The present invention relates to new compounds which are useful as ultraviolet absorbing agents (UVAs) and to a method of improving the sun protection factor (SPF) of textile fibre material treated with the new compounds.

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

Radiation of wavelengths 320-400 nm (termed UV-A radiation) is known to induce skin tanning 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 components in sunlight has been effected by directly applying to the skin a preparation containing a UV absorber. In areas of the world, e.g. Australia and America, which enjoy especially sunny climates, there has been a great increase in the awareness of the potential hazards of undue exposure to sunlight, compounded by fears of the consequences of alleged damage to the ozone layer. Some of the more distressing embodiments of skin damage caused by excessive, unprotected exposure to sunlight are development of melanomas or carcinomas on the skin.

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 components of sunlight. Accordingly, the mere wearing of clothing does not necessarily provide skin beneath the clothing with adequate protection against damage by UV radiation. Although clothing containing a deeply coloured 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 underneath 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 of less than 200 g/m² 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 SPF 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 under 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 SPF rating of 5 would extend the period of protection from 30 minutes to 2 hours and 30 minutes. 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, SPF ratings of at least 20 are desired for lightweight clothing.

U.S. Patent No. 4,895,945 discloses chloroepoxytriazines useful for introducing epoxy functional groups into nucleophilic polymers.

EP-A 0 388 356 describes the application of triazine derivatives as UV absorbing agents in lenses, in particular in contact lenses.

It is already known, e.g. from WO 94/4515, that the application of specified types of UVA to a light-weight textile materials in general can effect an increase in the SPF value of the textile so treated. The increase in SPF value achieved thereby, however, is relatively modest.

Certain new compounds have now been found which can be readily produced and which, unexpectedly, impart greatly increased SPF ratings to textile fibre materials treated with the new compounds.

Accordingly, the present invention provides a compound having the formula: in which m is 1 or 2; A is a residue selected from those having the formulae: or X is F, Cl or NHCH₂OH and X₁ is F, Cl, NHCH₂OH or a group having the formula: or B is -O-, -NH- or -SO₂-; and
D is a group having one of the formulae:
CH₂-C(=O)-NH(CH₂OH), CH₂-C(=O)-N(CH₂OH)₂ or -CH₂CH₂-OSO₃M in which M is hydrogen, sodium, potassium, calcium, magnesium, ammonium, mono-, di-, tri- or tetra-C₁-C₄alkylammonium or ammonium that is di- or tri-substituted by a mixture of C₁-C₄alkyl and C₁-C₄hydroxyalkyl groups, preferably sodium, or D may also be a group of formula: or in which M has its previous significance and n is 0 or 1, provided that at least one SO₃M group is present, or the formula: in which X, X₁ and M have their previous significance.

Preferred compounds of formula (1) include those having the formula: in which n has its previous significance, provided that at least one group -SO₃M is present, X is F or Cl and X₁ is F, Cl or a group having one of the formulae: or in which B and M have their previous significance; in which each X is the same and is F or Cl and each X₁ is the same and is F, Cl or a group having one of the formulae: or in which B and M have their previous significance, or in which M has its previous significance but is preferably Na.

The compounds of formula (1) may be produced by reacting, under known reaction conditions, a compound of formula A-(BH)_m in which A, B and m have their previous significance, with m moles of a compound L-D, in which D has its previous significance and L is a leaving group or atom, preferably a halogen atom, especially a chlorine atom.

The starting materials A-(BH)_m and L-D are known compounds which are readily available.

The present invention also provides a method for the treatment of a textile fibre material, comprising treating the textile fibre material with 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of one or more compounds having the formula (1).

The textile fibres treated according to the method of the present invention may be natural or synthetic fibres or mixtures thereof. Examples of natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres.

Preferably, textile fibres treated according to the method of the present invention have a density of less than 200 g/m² and have not been previously dyed in deep shades.

Some of the compounds of formula (1) used in the method of the present invention may be only sparingly soluble in water and may need to be applied in dispersed form. For this purpose, they may be milled with an appropriate dispersant, conveniently using quartz balls and an impeller, down to a particle size of 1-2 microns.

As dispersing agents for such sparingly-soluble compounds of formula (1) there may be mentioned:

• acid esters or their salts of alkylene oxide adducts, e.g., acid esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol, or phosphoric acid esters of the adduct of 6 to 30 moles of ethylene oxide with 1 mole of 4-nonylphenol, 1 mole of dinonylphenol or, especially, with 1 mole of compounds which have been produced by the addition of 1 to 3 moles of styrenes on to 1 mole of phenol;
• polystyrene sulphonates;
• fatty acid taurides;
• alkylated diphenyloxide-mono- or -di-sulphonates;
• sulphonates of polycarboxylic acid esters;
• addition products of 1 to 60, preferably 2 to 30 moles of ethylene oxide and/or propylene oxide on to fatty amines, fatty amides, fatty acids or fatty alcohols, each having 8 to 22 carbon atoms, or on to tri- to hexavalent C₃-C₆alkanols, the addition products having been converted into an acid ester with an organic dicarboxylic acid or with an inorganic polybasic acid;
• lignin sulphonates; and, in particular
• formaldehyde condensation products, e.g., condensation products of lignin sulphonates and/or phenol and formaldehyde; condensation products of formaldehyde with aromatic sulphonic acids, e.g., condensation products of ditolylethersulphonates and formaldehyde; condensation products of naphthalenesulphonic acid and/or naphthol- or naphthylaminesulphonic acids and formaldehyde; condensation products of phenolsulphonic acids and/or sulphonated dihydroxydiphenylsulphone and phenols or cresols with formaldehyde and/or urea; or condensation products of diphenyloxide-disulphonic acid derivatives with formaldehyde.

Depending on the type of compound of formula (1) used, it may be beneficial to carry out the treatment in a neutral, alkaline or acidic bath. The method is usually conducted in the temperature range of from 20 to 140°C.,for example at or near to the boiling point of the aqueous bath, e.g. at about 90°C.

Solutions of the compound of formula (1), or its emulsions in organic solvents may also be used in the method of the present invention. For example, the so-called solvent dyeing (pad thermofix application) or exhaust dyeing methods in dyeing machines may be used.

If the method of the present invention is combined with a textile treatment or finishing method, such combined treatment may be advantageously carried out using appropriate stable preparations which contain the compound of formula (1) in a concentration such that the desired SPF improvement is achieved.

In certain cases, the compound of formula (1) is made fully effective by an after-treatment. This may comprise a chemical treatment such as treatment with an acid, a thermal treatment or a combined thermal/chemical treatment.

It is often advantageous to use the compound of formula (1) in admixture with an assistant or extender such as anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, an alkali metal phosphate such as sodium or potassium orthophosphate, sodium or potassium pyrophosphate or sodium or potassium tripolyphosphate, or an alkali metal silicate such as sodium silicate.

In addition to the compounds of formula (1), a minor proportion of one or more adjuvants may also be employed in the method of the present invention. Examples of adjuvants include emulsifiers, perfumes, colouring dyes, opacifiers, optical whitening agents, bactericides, nonionic surfactants, fabric care ingredients, especially fabric softeners, stain release or stain repellant ingredients or water-proofing agents, 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 should not exceed 1% by weight on the treated fibre.

The method of the present invention, in addition to providing protection to the skin, also increases the useful life of a textile article treated according to the present invention. In particular, the tear resistance and/or lightfastness of the treated textile fibre material may be improved.

Accordingly, the present invention still further provides a method of increasing the SPF rating of textile fibre material, comprising treating the textile fibre material with 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of one or more compounds having the formula (1).

The present invention also provides a textile fabric produced from a fibre treated according to the method of the present invention as well as an article of clothing produced from the said fabric.

Such textile fabrics and articles of clothing produced from the said fabrics typically have an SPF rating of 20 and above whereas untreated cotton, for example, generally has an SPF rating of from 2 to 4.

The following Examples further illustrate the present invention.

6.3 g. of the compound of formula: are dissolved in 150 mls. of water at 60°C. and treated with 10 drops of 30 % caustic soda solution. After the dropwise addition of 32.4 g. of a 37 % formaldehyde solution, and subsequent stirring at 60-65°C. over 2.5 hours, 150 mls. of salt solution are added and the mixture is cooled to 10°C. The reaction mixture is filtered giving 7 g. of a solid product, corresponding to a yield of 93 % of the theoretical.
The product (107) has the following elemental analysis by weight: Req.% C 33.47; H 4.93; N 18.00; S 6.87; Na 4.93 Found % C 33.4; H 4.7; N 17.5; S 6.7; Na 5.0.

3.4 g. of cyanuric chloride are stirred in a mixture of 100 mls of acetone and 50 mls of water. The mixture is chilled to -10°C. and a solution of 5.5 g. of 4-aminostilbene-2-sulfonic acid sodium salt in 50 mls of water is added over 30 minutes, followed by 10 mls of 1M sodium carbonate solution.

The resulting mixture is stirred for 2 hours at -5 to -10°C. and the solid is filtered off and dried, giving 6.8 g. of a white product corresponding to a yield of 74% of theory.

The compound (108) has the following elemental analysis by weight: Req.% C 43.63; H 2.91; N 11.97; S 6.85; Cl 15.15; H₂O 4.85 Found % C 43.7; H 3.0; N 12.0; S 6.8; Cl 15.0.; H₂O 4.85.

Using the same procedure as in Example 2 but replacing 4-aminostilbene-2-sulfonic acid by 4-aminostilbene-2,2'-disulfonic acid disodium salt, 15.1 g. of the compound of formula (109) are obtained, corresponding to a yield of 55% of theory.

The compound (109) has the following elemental analysis by weight: Req.% C 32.37; H 3.03; N 8.88; S 10.17; Cl 11.24; H₂O 13.22 Found % C 32.4; H 3.0; N 8.9; S 10.0; Cl 11.5.; H₂O 13.23.

• A) Using the procedure described in Example 2, prior to the filtration step, Compound (108) is produced as a white dispersion.
• B) To this dispersion there are added 3 g. of 4-amino-ethylbenzoate, as a solid, followed by 10 mls of 1M sodium carbonate solution. The resulting pale yellow suspension is stirred for 18 hours at 25°C. and the solid product is filtered off and dried, giving 8.6 g. of the white compound of formula (110), corresponding to a yield of 83% of theory.

The compound (110) has the following elemental analysis by weight: Req.% C 47.9; H 4.4; N 10.75; S 4.9; Cl 6.21; H₂O 10.61 Found % C 47.9; H 4.4; N 10.8; S 4.8; Cl 6.5.; H₂O 10.76.

• A) Using the procedure described in Example 2, prior to the filtration step, Compound (108) is produced as a white dispersion.
• B) The procedure described in part B) of Example 4 is repeated except that 4-amino-ethylbenzoate is replaced by 4-amino-acetophenone. In this way, 4.8 g. of the white compound of formula (111) are produced, corresponding to a yield of 49% of theory.

The compound (111) has the following elemental analysis by weight: Req.% C 48.0; H 4.31; N 11.2; S 5.12; Cl 6.59; H₂O 11.40 Found % C 48.0; H 4.4; N 11.3; S 5.1; Cl 6.4.; H₂O 11.42.

• A) Using the procedure described in Example 3, prior to the filtration step, Compound (109) is produced as a dispersion.
• B) The procedure in part B) of Example 4 is used for the reaction of the compound of formula (109) with 4-amino-ethylbenzoate to obtain 31.9 g. of the yellow compound (112), corresponding to a yield of 78.6% of theory.

The compound (112) has the following elemental analysis by weight: Req.% C 38.4; H 3.94; N 8.6; S 7.8; Cl 6.5; H₂O 13.28 Found % C 38.9; H 3.9; N 9.2; S 7.7; Cl 6.6.; H₂O 12.67.

The procedure in Example 6 is repeated except that, in part B), 4-amino-acetophenone is used instead of 4-amino-ethylbenzoate. In this way, 6.3 g. of compound (113) are obtained, corresponding to a yield of 49% of theory.

The compound (113) has the following elemental analysis by weight: Req.% C 41.19; H 3.76; N 9.61; S 8.80; Cl 4.86; H₂O 11.39 Found % C 41.4; H 3.8; N 9.7; S 8.6; Cl 5.3.; H₂O 11.39.

The procedure in Example 6 is repeated except that, in part B), 2-amino-pyrimidine is used instead of 4-amino-ethylbenzoate. In this way, 9.2 g. of compound (114) are obtained, corresponding to a yield of 61% of theory.

The compound (114) has the following elemental analysis by weight: Req.% C 34.37; H 3.55; N 13.37; S 8.7; Cl 6.4; H₂O 14.7 Found % C 34.4; H 3.6; N 13.9; S 8.5; Cl 6.3.; H₂O 15.1.

The procedure in Example 6 is repeated except that, in part B), sulfanilic acid is used instead of 4-amino-ethylbenzoate. In this way, 16.9 g. of compound (115) are obtained, corresponding to a yield of 57.9% of theory.

The compound (115) has the following elemental analysis by weight: Req.% C 25.7; H 3.11; N 6.0; S 8.22; Cl 13.7; H₂O 16.45 Found % C 25.7; H 3.2; N 6.5; S 8.5; Cl 13.7.; H₂O 16.4.

The procedure in Example 6 is repeated except that, in part B), 2-(4-aminophenylsulfonyl)-ethylhydrogen sulfate is used instead of 4-amino-ethylbenzoate. In this way, 19.5 g. of compound (116) are obtained, corresponding to a yield of 60% of theory.

The compound (116) has the following elemental analysis by weight: Req.% C 29.50; H 3.63; N 6.88; S 13.86; Cl 3.49; H₂O 14.15 Found % C 29.5; H 3.50; N 7.0; S 13.7; Cl 3.7.; H₂O 14.38.

Using the procedure described in Example 2, 18.4 g. of cyanuric chloride are stirred in a mixture of 120 mls of acetone and 100 mls of water. The mixture is chilled to -10°C. and a solution of 25.4 g. of 4.4'-diaminostilbene-2,2'-disulfonic acid disodium salt in 50 mls of water is added over 30 minutes, followed by 50 mls of 1M sodium carbonate solution.

The resulting mixture is stirred for 2 hours at -5 to -10°C. and the solid is filtered off and dried, giving 24.1 g. of a white product corresponding to a yield of 67.9% of theory.

The compound (117) has the following elemental analysis by weight: Req.% C 30.01; H 2.51; N 14.00; S 8.01; Cl 17.62; Found % C 30.0; H 2.6; N 14.0; S 7.8; Cl 17.6..

To the white suspension of the compound of formula (117) obtained in Example 11, prior to the filtration step, there is added 4-amino-ethylbenzoate in the manner described in Example 4.

In this way, 44.5 g. of compound (118) are obtained, corresponding to a yield of 92% of theory.

The compound (118) has the following elemental analysis by weight: Req.% C 40.0; H 3.77; N 12.28; Cl 9.34; H₂O 10.26 Found % C 40.0; H 3.8; N 12.3; Cl 9.2.; H₂O 10.0.

Using the procedure described in Example 12 but replacing 4-amino-ethylbenzoate by 4-amino-acetophenone, 29.1 g. of compound (119) are obtained, corresponding to a yield of 94.6% of theory.

The compound (119) has the following elemental analysis by weight: Req.% C 35.15; H 4.71; N 11.38; Cl 7.50; S 5.20; H₂O 10.26 Found % C 35.1; H 4.8; N 11.5; Cl 7.7.; S 5.2; H₂O 23.5.

Using the procedure described in Example 12 but replacing 4-amino-ethylbenzoate by 2(4-aminophenylsulfonyl)-ethylhydrogensulfate, 46.2 g. of compound (120) are obtained, corresponding to a yield of 73.1% of theory.

The compound (120) has the following elemental analysis by weight: Req.% C 17.10; H 2.14; N 5.53; S 7.59; Cl 28.33; H₂O 8.58 Found % C 17.1; H 2.1; N 5.6; S 7.5; Cl 28.6; H₂O 8.58.

Using the procedure described in Example 12 but replacing 4-amino-ethylbenzoate by 4-aminopyrimidine, 16.4 g. of compound (121) are obtained, corresponding to a yield of 79% of theory.

The compound (121) has the following elemental analysis by weight: Req.% C 33.42; H 3.75; N 18.85; Cl 9.20; S 6.15 Found % C 33.3; H 3.5; N 19.0; Cl 9.3; S 6.1.

Using the procedure described in Example 2 but replacing 4-amino-stilbene-2-sulfonic acid sodium salt by a mixture of 2-(4-aminophenylsulfonyl)ethylhydrogen sulfate and 4-amino-ethylbenzoate, in the required stoichiometric proportions, 9.3 g. of the compound of formula (124) are obtained, corresponding to a yield of 73% of theory.

The compound (124) has the following elemental analysis by weight: Req.% C 25.40; H 2.75; N 7.41; S 6.77; H₂O 6.60 Found % C 25.4; H 2.6; N 7.4; S 6.2; H₂O 6.5.

Using the procedure described in Example 2 but replacing 4-amino-stilbene-2-sulfonic acid sodium salt by a mixture of 2-(4-aminophenylsulfonyl)ethylhydrogen sulfate and 4-aminoacetophenone, in the required stoichiometric proportions, 8.9 g. of the compound of formula (126) are obtained, corresponding to a yield of 83% of theory.

The compound (126) has the following elemental analysis by weight: Req.% C 36.10; H 4.00; N 11.70; S 10.71; Cl 5.92; H₂O 10.17 Found % C 37.0; H 4.1; N 11.8; S 10.3; Cl 5.8; H₂O 10.18.

Using the procedure described in Example 12, compound (129) is prepared and has the following elemental analysis by weight: Req.% C 38.80; H 4.06; N 9.53; S 5.45; Cl 6.03; H₂O 17.90 Found % C 38.2; H 4.0; N 9.4; S 5.3; Cl 6.2; H₂O 17.91.

Using the procedure described in Example 12, compound (130) is prepared and has the following elemental analysis by weight: Req.% C 40.01; H 4.07; N 13.72; S 6.28; Cl 6.95; H₂O 13.42 Found % C 41.1; H 3.8; N 14.3; S 5.8; Cl 7.5; H₂O 13.41.

Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing:

• 5 g/l MgCl₂
• 250 g/l product of Example 1

As the product of Example 1 is insoluble in water, it is added as a 5% (w/w) aqueous dispersion which is obtained by milling 5% of the product of Example 1 and 1% of Pluronic F 108 (polypropylene glycol containing 80% ethylene oxide) in the presence of glass beads in deionised water.

The foularding is conducted at either alkaline pH (pH adjusted to 10-11 with soda) or at acidic pH (pH adjusted to 4-4.5 with acetic acid). Drying of the treated cotton samples is effected at 80°C. for two minutes, followed by thermofixing for one minute at 170°C.

The Sun Protection Factor (SPF) is determined by measurement of the UV light transmitted through the swatch, using a double grating spectrophotometer fitted with an Ulbricht bowl. Calculation of SPF is conducted as described by B.L.Diffey and J.Robson in J. Soc. Cosm. Chem. 40 (1989), pp. 130-131.

In order to evaluate the wash fastness of the treated cotton samples, respective samples are washed once, five times or ten times in an aqueous bath containing 7g/l of a standard ECE detergent having the composition (weight %): 8.0% Sodium alkylbenzene sulfonate 2.9% Tallow alcohol-tetradecane-ethylene glycol ether (14 mols EO) 3.5% Sodium soap 43.8% Sodium tripolyphosphate 7.5% Sodium silicate 1.9% Magnesium silicate 1.2% Carboxymethyl cellulose 0.2% EDTA 21.2% Sodium sulfate Water to 100%.

Each wash is conducted at 60°C. for 15 minutes at a liquor ratio of 1:10.

The results obtained are set out in the following Table 1. Example Test UVA Concn. FWA Treatment SPF alkaline/ acidic number of washes none one five ten - none (control) - acidic 4.1 4.1 4.1 4.2 20 cpd. of Ex.1 0.1% 0.5% slightly acidic 10 15 12 12 23 26 27 27

Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing:

• 10 g/l Na₂SO₄
• 50 g/l product of relevant Example

As the products of the relevant Examples are insoluble in water, they are added as a 5% (w/w) aqueous dispersion which is obtained by milling 5% of the product of the relevant Example and 1% of Pluronic F 108 in the presence of glass beads in deionised water.

The remaining procedure is as described in Example 20.

The results obtained are set out in the following Table 2. Example Test UVA Concn. FWA Treatment SPF alkaline/ acidic number of washes none one five ten - none (control) - neutral 7 5 6 21 cpd. of Ex.2 0.2% neutral 34 22 29 29 22 cpd. of Ex.4 0.1% neutral 29 31 22 19 23 cpd.ofEx.5 0.1% neutral 39 36 22 23 24 cpd. of Ex.13 0.2% neutral 26 40 36 29 25 cpd. of Ex.15 0.1% neutral 21 19 13 11 26 cpd. of Ex.17 0.2% neutral 18 14 9 12 27 cpd. of Ex.18 0.2% neutral 30 34 31 28 28 cpd. of Ex.19 0.2% neutral 38 23 22 20 29 cpd. of Ex.11 0.2% neutral 18 13 7 15 30 cpd. of Ex.12 0.2% neutral 29 36 21 19 31 cpd. of Ex. 14 0.2% neutral 28 32 31 28

Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing:

• 4 g/l NaHCO₃H
• 50 g/l urea
• 50 g/l product of relevant Example

As the products of the relevant Examples are insoluble in water, they are added as a 5% (w/w) aqueous dispersion which is obtained by milling 5% of the product of the relevant Example and 1 % of Pluronic F 108 in the presence of glass beads in deionised water.

The remaining procedure is as described in Example 20 except that the thermofixing is conducted for 2 minutes at 130°C.

The results obtained are set out in the following Table 7. Example Test UVA Concn. UVA SPF number of washes none one five ten - none (control) - 7 5 5 4 32 cpd. of Ex.11 0.2% 28 15 15 24 33 cpd. of Ex.12 0.2% 45 49 45 34 34 cpd. of Ex.14 0.2% 33 35 36 48

The results in the Tables 1 to 3 demonstrate the substantial increase in the SPF values of cotton samples treated according to the present invention and that cotton samples treated according to the present invention are fast to washing.