_- to Cs-alkylsulfonyl, ammo, mono- or Dι-C _± - to Cs-alkylammo, carboxamido, which can carry em or two C 1 ~ to Cs-alkyl groups on the amide nitrogen, hydroxyl and saturated or unsaturated five- and six-membered heterocyclic radicals, which can be benzanellated, referred to, two adjacent substituents Z also one saturated or can form an unsaturated five- or six-membered ring, and if p = 0 an ortho-position carboxyl group together with the carbonyl group present, including an N atom directly bonded to this carbonyl group, can form cyclic imide,

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 m applied to textile material to protect human skin from damaging UV radiation.

3. Use of compounds (A) with at least one

Structural unit (I) according to claim 1 for protecting dyed textile material from fading of the color.

Use of compounds (A) which have the general formula (II)

have m

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 'has primary and / or secondary amino groups and hydroxyl groups which are capable of forming amide or ester groups with the structural unit (I), said grouping also having free and / or free tertiary compounds present on 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) m 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 have the general formula (II) according to claim 4, wherein the number m of structural units (I) m of the compounds (II) is 1, 2 or 3.

6. Use of compounds (A) which have the general formula (II) according to claim 4 or 5, where Y is for the remainder of an aliphatic or cycloaliphatic oligoamm having 2 to 6 N atoms and a total of 2 to 30 C atoms, which can still carry 1 to 3 hydroxyl groups, the oligoammers mentioned also being able to be quaternized on the compounds (II) in which the tertiary and / or free primary and / or secondary N atoms still present.

7. Use of compounds (A) which have the general formula (II) according to claim 4 or 5, wherein Y is for the remainder of a polyethylene imine of the general formula (III)

R ³ - [CH ₂ CH ₂ -NR ⁴ -] _X - [CH ₂ CH ₂ -N-] _y - [CH ₂ CH ₂ -NR ⁷ R ⁸ ] _z

| ^* (Uli

CH ₂ CH ₂ -NR ⁵ R ⁵

with an average molecular weight (M _w ) of 200 to 1,000,000, m of which the radicals R ³ to R ^{8 are,} independently of one another, hydrogen, linear or branched C 1 ~ to C ₂ o-alkyl, alkoxy, polyoxyethylene, -Hydroxyalkyl-, - (alkyl) carboxy-, -phosphonoalkyl, -alkylamino residues, C ₂ - to C ₂ o-alkenyl residues or Cζ- to C ₂ o ^_ aryl-, -Aryloxy-, -Hydroxyaryl-, -Arylcar boxy- or -Arylammoreste which are optionally further stituiert sub ^¬, and R ⁴ and R ⁵ furthermore represent another Po lyethylen-imm polymer chains, and x, y and z unabhan gig of each other denote 0 or an integer, said Polyethylene also on the compounds (II) present tertiary and / or still existing which free primary and / or secondary N atoms can be quatered.

8. The use of compounds (A), the mel ^¬ (II) having the general For, according to claim 4 or 5, wherein Y is the residue of a Polyamidoamms with an average molecular weight (M _w) of 500 to 100,000,000 which is obtainable by reacting C ₄ - to cio-dicarboxylic acids with poly (C ₂ - to C ₄ -alkylene) -polyamene with 3 to 20 basic nitrogen atoms in the molecule and which has at least m 'primary and / or secondary has known amino groups which are capable of forming amide or ester bonds with the structural unit (I), said polyamidoam also being present on the compounds (II), having tertiary and / or free existing primary and / or secondary N- Atoms can be quaternized.

9. Use of compounds (A) which have the general formula

(II) according to claim 4 or 5, wherein Y represents the remainder of a polyamm of the general formula (IV)

_R 9 _R 10 _N _ [ _CqH2q _ _NR ll_] _r -C _q H _2q -NR ⁹ RlO (IV)

with an average molecular weight (M _w ) of 100 to 100,000,000, m the radicals R ⁹ to R ¹¹ independently of one another hydrogen, linear or branched Ci _. - to C ₂ o ~ alkyl, alkoxy, polyoxyethylene, hydroxyalkyl, (alkyl) carboxy, phosphonoalkyl, alkylammo residues, C ₂ to C ₂ o alkenyl residues or C ₆ to C ₂ o-Aryl-, -Aryloxy-, -Hydroxyaryl-, -Arylcar- boxy-, or -Arylammoreste, which are optionally further substituted, mean q denotes an integer from 2 to 6 and r denotes an integer, the mentioned alkylamino residues of the type of Dendπmeren can be continued in the alkyl part and wherein said polyamm can also be quaternized on m the compounds (II) existing tertiary and / or free primary and / or secondary N atoms still present.

10. 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 (V)

R ¹² - [CH ₂ - CH -] _s - [CH ₂ - CHR ¹⁵ -] _t - R ¹⁶ (V) NR ¹³ R ¹⁴

with an average molecular weight (M _w ) of 300 to 100,000,000, m of which the radicals R ¹² to R ¹⁶ independently of one another are hydrogen, linear or branched Ci _. - to C ₂ o-alkyl,

Alkoxy, polyoxyethylene, hydroxyalkyl, (alkyl) carboxy, phosphonoalkyl, alkylammo radicals, C ₂ to C ₂₀ "alkenyl radicals or Cg to C ₂ o-aryl, aryloxy, Hydroxyaryl, arylcarboxy, or arylammo radicals, which are optionally further substituted, and R ¹⁵ furthermore means a formamidyl, pyrrolidonyl or imidazolyl radical, s denotes an integer and t denotes 0 or an integer stands, the said polyamm can also be quaternized on the tertiary and / or free primary and / or secondary N atoms present in the compounds (II).

5 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 each independently represent hydrogen, cyano or unsubstituted phenyl or where R ^{1 is} the

10 grouping -NH-CO-, which is bonded with its carbonyl carbon atom to the ortho position of the adjacent phenyl nucleus to form a benzopyrrolidone system, and R ² also denotes cyano, and n denotes the number 1.

15

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 Cι ~ to Cs-alkoxy, ammo, mono- or Dι-Cχ- to Cs-alkylammo and hydroxy denotes and

20 p means the number 1.

13. Use of compounds (A) with at least one structural unit (I) according to claims 1 to 12 as textile ^¬ fiber-affine UV absorber for textile material made of cellulose

25 is loose or contains cellulose.

14. A method 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 applied to textile material in textile finishing.

15. A method for protecting human skin from damaging UV radiation, characterized in that compounds 35 (A) having structural units of the general formula (I) according to Claims 1 and 4 to 12 on textile material during textile washing and / or Applying textile washing or textile washing treatment.

40 16. A method for protecting dyed textile material from fading of the color, characterized in that compounds (A) with structural units of the general formula (I) according to Claims 1 and 4 to 12 are applied to textile material in textile finishing.

45

17. A process for protecting dyed textile material from fading of the color, characterized in that compounds (A) with structural elements of the general formula (I) according to Claims 1 and 4 to 12 on textile material during textile washing and / or applying the pre-treatment or post-treatment of textile washing.

18. A method 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 applies to textile material in the textile equipment.

19. A method for increasing the UV protection factor UPF of textile material, characterized in that compounds (A) having structural units of the general formula (I) according to Claims 1 and 4 to 12 on textile material in textile washing and / or textile washing - or applying textile washing after-treatment.

20. Textile detergent formulation containing 0.01 to 20% by weight of at least one compound (A) having structural units of the general formula (I) according to Claims 1 and 4 to 12 in addition to the other usual constituents.

21. Textilwaschevor- and Textilwaschenachbehandlungs Formulie-tion containing 0.01 to 40 wt .-% of at least one Ver ^¬ compound (A) having structural units of the general formula (I) according to claims 1 and 4 to 12 in addition to the other customary constituents.

22. Textile washing pretreatment and textile washing treatment formulation according to claim 20, further comprising 1 to 50 wt .-% of one or more cationic surfactants from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamidoammonium salts, the amidoammoesters and Imidazolmium salts.

23. Compounds (A ') which have the general formula (Ha.

have m

Y 'for the rest of an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic grouping 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 secondary amino groups and hydroxyl groups which are capable of forming amide or ester bonds with the structural unit (I), the said grouping can also be quaternized on the tertiary and / or free primary and / or secondary N atoms present in the compounds (Ha),

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 (Ha) according to claim 23, characterized in that carboxylic acid derivatives of the general formula (Ia)

0

m the Y ″ stands for an alkoxyl group with 1 to 4 C atoms, a halogen atom, an amino group which may optionally carry em or two C 1 -C ₄ -alkyl groups or a hydroxyl group and the other variables have the meaning given above,

or precursors of carboxylic acid derivatives of the general formula (Ia), in which the structural unit responsible for UV absorption is formed only in a subsequent reaction step, with the compounds on which Y 'is based to form the corresponding carboxylic acid amide and / or carboxylic acid ester structures and, if appropriate, partial or complete quaternization of any tertiary and / or non-existent primary and / or secondary N atoms present in the compounds (Ila) .

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.