GB2290803A

GB2290803A - Textile treatment

Info

Publication number: GB2290803A
Application number: GB9512181A
Authority: GB
Inventors: Dieter Reinehr; Claude Eckhardt
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1994-07-01
Filing date: 1995-06-15
Publication date: 1996-01-10
Also published as: GB9512181D0

Abstract

There is provided a stable, concentrated fabric rinse composition comprising 0.3 to 10, preferably 0.3 to 3% by weight of a fluorescent whitening agent which is compatible with a fabric care ingredient, preferably a cationic, amphoteric or anionic fluorescent whitening agent, based on the total weight of the composition, and optionally a fabric care ingredient, preferably a fabric softener, a stain release or stain repellant ingredient or a water-proofing agent, the remainder being substantially water. The fabric rinse composition is preferably a fabric softener composition comprising 5 to 25, preferably 10 to 20% by weight of a cationic fabric softening agent and 0.3 to 10, preferably 0.3 to 3% by weight of a cationic, amphoteric or anionic fluorescent whitening agent, each based on the total weight of the composition, the remainder being substantially water. The present invention also provides method for the treatment of a textile article, comprising applying, to the previously washed article, the said fabric rinse composition, preferably the rinse cycle fabric softener composition, whereby the sun protection factor, and other properties such as the tear strength and lightfastness of articles so treated can be significantly increased.

Description

Textile Treatment The present invention relates to a composition for the treatment of textiles, in particular to a composition containing a fluorescent whitening agent and to a method of treating textiles with the composition for the improvement of the sun protection factor (SPF) of textile fibre material treated with the composition.

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, skin covered by clothing dyed in some dark shades may also require protection against 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.

Surprisingly, it has now been found that the application, to a washed article of clothing, of a rinse cycle fabric care formulation comprising a fluorescent whitening agent which is compatible with a fabric care ingredient, preferably a cationic, amphoteric or anionic fluorescent whitening agent, especially a rinse cycle fabric softener comprising a fluorescent whitening agent which is compatible with a fabric softener ingredient, preferably a cationic, amphoteric or anionic fluorescent whitening agent, containing a higher amount of fluorescent whitening agent than is used in conventional rinse cycle fabric care formulations, imparts an excellent whiteness and sun protection factor to the fibre material so treated.

The present invention provides, therefore, as a first aspect, a stable, concentrated fabric rinse composition comprising 0.3 to 10, preferably 0.3 to 3% by weight of a fluorescent whitening agent which is compatible with a fabric care ingredient, preferably a cationic, amphoteric or anionic fluorescent whitening agent, based on the total weight of the composition, and optionally a fabric care ingredient, preferably a fabric softener, a stain release or stain repellant ingredient or a water-proofing agent, the remainder being substantially water.

The fabric care ingredient is preferably present in an amount of from 2 to 25, preferably 5 to 20% by weight, based on the total weight of the composition.

The present invention provides, as a second aspect, a stable, concentrated rinse cycle fabric softener composition comprising 2 to 25, preferably 5 to 20% by weight of a fabric care ingredient, preferably a cationic fabric softening agent and 0.3 to 10, preferably 0.3 to 3% by weight of a fluorescent whitening agent which is compatible with a fabric care ingredient, preferably a cationic, amphoteric or anionic fluorescent whitening agent, each based on the total weight of the composition, the remainder being substantially water.

Preferred examples of cationic fabric softening agents include imidazolines, quaternary ammonium compounds, ester amide amine salts, as well as mixtures thereof.

Preferred imidazoline cationic fabric softening agents are those having the formula:

in which R is hydrogen or C1-C4alkyl; R1 is a C8-C30aliphatic residue; R2 is -C2H4-O(C=O)-R1 or -C2H4-NH(C=O)-R1; and A is an anion.

Preferably R is hydrogen or methyl; Rlis C14-C18alkyl or C14-C18alkenyl; and R2 is -C2H4-O(C=O)-C14-C1 8alkyl or -C14-C1 8alkenyl, or -C2H4-NH(C=O)-Cl4-Cl8alkyl or -C14-C18alkenyl.

Other preferred imidazoline cationic fabric softening agents are those having the formula:

in which R1 and A have their previous significance; R3 and R4, independently, are a C8-C30aliphatic residue, C1-C4alkyl, C1-C4halogenoalkyl, C1-C4hydroxyallcyl or a group -C2H4-N(Rs)-C(=O)-R6 in which R5 is hydrogen or Cs-C30aIkA and R6 is hydrogen or Cl-C4aLkyl.

Preferably Rlis C14-C18alkyl or C14-C18alkenyl; R3 is C14-Cl8alkyl, C14-C18alkenyl, Cl-C4aLkyl, C1-C4halogenoalkyl or Cl-C4hydroxyalkyl; and R4 is a group -C2H4-N(Rs)-C(=O)-R6 in which R5 is hydrogen or C8-C30alkyl and R6 is hydrogen or Cl-C4aLkyl.

Preferred anions A include chloride, bromide, iodide, fluoride, sulfate, methosulfate, nitrite, nitrate or phosphate anions, as well as carboxylate anions such as acetate, adipate, phthalate, benzoate, stearate or oleate anions.

Specific examples of preferred compounds of formula (1) include: 2-tallow- l-(2-stearoyloxyethyl)-imidazoline chloride, 2-tallow- 1 -(2-stearoyloxyethyl)-imidazoline sulfate, 2-tallow-1 -(2-stearoyloxyethyl)-imidazoline methosulfate, 2-tallow- 1 -methyl-3-(2-stearoylamidoethyl)-imidazoline chloride, 2-tallow- 1 -methyl-3-(2-stearoylamidoethyl)-imidazoline sulfate and 2-tallow- 1 -methyl-3-(2-stearoylamidoethyl)-imidazoline methosulfate.

Specific examples of preferred compounds of formula (2) include: 2-heptadecyl- 1-methyl- 1-oleylamidoethyl-imidazolinium-metho-sulfate, 2-heptadecyl- 1-methyl- 1-(2-stearoylamido)ethyl-imidazolinium-sulfate, 2-heptadecyl- 1-methyl- 1 (2-stearoylamido)ethyl-imidazolinium- chloride 2-coco- 1 -(2-hydroxyethyl)- 1 -benzyl-imidazolinium-chloride 2-coco- 1-(2-hydroxyethyl)- 1 -(4-chlorobutyl)-imidazoliniumchloride 2-coco- 1 -(2-hydroxyethyl)- 1 -octadecenyl-imidazolinium-chloride 2-tallow-1-(2-hydroxyethyl)-1-benzyl-imidazolinium-chloride 2-tallow-1-(2-hydroxyethyl)-1-(4-chlorobutyl)-imidazolinium-chloride 2-heptadecenyl-1-(2-hydroxyethyl)-1-(4-chlorobutyl)-imidazolinium-chloride 2-heptadecenyl-1-(2-hydroxyethyl)-1-benzyl-imidazolinium-chloride and 2-heptadecenyl- 1-(2-hydroxyethyl)- 1-octadecyl-imidazolinium-chloride One class of preferred quaternary ammonium compounds is that having the formula:

in which R7 is a C8-C30aliphatic residue, Rg, Rg, Rlo, R11 and R12, independently, are hydrogen, C1-C4alkyl or C1-C4hydroxyalkyl, A has its previous significance, m is an integer from 1 to 5 and n is an integer from 2 to 6.

Preferred compounds of formula (3) are those in which R7 is C12-C18alkyl and R8, Rg, R1o, R11 and R12, independently, are C1-C4alkyl, especially methyl.

Specific examples of preferred compounds of formula (3) are: N- (tallow)-N,N,N',N'-tetramethyl- 1,3 ,3-propanediammoniumdimethosulfate N-(tallow)-N,N',N'-trimethyl- 1 ,3-propanediammoniumdimetho sulfate N- (tallow)-N,N,N',N',N'-pentamethyl- 1 ,3-propanediammoniumdimethosulfate N-oleyl-N,N,N',N',N'-pentamethyl- 1 ,3-propanediammoniumdime thosulfate N-stearyl-N,N,N',N',N'-pentamethyl- 1 ,3-propanediammoniumdime thosulfate and N- stearyloxypropyl-N,N',N'-tris(3-hydroxypropyl)- 1 ,3-propanediammoniumdiacetate.

A further class of preferred quaternary ammonium compounds is that having the formula:

in which A has its previous significance and the groups R13 may be the same or different and each is a Cl-C30aliphatic residue, C1-C4hydroxyallcyl, C2H40C(=O)-R1, C2H4NHC(=O)-R1 or CH2CH[OC(=O)-R1][CH2OC(=O)-R1], provided that at least one group R13, and preferably two groups R13 are C14-C30alkyl, C2H4OC(=O)-C14-C30aIkyl, C2H4NHC(=O)-Cl4-C30alkyl or CH2CH[OC(=O)-C14-C30alkyl] [CH2OC(=O)-C14-C30alkyl]. Preferably, the remaining groups R13 are C1-C4alkyl, especially methyl or ethyl, or C1-C4hydroxyalkyl, especially hydroxymethyl or hydroxyethyl.

Specific examples of preferred compounds of formula (4) are: distearyldimethylammonium chloride dilauryldimethylammonium chloride dihexadecyldimethylammonium chloride dis tearyldimethylammonium bromide distearyldimethylammonium methosulfate and distearyldi-(isopropyl)-ammonium chloride distearoyl(hydroxyethyl)methylammonium methosulfate.

Preferred ester amide amine cationic fabric softening agents are those having the formula:

in which R13 has its previous significance and A1 is an inorganic or organic acid from which an anion A is derived, wherein A has its previous significance, provided that at least one group R13, and preferably two groups R13 are C14-C30alkyl, (CH2)nOC(=O)-Cl4-C30alkyl, (CH2)nNHC(=O)-C14-C30aLkyl or CH2CHrOC(=O)-Cl4-C30alkyl][CH20C(=O)-Cl4-C30alkyl], in which n has its previous significance. Preferably, the remaining groups R13 are C1-C4alkyl, especially methyl or ethyl, or C1-C4hydroxyalkyl, especially hydroxymethyl or hydroxyethyl.

A preferred compound of formula (5) is: 3-stearoylamidopropyl-2-stearoyloxymethyl-methylamine hydrochloride.

The cationic, amphoteric or anionic fluorescent whitening agent used may be one or more of the wide range of cationic, amphoteric or anionic fluorescent whitening agents, especially those which readily absorb UV light in the range B=280-400 nm and convert the absorbed energy, by a chemical intermediate reaction, into non-interfering, stable compounds or into non-interfering forms of energy. The cationic, amphoteric or anionic fluorescent whitening agent should preferably be compatible with the rinse cycle fabric care agent and should be capable of absorption on to the washed textile material during a rinse cycle fabric care treatment.

The cationic fluorescent whitening agent is preferably of the bistyrylphenyl class or phosphinic acid salt class; the amphoteric fluorescent whitening agent is preferably of the styrene or amine oxide class; and the anionic fluorescent whitening agent is preferably of the aminostilbene, dibenzofuranylbiphenyl or bistyrylphenyl class.

One preferred class of cationic bistyrylphenyl fluorescent whitening agent is that having the formula:

in which Y is arylene, preferably 1,4-phenylene or 4,4'-diphenylene, each optionally substituted by chloro, methyl or methoxy; q is 1 or 2; R14 is hydrogen, chloro, C1-C4-a:lky1, C1-C4-alkoxy, cyano or C1-C4-alkoxycarbonyl; Ris and R16 are C1-C4-alkyl, chloroethyl, methoxyethyl"ss-ethoxyethyl, 5-acetoxyethyl or ss-cyanoethyl, benzyl or phenylethyl;R17 is C1-C4-alkyl, C2-C3-hydroxyalkyl, ss-hydroxy-y-chloropropyl, ss-cyanoethyl or C1-C4-alkoxy-carbonylethyl; and A is an anion, preferably the chloride, bromide, iodide, methosulfate, ethosulfate, benzenesulfonate or p-toluenesulfonate anion when R17 is C1-C4-alkyl or A is preferably the formate, acetate, propionate or benzoate anion when R17 is '3-hydroxy-y-chloropropyl, 5-cyanoethyl or C1-C4-allcoxy-carbonylethyl.

Preferred compounds of formula (6) are those in which Y is 1 ,4-phenylene or 4,4'-diphenylene; R14 is hydrogen, methyl or cyano; R15 and R16 are each methyl or cyano; and R17 and A have their previously indicated preferred meanings.

One particularly preferred compound of formula (6) is that having the formula:

The compounds of formula (6) and their production are described in US-A-4 009 193.

A further preferred class of cationic bistyrylphenyl fluorescent whitening agent is that having the formula:

in which R14 and q have their previous significance; Y1 is C2-C4-alkylene or hydroxypropylene; R18 is C1-C4-alkyl or, together with R19 and the nitrogen to which they are each attached, R18 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R19 is C1-C4-alkyl or, together with R15 and the nitrogen to which they are each attached, R19 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R20 is hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C1-C4-akoxycarbonylmethyl, benzyl, C2-C4-hydroxyalkyl, C2-C4-cyanoalkyl or, together with R18 and R19 and the nitrogen atom to which they are each attached, R20 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring;A has its previous significance; and p isO or 1.

Preferred compounds of formula (8) are those in which q is 1; R14 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; Y1 is (CH2)2; R18 and R19 are the same and each is methyl or ethyl; R20 is methyl or ethyl; p is 1; and A is CH30SO3 or C2H5OSO3.

The compounds of formula (8) and their production are described in US-A-4 339 393.

in which R14, Y1, A, p and q have their previous significance; R21 and R22, independently, are C1-C4-alkyl or C2-C3-alkenyl or R21 and R22 together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R23 is hydrogen, C1-C4-alkyl or C2-C3-alkenyl or R21, R22 and R23, together with the nitrogen atom to which they are attached, form a pyridine or picoline ring; and Z is sulfur, -SO2-, -SO2NH-, -O-Cl-C4-alkylene-COO- or -OCO-.

Preferred compounds of formula (9) are those in which R14 is hydrogen, chlorine, Cl-C4-alkyl or C1-C4-alkoxy; R21 and R22, independently, are C1-C4-alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R23 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl or R21, R22 and R23, together with the nitrogen atom to which they are attached, form a pyridine ring; and Z is sulfur, -SO2- or -SO2NH-,.

The compounds of formula (9) and their production are described in US-A-4 486352.

in which R14, R21, R22, R23, Y1, A, p and q have their previous significance.

Preferred compounds of formula (10 are those in which q is 1; R14 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; R21 and R22, independently, are C1-C4-alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R23 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl or R21, R22 and R23, together with the nitrogen atom to which they are attached, form a pyridine ring.

The compounds of formula (10) and their production are described in US-A-4 602087.

One preferred class of amphoteric styrene fluorescent whitening agent is that having the formula:

in which R14, R21, R22, Y1 and q have their previous significance and Z1 is oxygen, sulfur, a direct bond, -COO-, -CON(R24)- or -SO2N(R24)- in which R24 is hydrogen, C1-C4-alkyl or cyanoethyl; and Q is -COO-or -S03.

Preferred compounds of formula (11) are those in which Z1 is oxygen, a direct bond, -CONH-, -SO2NH- or -COO-, especially oxygen; q is 1; R21 is hydrogen, C1-C4-alkyl, methoxy or chlorine; and R22, R23, Y1 and Q have their previous significance.

The compounds of formula (11) and their production are described in US-A-4 478 598.

One preferred class of amine oxide fluorescent whitening agent is that having the formula:

in which q has its previous significance; B is a brightener radical selected from a 4,4'-distyrylbiphenyl, 4,4'-divinyl-stilbene, and a 1 A'-distyrylbenzene, each optionally substituted by one to four substituents selected from halogen, C1-C4-alkyl, C 1-C4-hydroxyalkyl, C1-C4-halogenoalkyl, Cl-C4-cyanoalkyl, C1 -C4-alkoxy-C 1-C4-alkyl, phenyl-C1-C4-alkyl, carboxy-C1-C4-alkyl, carb-C1-C4-alkoxy-C1 -C4-alkyl, C1-C4-alkenyl, Cs-C8-cycloaLkyl, Cl-C4-alkoxy, Cl-C4-alkenoxy, Cl-C4-alkoxycarbonyl, carbamoyl, cyano, C1-C4-alkyl-sulfonyl, phenylsulfonyl, C1-C4-alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo and trifluoromethyl; Z2 iS a direct bond between B and Y2, an oxygen atom, a sulfur atom, -SO2-, -SO2-O-, -COO-, -CON(R27)- or -SO2N(R27)- in which R27 is hydrogen or C1-C4-alkyl optionally substituted by halogen, cyano, hydroxyl, C2-C5-carbalkoxy, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl;Y2 is C2-C4-alkylene or C2-C4-alkyleneoxy-C2-C4-alkylene, each optionally substituted by halogen, hydroxyl, C2-C5-carbalkoxy, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; and R2 and R26, independently, are C5-C8-cycloalkyl, C1-C4-alkyl or phenyl, each optionally substituted by halogen, hydroxyl, C2-C-carbalkoxy, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; in which, in all the carbamoyl or sulfamoyl groups, the nitrogen atom is optionally substituted by one or two C1-C4-alkyl, C1-C4-hydroxyalkyl, C2-C5-cyanoalkyl, C1-C4-halogenoalkyl, benzyl or phenyl groups.

Preferred brightener radicals B are those having the formula:

in which q has its previous significance and the rings are optionally substituted as indicated above.

Preferably Z2 is oxygen, -SO2- or -SO2N(R23)- in which R25 is hydrogen or Cl-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; and Ru and R26, independently, are C1-C4-alkyl optionally substituted by halogen, cyano, hydroxyl, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl or C2-C5-alkoxycarbonyl. Other preferred compounds of formula (10) are those in which Z) is oxygen, sulfur, -SO2-, -CON(R28)- or -SO2N(R28)- in which R25 is hydrogen or Cl-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; and Y2 is C1-C4-alkylene.

The compounds of formula (12) and their production are described in US-A-4 539 161.

One preferred class of cationic phosphinic acid salt fluorescent whitening agent is that having the formula:

in which q has its previous significance; B1 is brightener radical; Z3 is a direct bond, -SO2-C2-C4-alkyleneoxy, -SO2-C2-C4-alkylene-COO-, -S 02-, -COO-, -SO2-C2-C4-aIkylene-CON(R33)- or -SO2N(R33)- in which R33 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano;R28 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hyxdroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy, or R28 is benzyl, optionally substituted by halogen , C1-C4-alkyl or C1-C4-alkoxy, or R28, together with R29 or Z3, forms a pyrrolidine, piperidine or morpholine radical; R29 is C1-C4-alkyl or C2- C4- alkenyl, each optionally substituted by halogen, cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy, or R29 is benzyl, optionally substituted by halogen, Cl-C4-alkyl or C1-C4-alkoxy, or R29, together with R28, forms a pyrrolidine, piperidine or morpholine radical; R30 is C1-C4-alkyl; R31 is hydrogen or C1-C4-alkyl, optionally substituted by cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy; and R32 is C1-C4-alkyl.

Preferably, brightener radical B1 has the formula:

or the formula:

each optionally substituted by one to four substituents selected from halogen, C1-C4-alkyl, C1-C4-hydroxyalkyl, C1-C4-halogenoalkyl, C1-C4-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl-Cl-C4-alkyl, carboxy-Cl-C4-alkyl, carb-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkenyl, C5-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-alkenoxy, C1-C4-alkoxycarbonyl, carbamoyl, cyano, C1-C4-alkyl-sulfonyl, phenylsulfonyl, C1-C4-alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo and trifluoromethyl.

The compounds of formula (13) and their production are described in GB-A-2 023 605.

Preferred bis(triazinyl)diaminostilbene anionic fluorescent whitening agents for use in the present invention are those having the formula:

Preferred dibenzofuranylbiphenyl anionic fluorescent whitening agents for use in the present invention are those having the formula:

Preferred anionic bistyrylphenyl fluorescent whitening agents for use in the present invention are those having the formula:

In the formulae (14) to (16), R33 is phenyl optionally substituted by one or two SO3M groups and R34 is NH-C1-C4-alkyl, N(C1-C4-alkyl)2, NH-C1-C4-alkoxy, N(C1-C4-alkoxy)2, N(C1 -C4-alkyl) (C1-C4-hydroxyalkyl), N(C1 -C4-hydroxyalkyl)2; R35 is H, C1-C4-allcyl, CN, Cl or SO3M;R36 and R37, independently, are H, C1-C4-alkyl, SO3M, CN, C1 or O-C1-C4-alkyl, provided that at least two of R35, R36 and R37 are SO3M and the third group has solubilising character; R38 is H, SO3M, O-C1-C4-alkyl, CN, Cl, COO-C1-C4-alkyl, or CON(C1-C4-alkyl)2; M is is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C1-C4-alkylammonium, mono-, di- or tri-C1-C4-hydroxyalkylammonium or ammonium that is di- or tri-substituted with by a mixture of C1-C4-alkyl and C1-C4-hydroxyalkyl groups; and r is 0 or 1.

In the compounds of formulae (14) to (16), Cl-C4-alkyl groups are, e.g., methyl, ethyl, propyl, isopropyl and n-butyl, especially methyl. Aryl groups are naphthyl or, especially, phenyl.

Specific examples of preferred compounds of formula (14) are those having the formulae:

Preferred examples of compounds of formula (15) are those of formulae:

Preferred examples of compounds of formula (16) are those having the formulae:

The compounds of formulae (14) to (16) are known and may be obtained by known methods.

In addition to the fluorescent whitening agent, 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, UV absorbers, 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 should not exceed 2% by weight of the composition.

The present invention also provides, as a third apect, a method for the treatment of a textile article, comprising applying, to a previously washed article, a fabric rinse composition comprising 0.3 to 10% by weight of a cationic, amphoteric or anionic fluorescent whitening agent, based on the total weight of the composition, and optionally a fabric care ingredient, the remainder being substantially water.

Preferably, the fabric care ingredient is a fabric softener, a stain release or stain repellant ingredient or a water-proofing agent, which is preferably present in an amount of from 5 to 25%, especially from 10 to 20% by weight, based on the total weight of the composition.

A preferred method for the treatment of a textile article, comprises applying, to the previously washed article, a rinse cycle fabric softener composition comprising 5 to 25, preferably 10 to 20% by weight of a cationic fabric softening agent and 0.3 to 10, preferably 0.3 to 3% by weight of a cationic, amphoteric or anionic fluorescent whitening agent, each based on the total weight of the composition, the remainder being substantially water.

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

The method and composition of the present invention, in addition to providing an improved SPF to the washed textile article, and thereby enhanced protection to the skin, also increase the useful life of a textile article treated according to the present invention, e.g. by improving the tear strength and lightfastness of textile articles so treated.

The following Examples further illustrate the present invention.

Example 1 The following rinse cycle softener base composition is made up: 7.0g. distearyldimethylammonium chloride (72% active ingedient) 0.5g. fatty alcohol ethoxylate 92.5g. deionised water.

To this is added 0.3g., 0.9g. or 2.7g., respectively, of the amphoteric fluorescent whitening agent of formula:

Example 2 The following rinse cycle softener base composition is made up: 7.0g. distearyldimethylammonium chloride 0.5g. fatty alcohol ethoxylate 92.5g. deionised water.

To this is added 0.3g., 0.9g. or 2.7g., respectively, of the cationic fluorescent whitening agent of formula:

Examples 3 and 4 5g. of cotton fabric are first washed with 4g/l of ECE standard detergent using a liquor ratio of 1:20 at 600C. The washed goods are then rinsed and are subjected, while still wet, to a rinse softener treatment. The amount of the rinse cycle softener base composition of Example 1 or 2 used is 5gel. The liquor ratio is 1:40 using tap water and the treatment is effected at 250C. for 10 minutes. The softener-treated goods are then spin-dried at 600C.

The whiteness and SPF values of the dried softener-treated goods are measured.

The dried softener-treated goods are then re-washed using the same detergent and washing conditions that are used for the initial wash except that, after the rinse, the re-washed goods are spin-dried at 600 C. without being subjected to a rinse softener treatment. The whiteness and SPF values of the re-washed, dried goods are measured.

The whiteness values of the respective dried goods are measured with a DCI/SF 500 spectrophotometer according to the Ganz method.The Ganz method is described in detail in the Ciba-Geigy Review, 1973/1, and also in the article "Whiteness Measurement", ISCC Conference on Fluorescence and the Colorimetry of Fluorescent Materials, Williamsburg, February 1972, published in the Journal of Color and Appearance, 1, No.5 (1972).

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.

The results are shown in the following Table.

Table

Without re-wash With re-wash Example Rinse Composition Conc. FWA GW SPF GW SPF - control(noFWA) (no FWA) 67 3 75 3 0.3 194 9 181 8 3 RinseofExample 1 0.9 197 15 199 11 2.7 169 24 200 16 0.3 199 14 182 13 4 Rinse of Example 2 0.9 206 17 202 20 2.7 193 29 193 26 The concentration of FWA denotes the concentration of active FWA compound based on the total weight of the rinse formulation.

The results in the Table clearly demonstrate the improvement in the Ganz Whiteness and SPF values of a cotton substrate treated with a rinse composition according to the present invention, both before and after a subsequent re-wash.

Similar results are obtained when the fluorescent whitening agent used in Example 1 or 2 is replaced by a compound having one of the following formulae:

Claims

Claims 1. A stable, concentrated fabric rinse composition comprising 0.3 to 10% by weight of a fluorescent whitening agent which is compatible with a fabric care ingredient, based on the total weight of the composition, and optionally a fabric care ingredient, the remainder being substantially water.
2. A composition according to claim 1 in which the fabric care ingredient is a fabric softener, a stain release or stain repellant ingredient or a water-proofing agent.
3. A composition according to claim 1 or 2 in which the fabric care ingredient is present in an amount of from 5 to 25% by weight, based on the total weight of the composition.
4. A composition according to claim 3 in which the fabric care ingredient is present in an amount of from 10 to 20% by weight, based on the total weight of the composition.
5. A stable, concentrated rinse cycle fabric softener composition comprising 5 to 25% by weight of a cationic fabric softening agent and 0.3 to 10% by weight of a a fluorescent whitening agent which is compatible with a cationic fabric softening agent, each based on the total weight of the composition, the remainder being substantially water.
6. A composition according to claim 5 comprising 10 to 20% by weight of a cationic fabric softening agent and 0.3 to 3% by weight of a fluorescent whitening agent which is compatible with a cationic fabric softening agent, each based on the total weight of the composition, the remainder being substantially water
7. A composition according to any of the preceding claims in which the fluorescent whitening agent is a cationic amphoteric or anionic fluorescent whitening agent.
8. A composition according to any of claims 5 to 7 in which the cationic fabric softening agent is an imidazoline, a quaternary ammonium compound, an ester amide amine salt or a mixture thereof.
9. A composition according to claim 8 in which the imidazoline cationic fabric softening agent has the formula:

in which R is hydrogen or C1-C4alkyl; R1 is a C3-C30aliphatic residue; R2 is -C2H4-O(C=O)-R1 or -C2H4-NH(C=O)-R1; and A is an anion.
10. A composition according to claim 9 in which R is hydrogen or methyl; Rlis Cl4-Cl8alkyl or C14-C18alkenyl; and R2 is -C2H4-O(C=O)-Cl4-Cl8alkyl or -C14-C18alkenyl, or -C2H4-NH(C=O)-C14-C1 8alkyl or -Cl4-Cl8alkenyl.
11. A composition according to claim 8 in which the imidazoline cationic fabric softening agent has the formula:

in which R1 is a C8-C30aliphatic residue; R3 and R4, independently, are a C8-C30aliphatic residue, C1-C4alkyl, C1 -C4halogenoalkyl, C1-C4ydroxyalkyl or a group -C2H4-N(R5)-C(=O)-R6 in which R5 is hydrogen or C8-C30alkyl and R6 is hydrogen or Cl-C4alkyl; and A is an anion.
12. A composition according to claim 11 in which Rlis Cl4-C18alkyl or Cl4-Cl8alkenyl; R3 is C14-C18alkyl, C14-C18galkenyl, Cl-C4alkyl, C1-C4halogenoalkyl or C1-C4hydroxyalkyl; and R4 is a group -C2H4-N(R5)-C(=O)-R6 in which R5 is hydrogen or C8-C30alkyl and R6 is hydrogen or C1-C4alkyl.
13. A composition according to claim 8 in which the quaternary ammonium compound has the formula:

in which R7 is a C8-C30aliphatic residue, R8, R9, R1o, R11 and R12, independently, are hydrogen, C1-C4alkyl or C1-C4hydroxyalkyl, A is an anion, m is an integer from 1 to 5 a n is an integer from 2 to 6.
14. A composition according to claim 13 in which R7 is C12-Cl8alkyl and R8, R9, Rlo, R1 and R12, independently, are Cl-C4alkyl.
15. A composition according to claim 14 in which Rg, Rg, Rlo, R11 and R12, independently, are methyl.
16. A composition according to claim 8 in which the quaternary ammonium compound has the formula:

in which A is an anion and the groups R13 may be the same or different and each is a Cl-C30aliphatic residue, Cl-C4hydroxyalkyl, C2H40C(=O)-R1, C2H4NHC(=O)-R1 or CH2CH[OC(=O)-Rl][CH2OC(=O)-Rl], provided that at least one group R13 is Cl4-C30alkyl, C2H40C(=O)-Cl4-C30alkyl, C2H4NHC(=O)-Cl4-C30alkyl or CH2CH[OC(=O)-C14-C30alkyl] [CH2OC(=O)-C14-C30alkyl].
17. A composition according to claim 16 in which two groups R13 are C14-C30alkyl, C2H40C(=O)-Cl4 C30alkyl, C2H4NFIC(=O)- C14-C30alkyl or CH2CH[OC(=O)-C14-C30alkyl] [CH2OC(=O)-C14-C30alkyl].
18. A composition according to claim 16 or 17 in which the remaining groups Rl3 are Cl-C4alkyl or C1-C4hydroxyalkyl.
19. A composition according to claim 18 in which the remaining groups R13 are methyl, ethyl, hydroxymethyl or hydroxyethyl.
20. A composition according to claim 8 in which the imidazoline cationic fabric softening agent has the formula:

in which R13 is as defined in claim 16 and Al is an inorganic or organic acid from which an anion A is derived, wherein A is as defined in claim 16, provided that at least one group R13 is C14-C30alky1, (CH2)nOC(=O)-C14-C30alkyl, (CH2)nNHC(=O)-Cl4-C30alkyl or CH2CH[OC(=O)-C14-C30alkyl] [CH2OC(=O)-C14-C30alkyl], in which n is as defined in claim 13.
21. A composition according to claim 20 in which two groups R13 are C14-C30alkyl, C2H40C(=O)-Cl4-C30alkyl, C2H4NHC(=O)-Cl4-C30alkyl or CH2CH[OC(=O)-C-C30aikyl [CH2OC(=O)-C14-C30aIkyl].
22. A composition according to claim 20 or 21 in which the remaining groups R13 are C1-C4alkyl or Cl-C4hydroxyalkyl.
23. A composition according to claim 22 in which the remaining groups R13 are methyl, ethyl, hydroxymethyl or hydroxyethyl.
24. A composition according to any of claims 9 to 23 in which A is a chloride, bromide, iodide, fluoride, sulfate, methosulfate, nitrite, nitrate or phosphate anion, or a carboxylate anion.
25. A composition according to claim 24 in which the carboxylate anion is an acetate, adipate, phthalate, benzoate, stearate or oleate anion.
26. A composition according to claim 9 in which the compound of formula (1) is: 2-tallow-1-(2-stearoyloxyethyl)-imidazoline chloride, 2-tallow-1-(2-stearoyloxyethyl)-imidazoline sulfate, 2-tallow-1-(2-stearoyloxyethyl)-imidazoline methosulfate, 2-tallow-1-methyl-3-(2-stearoylamidoethyl)-imidazoline chloride, 2-tallow-1-methyl-3-(2-stearoylamidoethyl)-imidazoline sulfate or 2-tallow-1-methyl-3-(2-stearoylamidoethyl)-imidazoline methosulfate.
27. A composition according to claim 11 in which the compound of formula (2) is: 2-heptadecyl- 1-methyl-i -oleylamidoethyl-imidazolinium-metho-sulfate, 2-heptadecyl- l-methyl- -(2-stearoylamido)ethyl-imidazolinium-sulfate, 2-heptadecyl- 1-methyl-I -(2-stearoylamido)ethyl-imidazolinium- chloride 2-coco- 1 -(2-hydroxyethyl)- 1 -benzyl-imidazolinium-chloride 2-coco- 1 -(2-hydroxyethyl)- 1 -(4-chlorobutyl)-imidazoliniumchloride 2-coco- 1 -(2-hydroxyethyl)- 1-octadecen)l-imidazolinium-chloride 2-tallow- 1-(2-hydroxyethyl)-1-benzyl-imidazolinium-chloride 2-tallow- 1-(2-hydroxyethyl)- 1 -(4-chlorobutyl)-imidazolinium-chloride 2-heptadecenyl-1 -(2-hydroxyethyl)- 1 -(4-chlorobutyl)-imidazolinium-chloride 2-heptadecenyl 1 -(2-hydroxyethyl)- 1 -benzyl-imidazolinium-chloride or 2-heptadecenyl- 1 -(2-hydroxyethyl)- 1 -octadecyl-imidazolinium-chloride.
28. A composition according to claim 13 in which the compound of formula (3) is: N-(tallow)-N,N,N',N'-tetramethyl- 1 ,3-propanediammoniumdimethosulfate N-(tallow)-N,N',N'-trimethyl- 1 ,3-propanediammoniumdimetho sulfate N-(tallow)-N,N,N',N',N'-pentamethyl- I ,3-propanediammoniumdimethosulfate N-oleyl-N,N,N',N',N'-pentamethyl- 1 ,3-propanediammoniumdime thosulfate N-stearyl-N,N,N',N',N'-pentamethyl- 1 ,3-propanediammoniumdime thosulfate or N-stearyloxypropyl-N,N',N'-tris(3-hydroxypropyl)- 1 ,3-propanediammoniumdiacetate.
29. A composition according to claim 16 in which the compound of formula (4) is: distearyldimethylammonium chloride dilauryldimethylammonium chloride dihexadecyldimethylammonium chloride distearyldimethylammonium bromide distearyldimethylammonium methosulfate distearyldi(isopropyl)ammonium chloride or distearoyl(hydroxyethyl)methylammonium chloride.
30. A composition according to claim 20 in which the compound of formula (5) is: 3-stearoylamidipropyl-2-stearoyloxymethyl-methylamine hydrochloride.
31. A composition according to any of claims 7 to 30 in which the cationic fluorescent whitening agent is of the bistyrylphenyl or phosphinic acid salt class; the amphoteric fluorescent whitening agent is of the styrene or amine oxide class; and anionic fluorescent whitening agent is of the aminostilbene, dibenzofuranylbiphenyl or bistyrylphenyl class.
32. A composition according to claim 31 in which the cationic bistyrylphenyl fluorescent whitening agent has the formula:

in which Y is arylene; q is 1 or 2; Rl4 is hydrogen, chloro, C1-C4-alkyl, C1-C4-alkoxy, cyano or C1-C4-alkoxycarbonyl; R15 and R16 are C1-C4-alkyl, chloroethyl, methoxyethyl, ss-ethoxyethyl, ss-acetoxyethyl or ss-cyanoethyl, benzyl or phenylethyl; R16 is C1-C4-aIky1, C2- C3- hydroxyalkyl, P-hydroxy-y-chloropropyl, ss-cyanoethyl or C1-C4-alkoxy-carbonylethyl; and A is an anion.
33. A composition according to claim 32 in which in which Y is 1 ,4-phenylene or 4,4'-diphenylene, each optionally substituted by chloro, methyl or methoxy; R14, R15, R16, R17 and q are as defined in claim 32; and A is a chloride, bromide, iodide, methosulfate, ethosulfate, benzenesulfonate or p-toluenesulfonate anion when R17 is C1-C4-alkyl or A is a formate, acetate, propionate or benzoate anion when R17 is I3-hydroxy-y-chloropropyl, P-cyanoethyl or Cl-C4-alkoxy-carbonylethyl.
34. A composition according to claim 33 in which R17 and A are as defined in claim 33; Y is 1,4-phenylene or 4,4'-diphenylene; R14 is hydrogen, methyl or cyano; q is 1; and R15 and R16 are each methyl or cyano.
35. A composition according to claim 32 in which the compound of formula (6) is that having the formula:
36. A composition according to claim 31 in which the cationic bistyrylphenyl fluorescent whitening agent has the formula:

in which R14 and q are as defined in claim 32; Y1 is C2-C4-alkylene or hydroxypropylene; R18 is C1-C4-alkyl or, together with R19 and the nitrogen to which they are each attached, R18 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; Rlg is C1-C4-alkyl or, together with R18 and the nitrogen to which they are each attached, R19 forms a pyrrolidine, piperidine, hexamethyleneirnine or morpholine ring;R20 is hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C1-C4-akoxycarbonylmethyl, benzyl, C2-C4-hydroxyalkyl, C2-C4-cyanoalkyl or, together with R18 and R19 and the nitrogen atom to which they are each attached, R20 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; A is as defined in claim 16; and p isO or 1.
37. A composition according to claim 36 in which Y1 is (CH2)2; R18 and R19 are the same and each is methyl or ethyl; R20 is methyl or ethyl; p is 1; and A is CH30SO3 or C2HsOSO3.
38. A composition according to claim 31 in which the cationic bistyrylphenyl fluorescent whitening agent has the formula:

in which R14, Y1, A, p and q are as defined in claim 36; R21 and R22, independently, are C1-C4-alkyl or C2-C3-alkenyl or R21 and R22, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; Rp is hydrogen, C1-C4-alkyl or C2-C3-aikenyl or R21, R22 and R23, together with the nitrogen atom to which they are attached, form a pyridine or picoline ring; and Z is sulfur, -SO2-, -SO2NH-, -O-C1-C4-alkylene-COO- or -OCO-.
39. A composition according to claim 38 in which q is 1; R14 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; R21 and R22, independently, are C1-C4-alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R23 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl or R21, R22 and R23, together with the nitrogen atom to which they are attached, form a pyridine ring; and Z is sulfur, -S02- or -SO2NH-.
40. A composition according to claim 31 in which the cationic bistyrylphenyl fluorescent whitening agent has the formula:

in which R14 is as defined in claim 32; and R21, R22, R23, Y1, A, p and q are as defined in claim 38.
41. A composition according to claim 40 in which R14 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; R21 and R22, independently, are C1-C4-alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R23 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl or R21, R22 and R23, together with the nitrogen atom to which they are attached, form a pyridine ring.
42. A composition according to claim 31 in which the amphoteric styrene fluorescent whitening agent has the formula:

in which R14, R21, R22, Y1 and q are as defined in claim 40; Z1 is oxygen, sulfur, a direct bond, -COO-, -CON(R24)- or -SO2N(R24)- in which R24 is hydrogen, C1-C4-alkyl or cyanoethyl; and Q is -COO-or -SO3.
43. A composition according to claim 42 in which Z1 is oxygen, a direct bond, -CONH-, -SO2NH- or -COO-; q is 1; R14 is hydrogen, C1-C4-alkyl, methoxy or chlorine; and R21, R, Y1 and Q are as defined in claim 42.
44. A composition according to claim 43 in which Z1 is oxygen.
45. A composition according to claim 31 in which the amine oxide fluorescent whitening agent has the formula:

in which q is as defined in claim 42; B is a brightener radical selected from a 4,4'-distyrylbiphenyi, 4,4'-divinyl-stilbene, and a 1 ,4'-distyrylbenzene, each optionally substituted by one to four substituents selected from halogen, C1-C4-alkyl, C1-C4-hydroxyalkyl, C1-C4-halogenoalkyl, Cl-C4-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl-C1-C4-alkyl, carboxy-C1-C4-alkyl, carb-Cl-C4-alkoxy-Cl-C4-alkyl, C1- C4-alkenyl, C5-C8-cycloalkyl, Cl-C4-alkoxy, C1-C4-alkenoxy, C alkenoxy, Cl-C4-alkoxycarbonyl, carbamoyl, cyano, C1-C4-alkyl-sulfonyl, phenylsulfonyl, C1 -C4-alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo and trifluoromethyl; Z2 is a direct bond between B and Y2, an oxygen atom, a sufur atom, -SO2-, -S 02-0-, -COO-, -CON(R27)- or -SO2N(R27)- in which R27 is hydrogen or Cl-C4-alkyl optionally substituted by halogen, cyano, hydroxyl, CrCs-carbalkoxy, Cl-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; Y2 is C2-C4-alkylene or C2-C4-alkyleneoxy-C2-C4-alkylene, each optionally substituted by halogen, hydroxyl, C2-Cs-carbalkoxy, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; and R25 and R26, independently, Cs-C8-cycloalkyl, C1-C4-alkyl or phenyl, each optionally substituted by halogen, hydroxyl, C2-C5-carbalkoxy, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; in which, in all the carbamoyl or sulfamoyl groups, the nitrogen atom is optionally substituted by one or two C1-C4-alkyl, C1-C4-hydroxyalkyl, C2-C5-cyanoalkyl, C1-C4-halogenoalkyl, benzyl or phenyl groups.
46. A composition according to claim 45 in which brightener radicals B are those having the formula:

in which q is as defined in claim 42; and B is optionally substituted as defined in claim 45.
47. A composition according to claim 45 in which Z2 is oxygen, -SO2- or -SO2N(R28)- in which R28 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; and R25 and R26, independently, are C1-C4-alkyl optionally substituted by halogen, cyano, hydroxyl, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl or C2-Cs-alkoxycarbonyl, or in which z2 is oxygen, sulfur, -SO2-, -CON(R28)- or -SO2N(R28)- in which R28 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; and Y2 is C1-C4-alkylene.
48. A composition according to claim 31 in which the cationic phosphinic acid salt fluorescent whitening agent is that having the formula:

in which q is as defined in claim 42; B1 is brightener radical; Z3 is a direct bond, -SO2-C2-C4-alkyleneoxy, -SO2-C2-C4-alkylene-COO-, -S02-, -COO-, -SO2-C2-C4-alkylene-CON(R33)- or -SO2N(R33)- in which R33 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano;R28 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hyxdroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy, or R28 is benzyl, optionally substituted by halogen , C1-C4-alkyl or C1-C4-alkoxy, or R28, together with R29 or Z3, forms a pyrrolidine, piperidine or morpholine radical; R29 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy, or R29 is benzyl, optionally substituted by halogen, C1-C4-alkyl or C1-C4-alkoxy, or R29, together with R28, forms a pyrrolidine, piperidine or morpholine radical; R30 is C1-C4-alkyl; R31 is hydrogen or C1-C4-alkyl, optionally substituted by cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy; and R32 is C1-C4alkyl.
49. A composition according to claim 48 in which brightener radical B1 has the formula:

or the formula:

each optionally substituted by one to four substituents selected from halogen, C1-C4-alkyl, C1-C4-hydroxyalkyl, Cl-C4-halogenoalkyl, C1-C4-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl-C1-C4-alkyl, carboxy-C1-C4-alkyl, carb-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkenyl, C5-Cs-cycloalkyl, C1-C4-alkoxy, C1-C4-alkenoxy, C1-C4-alkoxycarbonyl, carbamoyl, cyano, C1 -C4-alkyl-sulfonyl, phenylsulfonyl, C1-C4-alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo and trifluoromethyl.
50. A composition according to claim 31 in which the bis(triazinyl)diaminostilbene anionic fluorescent whitening agent has the formula:

in which R33 is phenyl optionally substituted by one or two SO3M groups and R34 is NH-C1-C4-alkyl, N(C1-C4-alkyl)2, NH-C1 -C4-alkoxy, N(C1-C4-alkoxy)2, N(C1-C4-alkyl) (C1-C4-hydroxyalkyl), N(C1-C4-hydroxyalkyl)2.
51. A composition according to claim 31 in which the dibenzofuranylbiphenyl anionic fluorescent whitening agent has the formula:

in which R36 is H, C1-C4-alkyl, CN, Cl or SO3M; R37 and R38, independently, are H, C1-C4-alkyl, SO3M, CN, C1 or O-C1-C4-alkyl, provided that at least two of R36, R37 and R38 is SO3M and the third group has solubilising character.
52. A composition according to claim 31 in which the anionic bistyrylphenyl fluorescent whitening agent has the formula:

in which R38 is H, SO3M, O-C1-C4-alkyl, CN, Cl, COO-C1-C4-alkyl, or CON(C1-C4-alkyl)2; M is is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C1-C4-alkylammonium, mono-, di- or tri-C1-C4-hydroxyalkylammonium or ammonium that is di- or tri-substituted with by a mixture of C-C4-alkyl and C1-C4-hydroxyalkyl groups; and r is 0 or 1.
53. A composition according to any of the preceding claims which also contains an adjuvant selected from an emulsifier, perfume, colouring dye, opacifier, a UV absorber, bactericide, nonionic surfactant, anti-gelling agent and corrosion inhibitor.
54. A composition according to claim 53 in which the anti-gelling agent is a nitrite or nitrate of an alkali metal and the corrosion inhibitor is sodium silicate.
55. A method for the treatment of a textile article, comprising applying, to the previously washed article, a fabric rinse composition comprising 0.3 to 10% by weight of a fluorescent whitening agent which is compatible with a fabric care ingredient, based on the total weight of the composition, and optionally a fabric care ingredient, the remainder being substantially water.
56. A method according to claim 55 in which the fluorescent whitening agent is a cationic, amphoteric or anionic fluorescent whitening agent.
57. A method according to claim 55 or 56 in which the fabric care ingredient is a fabric softener, a stain release or stain repellant ingredient or a water-proofing agent.
58. A method according to any of claims 55 to 57 in which the fabric care ingredient is present in an amount of from 5 to 25% by weight, based on the total weight of the composition.
59. A method according to claim 55 in which the fabric care ingredient is present in an amount of from 10 to 20% by weight, based on the total weight of the composition.
60. A method for the treatment of a textile article, comprising applying, to the previously washed article, a rinse cycle fabric softener composition comprising 5 to 25% by weight of a cationic fabric softening agent and 0.3 to 10% by weight of a fluorescent whitening agent which is compatible with a cationic fabric softening agent, each based on the total weight of the composition, the remainder being substantially water.
61. A method according to claim 60 in which the rinse cycle fabric softener composition comprises 10 to 20% by weight of a cationic fabric softening agent and 0.3 to 3% by weight of a fluorescent whitening agent which is compatible with a cationic fabric softening agent, each based on the total weight of the composition, the remainder being substantially water.
62. A method according to claim 60 or 61 in which the fluorescent whitening agent is a cationic, amphoteric or anionic fluorescent whitening agent.
63. A method according to any of claims 60 to 62 in which the textile article treated is composed of wool, polyamide, cotton, polyester, polyacrylic, silk or any mixture thereof.
64. A method according to any of the preceding claims whereby the tear strength and/or the lightfastness of the textile article so treated is improved.