It is known that light radiation of wavelengths 280-400 hm permits tanning of the epider- mis. Also known is that rays of wavelengths 280-320 nm (termed UV-B radiation), cause ery- themas and skin burning, which can inhibit skin tanning.

Radiation of wavelengths 320-400 nm (termed UV-A radiation) is known to induce skin tan- ning but can also cause skin damage, especially to sensitive skin, which is exposed to sunlight for long periods. Examples of such damage include loss of skin elasticity and the appearance of wrinkles, promotion of the onset of erythemal reaction and the inducement of phototoxic or photoallergic reactions.

Any effective protection of the skin from the damaging effects of undue exposure to sunlight clearly needs to include means for absorbing both UV-A and UV-B components of sunlight before they reach the skin surface.

Traditionally, protection of exposed human skin against potential damage by the UV com- ponents in sunlight has been effected by directly applying to the skin a preparation contain- ing a UV absorber.

One aspect of the desire to increase the level of skin protection against sunlight has been the consideration of additional measures, over and above the direct protection of the skin.

For example, consideration has been given to the provision of protection to skin covered by clothing and thus not directly exposed to sunlight.

Most natural and synthetic textile materials are at least partially permeable to UV compo- nents of sunlight. Accordingly, the mere wearing of clothing does not necessarily provide skin beneath the clothing with adequate protection against damage by UV radiation. Al- though clothing containing a deeply colored dye and/or having a tight weave texture may provide a reasonable level of protection to skin beneath it, such clothing is not practical in hot sunny climates, from the standpoint of the personal comfort of the wearer.

There is a need, therefore, to provide protection against UV radiation for skin which lies un- derneath clothing, including lightweight summer clothing, which is undyed or dyed only in pale shades. Depending on the nature of the dyestuff, even skin beneath clothing dyed in some dark shades may also require protection from UV radiation.

Such lightweight summer clothing normally has a density of less than 200 g/m and has a sun protection factor rating between 1.5 and 20, depending on the type of fibre from which the clothing is manufactured.

The UPF rating of a sun protectant (sun cream or clothing) may be defined as the multiple of the time taken for the average person wearing the sun protectant to suffer sun burning un- der average exposure to sun. For example, if an average person would normally suffer sun burn after 30 minutes under standard exposure conditions, a sun protectant having an UPF rating of 5 would extend the period of protection from 30 minutes to 2 hours and 30 min- utes. For people living in especially sunny climates, where mean sun burn times are minimal, e. g. only 15 minutes for an average fair-skinned person at the hottest time of the day, UPF ratings of about 20 are desired for lightweight clothing.

The selection of a suitable UVA, for use in a method for effecting an increase in the UPF value of a textile fiber material (often referred to as a"UV cutting"treatment method), has to take into account the fact that the treated textile fiber material must satisfy performance cri- teria in a wide range of areas, such as washfastness, lightfastness and tear resistance, apart from its UPF value.

Another major problem for consumers in many parts of the world is the fading of colored fabrics by sunlight (so-called"photo-fading") during wear and during drying. Thus suscep- tible fabrics in temperature and high latitude regions in addition to those in the tropics can be severely faded. Photo-fading of fabrics is of specific concern to consumers because the contrast between exposed and unexposed areas makes it particularly noticeable.

Surprisingly it was found that the use of specific UV absorbers in a fabric rinse composition imparts enhanced UPF, and simultaneously effectively prevents the photo-fading of said fab- ric.

Therefore the present invention provides a stable, concentrated fabric rinse composition comprising a) 0.1 to 10, preferably 0.1 to 5 % by weight of a UV absorber of formula U is a radical of a UV absorber selected from hydroxyphenyl-benztriazole, hydroxy- phenyltriazine and benzophenone; A direct bond; C,-Cbalkylen ; C,-C6alkyliden ; or a group of formula Y direct bond; or the group-CO- ;-COO- ;-OOC- ;-CO-N (R)- ;- (R') N-CO- ;-SO,-N (R')- ; - (R') N-SQ ; a group of formula B direct bond; C2-c 6alkylene orC2-C, alkylidene which is substituted by OH and which can be interrupted by-O-or by one or two N'X' (R')2-; or is a group of formula (1 g) or the group x~ is a saturated or unsaturated mononuclear or trinu- clear N-heterocyclic radical containing 1-4 N-atoms as ring members, at least one of which is quaternized; Rlf R2 and R3 independently from each other are hydrogen; C1-C8alkyl ; or C,-C8alkyl which is substituted by 1-COOR"group or by 1 to 3 OH groups, C2-CBhydroxyalkyl which is interrupted by one or more -O- groups, -(C1-C8)alkylene-COO-, -(C1- C8)alkylidene-COO-, -(C2-C8)alkylidene-SO3- each of which is substituted by one OH group; C3-C5alkenyl ; C,-C, cycloalkyl ; phenyl ; tolyl ; benzyl ; or glycidyl ; or R, togehter with R2 and if appropriate with R3 and together with the N+-atom to which they are attached, form a N-heterocyclic radical which can contain 1-3 N-atoms or one O- atom as ring members R'is hydrogen; C1-C4alkyl or c2-C3hydroxyalkyl ; R"is hydrogen; or C,-C4alkyl ; X if not present in R,, R2or R3is a colourless organic or inorganic anion; B° is-(CH2) m-; or one of the following groups: m and r are independently from each other 2 or 3; pis1 to6 ; n is 1 to 4 ; g is 0 or 1 ; with the proviso that A, Y and B are not at the same time the direct bond; b) 5 to 25% by weight, based on the total weight of the composition of a fabric softener agent; and c) water.

The invention preferably relates to the use of a composition, wherein U in formula (1) corre- sponds to a UV absorber radical of formula R4 is hydrogen; C1-C4alkyl; C1-C4-Alkoxy ; or halogen ; and n is from 0 to 3.

Most preferably a UV absorber of formula is used as component (a), wherein B is C2-C6alkylene ; or C2-C6alkylene which is substituted by OH and which can be inter- rupted by-0-or by one of-N+X (R') 2-; most preferably R1, R2, R3, R', X and n are defined as in formula (1) and R4 is as defined in formula (2).

Preferably U corresponds to a UV absorber radical of formula wherein R5, R6, R7, R8, R9 and R10 are each independently of the others hydrogen, C1-C18alkyl ; C,-C, cycloalkyl ; halogen ; or a radical of formula (3a,) R1, R2, R3, A, B, X, Y and g are defined as in formula (1).

Most preferably the UV-absorber corresponds to formula Y is the group -CO-; -COO-; -OOC-; -CO-N(R')-; -(R')N-CO-; -SO2-N(R')-; -(R')N-SO2; B is C2-C6alkylene or C2-C6alkylidene which is substituted by OH and which can be inter- rupted by-O-or by one or two Nix (R')2-; or is a saturated or unsaturated mononuclear or trinuclear N-heterocyclic radical containing 1-4 N-atoms as ring members, at least one of which is quaternized; and R1, R2, R3, R'and X are defined as in formula (1); and R R6, R7, R8, R9, Rao are as defined in formula (3a) or (3b).

Most preferred are UV absorbers of formula (3a,) wherein Y is-CO- ;-COO- ;-OOC- ;-CO-N (R')- ; or- (R') N-CO- ; B is C2-C6alkylene, which is substituted by OH; R7 is hydrogen; or alkyl ; Rs R6 R8, R9 and Rio are independently from each other hydrogen or C,-C6alkyl and R1, R2, R3 and R'are defined as in formula (1).

Further preferred are UV-absorbers of formula Y is the group-CO- ;-COO- ;-OOC- ;-CO-N (R')- ;- (R') N-CO- ;-SO,-N (R')- ;- (R') N-SO, ; B is C2-C6alkylene or C2-C6alkylidene which is substituted by OH and which can be inter- rupted by-O-or by one or two N'X- (R'),- ; and R"R2, R3, R'and X are defined as in formula (1); and R5, R6, R7, R8, R9 and Rio are as defined as in formula (3a) or (3b).

Furthermore, U preferably corresponds to a UV absorber radical of formula Rill R12, r13 and R14 independently is hydrogen, halogen, OH, C1-C6alkyl ; or C1-C6alkoxy or a group of formula -O-CH2-CH (OH) CH2X, and X is-SO3H or an alkali metal salt thereof.

Preferred UV absorbers according to component (a) correspond to the formula wherein B is C2-C6alkylene or C2-C6alkylene which substituted by OH and which can be interrupted by -O-; and R,, R and R3 are defined as in formula (1); and R", R12, R13 and R, 4 are defined as in formula (4). The following cationic UV absorbers used according to the invention may be mentioned by way of example : The UV absorber used in the present composition readily absorbs UV light, especially in the range I = 300 to 400 nm, and converts the absorbed energy, by a chemical intermediate reaction, into non-interfering, stable compounds or into non-interfering forms of energy.

The UV absorber should, of course, be compatible with the rinse cycle fabric softener com- position.

Preferably, the UV absorber used is one which is capable of being absorbed on to the washed textile article during a rinse cycle fabric softener treatment.

Fabric softeners (component (b)) suitable for use herein are selected from the following classes of compounds: (i) Cationic quaternary ammonium salts. The counter ion of such cationic quaternary am- monium salts may be a halide, such as chloride or bromide, methyl sulfate, or other ions well known in the literature. Preferably the counter ion is methyl sulfate or any alkyl sulfate or any halide, methyl sulfate being most preferred for the dryer-added articles of the inven- tion.

Examples of cationic quaternary ammonium salts include but are not limited to: 1. Acyclic quaternary ammonium salts having at least two C8 to C30, preferably C,, to C,, al- kyl or alkenyl chains, such as: ditallowdimethyl ammonium methylsulfate, di (hydrogenated tallow) dimethyl ammonium methylsulfate, distearyldimethyl ammonium methylsulfate or chloride, dicocodimethyl ammonium methylsulfate and the like. It is especially preferred if the fabric softening compound is a water insoluble quaternary ammonium material which comprises a compound having two C, to to alkyl or alkenyl groups connected to the mole- cule via at least one ester link. It is more preferred if the quaternary ammonium material has two ester links present. An especially preferred ester-linked quaternary ammonium material for use in the invention can be represented by the formula: wherein each Rus group is independently selected from C1-C4alkyl, hydroxyalkyl or C2 to C4 alkenyl groups; T is either a radical of formula (1 2a) wherein each R, 6 group is independently selected from C8-C28 alkyl or C8-CZealkenyl groups; and e is an integer from 0 to 5.

A second preferred type of quaternary ammonium material can be represented by the for- mula : wherein Rls, Rl6 and e are as defined in formula (12).

2. Cyclic quaternary ammonium salts of the imidazolinium type such as di (hydrogenated tallow) dimethyl imidazolinium methylsulfate, 1-ethylene-bis (2-tallow-1-methyl) imidazolin- ium methylsulfate and the like ; 3. Diamido quaternary ammonium salts such as: methyl-bis (hydrogenated tallow ami- doethyl)-2-hydroxethyl ammonium methyl sulfate, methyl bi (tallowamidoethyl)-2- hydroxypropyl ammonium methylsulfate and the like ; 4. Biodegradable quaternary ammonium salts such as N, N-di (tallowoyl-oxy-ethyl)-N, N- dimethyl ammonium methyl sulfate and N, N-di (tallowoyl-oxy-propyl)-N, N-dimethyl ammonium methyl sulfate. Biodegradable quaternary ammonium salts are described, for example, in U. S. Patents 4,137,180,4,767,547 and 4,789,491 incorporated by reference herein.

Preferred biodegradable quaternary ammonium salts include the biodegradable cationic diester compounds as described in U. S. Patent 4,137,180, herein incorporated by reference.

(ii) Tertiary fatty amines having at least one and preferably two CB C30Z preferably Cl2-C22 alkyl chains. Examples include hardened tallow-di-methylamine and cyclic amines such as 1- (hydrogenated tallow) amidoethyl-2-(hydrogenated tallow) imidazoline. Cyclic amines which may be employed for the compositions herein are described in U. S. Patent 4,806,255 incor- porated by reference herein.

(iii) Carboxylic acids having 8 to 30 carbons atoms and one carboxylic group per molecule.

The alkyl portion has 8 to 30, preferably 12 to 22 carbon atoms. The alkyl portion may be linear or branched, saturated or unsaturated, with linear saturated alkyl preferred. Stearic acid is a preferred fatty acid for use in the composition herein. Examples of these carboxylic acids are commercial grades of stearic acid and palmitic acid, and mixtures thereof which may contain small amounts of other acids. iv) Esters of polyhydric alcohols such as sorbitan esters or glycerol stearate. Sorbitan esters are the condensation products of sorbitol or iso-sorbitol with fatty acids such as stearic acid.

Preferred sorbitan esters are monoalkyl. A common example of sorbitan ester is SPAN 60 (ICI) which is a mixture of sorbitan and isosorbide stearates.

(v) Fatty alcohols, ethoxylated fatty alcohols, alkyphenols, ethoxylated alkyphenols, ethoxy- lated fatty amines, ethoxylated monoglycerides and ethoxylated diglycerides.

(vi) Mineral oils, and polyols such as polyethylene glycol.

These softeners are more definitively described in U. S. Patent 4,134,838 the disclosure of which is incorporated by reference herein. Preferred fabric softeners for use herein are acy- clic quaternary ammonium salts. Di (hydrogenated) tallowdimethyl ammonium methylsulfate is most widely used for dryer articles of this invention. Mixtures of the above mentioned fab- ric softeners may also be used.

In addition, the composition according to the present invention may also contain a minor proportion of one or more adjuvants. Examples of adjuvants include emulsifiers, perfumes, colouring dyes, opacifiers, fluorescent whitening agents, bactericides, nonionic surfactants, anti-gelling agents such as nitrites or nitrates of alkali metals, especially sodium nitrate, and corrosion inhibitors such as sodium silicate.

The amount of each of these optional adjuvants preferably ranges from 0.05 to 5% by weight of the composition.

A particularly preferred optional adjuvant is a cationic, amphoteric or anionic fluorescent whitening agent as disclosed in EP-A-0,659,877, from page 9 to page 15, line 56.

The present invention also provides a method for the improvement of UPF of a textile article, comprising applying, to a previously washed article, a fabric rinse composition comprising: a) 0.1 to 10, preferably 0. 1 to 5 % by weight of a UV absorber of formula (1), based on the total weight of the composition; b) 5 to 25%, especially from 10 to 20% by weight, based on the total weight of the com- position, of a fabric care ingredient; and c) water.

The method and composition of the present invention, in addition to providing protection to the skin, also increase the useful life of a textile article treated according to the present invention, for example by preserving its tear strength and/or its lightfastness or reducing the fading from sunlight.

Therefore the present invention also provides a method for the reducing of the fading of fabrics from sunlight, comprising applying, to a previously washed article, a fabric rinse composition comprising: a) 0.1 to 10, preferably 0.1 to 5 % by weight of a UV absorber of formula (1), based on the total weight of the composition; b) 5 to 25%, especially from 10 to 20% by weight, based on the total weight of the com- position, of a fabric care ingredient; and c) water.

The composition deposit from about 0. 5 mg/g fabric to about 5 mg/g fabric of the UV ab- sorber of formula (1) onto the fabric to reduce the sun fading of fabric.

The textile article treated according to the method of the present invention may be com- posed of any of a wide range of types of fibers such as wool, polyamide, cotton, polyester, polyacrylic, silk or any mixture thereof.

Treatment of fabric with compositions of the present invention repeatedly during the rinse cycle of a typical laundering process may result in higher deposition levels, which contrib- utes even further to the sun-fading benefit.

The following Examples further illustrate the present invention. Example 1: Preparation of compound of formula (5) : Reactionscheme: 100 g of the compound of formula (5a) are suspended in 650 ml t-amyl alcohol. Then 17.3 g of pulverized potassium hydroxide are added and the reaction mass is warmed up indi- rectly to 80°C and then stirred for one hour at 80°C. Then within 5 min 77 g of an aqueous solution of 3-chloro-2-hydroxypropyl) trimethyl ammonium chloride are added dropwise and stirred at 80°C. After 30 minutes spontaneous crystallization occurs forming a yellow suspension. Then the reaction mass is cooled indirectly to 60°C and then filtered over a prewarmed pressure filter funnel.

620 ml of a yellowish clear filtrate is obtained. The suction cake is washed 4 times with 50 ml of acetone, first air-dried and then at 70°C in vacuum.

148 g of a beige powder is obtained.

'H-NMR d6-DMSO, values in ppm: 13.36 s, 1H 8.47 d, 1H 8.03 d, 2H 7.28 m, 4H 6.73 d, 1H 6.62 s, 1H 6.11 d, 1H 4.50 m, 1H 4.09 m, 2H 3.56 m, 2H 3.21 s, 9H 2.70 s, 3H 2.40 s, 3H Example 2: Preparation of compound of formula (6) : ReactionScheme: The process is carried out according to the proceeding of Example 1 with the difference that compound (6a) is the starting compound and cyclohexanol is used as solvent.

1 H-NMR in d6-DMSO, values in ppm: 13.36s, 1H 7.89 d, 4H 7.78 d, 1H 7. 45 t, 2H 7.29 t, 4H 6.18d, 1H 3.17 s, 9H 5. 980 s, 1 H 4. 32 s, 1H 3.66 m, 2H 3.40 m, 2H Example 3: Preparation of compound of formula (14): ReactionScheme: The process is carried out according to the proceeding of Example 1 with the difference that (3-chloro-2-hydroxypropyl)-dodecyl-dimethyl-ammoniumchloride as reactant and 2-methyl- 2-butanol as solvent are used.

1 H-NMR in d6-DMSO, values in ppm 13. 35 s, 1H 8.46 d, 1 H 8.02 d, 2H 7.26 m, 4H 6.71 d, 1 H 6. 62 s, 1 H 6. 15 s, 1H 4.48 m, 1H 4. 11 m, 2H 3. 52 t, 2H 3. 41 t, 2H 3. 17s, 6H 2.7 s, 6H 2. 40 s, 6H 1. 71 m, 2H 1. 22 m, 18H 0.81 t, 3H Example 4: Improvement of UPF 5 g of bleached cotton fabric (weave) are washed/rinsed in a linitest applying the following conditions : Mainwash: Detergent dosage: 4 gui EE 77 (phosphate containing standard detergent which is free of fluorescent whitening and bleaching agents) Liquor ratio: 1: 20 Duration: 15 minutes Temperature: 25°C Rinsing is carried out with tap water for 30 seconds and the spin dried.

Rinsebath: Softener dosage: 1,66 g/i concentrated Esterquat or 5 g/l diluted DSDMAC Liquor ration: 1: 40 Duration: 15 minutes Temperature: 25°C The fabric is spin dried at 60°C ; 1 and 3 wash cycles.

Table 1: Softener formulation : Esterquat formulation DSDMAC formulation Di-(palmcarboxyethyl)-hydroxyethyl- 15 % active matter -- methylammonium-methosulfate (Re- woquat WE 38 DPG) Distearyl-dimethylammoniumchloride 5 % active matter (Arquad 2 HT-75) C, 2-C, 3fatty alcohol ethoxylate with an 0. 5 % average of 6 EO units (Dobanol 23-6,5) MgCl2 0. 1 % Table 1: Softener formulation : Esterquat formulation DSDMAC formulation UV-Absorber 2.4 % 0.8 % water ad 100 % ad 100 % The UPF of the dried softener treated goods are determined by measurement of the UV light transmitted through the textile, using a double grating spectrophotometer fitted with an Ulbricht bowl. Calculation of UPF is conducted as described by B. L. Diffey and J. Robson in J.

Soc. Cosm. Chem. 40 (1989), pp. 130-131.

The results are shown in Table 1: Table 2 : Compound of formula softener for-softener for-softener for-softener for- mulation mulation with mulation with mulation with without UV UV absorber UV absorber UV absorber of absorber of formula (8) of formula (7) formula (5) DSDMAC formulation 15'wash/rinse 13 12 10 3rd wash/rinse 3 31 21 20 Esterquat formulation 15 wash/rinse 3 11 8 11 3rd wash/rinse 17 15 17 The results in Table 2 clearly demonstrate the improvement of the UPF values of the cotton substrates treated with rinse compositions according to the present invention.

Example 2: Photo Fading Inhibition Six differently colored cotton fabrics A: Reactive Black 005 B: Reactive Red 226 C: Reactive Blue 013 D: Reactive Red 264 E: Reactive Red 228 F: Reactive Red 002 are separately washed and rinsed in a Linitest applying the following conditions: Main wash: Detergent dosage: 4 g/t ECE77 Liquor Ration: 1: 20 Duration: 15 minutes Temperature: 25°C The fabrics are rinsed with tap water for 30 seconds and spin dried.

Rinse bath: Softener dosage: 4 g/l DSDMAC formulation Liquor ration: 1: 20 Duration: 15 minutes Temperature: 25°C The fabric is spin dried at 60°C and irradiated in an ATLAS Weather-O-Meter Ci65A under the following conditions: Filter : Boro/Boro Irradiation lamp : 3.5 kw Irradiation onto the fabric: 0.22 W/m2 Dry bulb : 29.3°C Wet bulb : 21.9°C Wet bulb depression: 7.3°C Rel. humidity 43% Duration: 7 h 10 wash/rinse/irradiation cycles Table 3: Softener formulation : DSDMAC formulation Distearyl-dimethylammoniumchloride (Arquad 2 HT-75) Cl2-Cl3fatty alcohol ethoxylate with an 0.5 % average of 6 EO units (Dobanol 23-6,5) UV-Absorber 0.4 % of compound of formula (5) water ad 100 % Effect Evaluation CIE Color Measurement The CIE color system evaluates the color of a fabric sampel in terms of the L*, a*, b* coordi- nates which are determinded from spectrophotometer readings. (L*, a*, b* are as described in Colorimetry, 2nd Edition, CIE Publication no. 15.2, published by Bureau, Central de la CIE, Paris 1982).

The AE value is defined by the following equation: AE = { *)2 + (af* - ai*)2 + (bf* - bi*)2}1/2 where the subscripts i and f refer to the values as measured with or without irradiation of the sample, respectively.

The CIE color measurements of the colored fabric washed/rinsed without UV- aborber/irradiated (reference = not irradiated) and the colored fabric washed/rinsed with UV-absorber/irradiated (reference = not irradiated) obtained the following results : Table 4: AE 10 Cycles without compound of formula (5) with compound of formula (5) A: 9. 1 8. 0 B: 17.2 16.6 C: 6.5 5.9 D: 14.6 12.6 E: 14.2 12.3 F : 6. 9 6. 3 The results in the table show that the colored cotton fabrics treated according to the process of the present invention show a remarkable photo-fading inhibition.