EP0682145B1 - Textile treatment - Google Patents

Textile treatment Download PDF

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Publication number
EP0682145B1
EP0682145B1 EP95810288A EP95810288A EP0682145B1 EP 0682145 B1 EP0682145 B1 EP 0682145B1 EP 95810288 A EP95810288 A EP 95810288A EP 95810288 A EP95810288 A EP 95810288A EP 0682145 B1 EP0682145 B1 EP 0682145B1
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EP
European Patent Office
Prior art keywords
alkyl
formula
fluorescent whitening
whitening agent
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95810288A
Other languages
German (de)
French (fr)
Other versions
EP0682145A3 (en
EP0682145A2 (en
Inventor
Dieter Dr. Reinehr
Claude Dr. Eckhardt
Werner Dr. Kaufmann
Peter Dr. Fankhauser
Rolf Dr. Hilfiker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Filing date
Publication date
Priority claimed from GB9409466A external-priority patent/GB9409466D0/en
Priority claimed from GB9409465A external-priority patent/GB9409465D0/en
Priority claimed from GB9413270A external-priority patent/GB9413270D0/en
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Publication of EP0682145A2 publication Critical patent/EP0682145A2/en
Publication of EP0682145A3 publication Critical patent/EP0682145A3/en
Application granted granted Critical
Publication of EP0682145B1 publication Critical patent/EP0682145B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments

Definitions

  • the present invention relates to a use of a fluorescent whitening agent in a composition for improving the sun protection factor (SPF) of textile fibre material, wherein said fluorescent whitening agent absorbs radiation in the wavelength range 280-400 nm.
  • SPDF sun protection factor
  • US-A-4 460 485 discloses fluorescent whitening agents, which are applied to textile fiber material.
  • US-A-4 339 393 discloses distyrylbiphenyls as fluorescent whitening agents for textiles.
  • wavelengths 280-400 nm permits tanning of the epidermis.
  • rays of wavelengths 280-320 nm (termed UV-B radiation), cause erythemas and skin burning which can inhibit skin tanning.
  • UV-A radiation 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.
  • 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.
  • 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.
  • Such lightweight summer clothing normally has a density of 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 SPF rating of a sun protectant 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.
  • the present invention provides a use of a fluorescent whitening agent for improving the sun protection factor (SPF) of textile fibre material, wherein said fluorescent whitening agent absorbs radiation in the wavelength range 280-400 nm, in a composition, which is
  • the textile fibre material treated according to the use of the present invention may be composed of a wide variety of natural or synthetic fibres, e.g., wool, polyamide, cotton, polyester, polyacrylic, silk, polypropylene or mixtures thereof, preferably cotton.
  • the textile fibre material may be in the form of endless filaments (stretched or unstretched), staple fibres, flocks, hanks, textile filament yams, threads, nonwovens, felts, waddings, flocked structures or woven textile or bonded textile fabrics or knitted fabrics.
  • the amount of fluorescent whitening agent present in the composition used according to the use of the present invention may vary within a wide range, e.g. from 0.005 to 20 %, based on the weight of the textile fibre material, depending on the particular composition used in the used of the present invention.
  • the amount of fluorescent whitening agent present in the composition preferably ranges from 0.01 to 3%, especially from 0.05 to 1%, based on the weight of the textile fibre material.
  • the amount of fluorescent whitening agent present in the composition preferably ranges from 0.005 to 2%, especially from 0.01 to 1%, based on the weight of the textile fibre material.
  • the amount of fluorescent whitening agent present in the composition preferably ranges from 0.1 to 20%, especially from 1 to 10%, based on the weight of the textile fibre material.
  • preferred 4,4'-bis-(triazinylamino)-stilbene-2,2'-disulfonic acids are those having the formula: in which R 1 and R 2 , independently, are phenyl, mono- or disulfonated phenyl, phenylamino, mono- or disulfonated phenylamino, morpholino, N(CH 2 CH 2 OH) 2 , -N(CH 3 )(CH 2 CH 2 OH), -NH 2 , -N(C 1 -C 4 alkyl) 2 , -OCH 3 , -Cl, -NH-CH 2 CH 2 SO 3 H or NH-CH 2 CH 2 OH; and M is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra- C 1 -C 4 -alkylammonium, mono-
  • each R 1 is 2,5-disulfophenyl and each R 2 is morpholino; or each R 1 is 2,5-disulfophenyl and each R 2 is N(CH 2 CH 2 ); or each R 1 is 3-sulfophenyl and each R 2 is NH(CH 2 CH 2 OH) or N(CH 2 CH 2 OH) 2 ; or each R 1 is 4-sulfophenyl and each R 2 is N(CH 2 CH 2 OH) 2 ; and, in each case, the sulfo group is SO 3 M in which M is sodium.
  • Preferred 4,4'-bis-(triazol-2-yl)stilbene-2,2'-disulfonic acids are those having the formula: in which R 3 and R 4 , independently, are H, C 1 -C 4 -alkyl, phenyl or monosulfonated phenyl; and M has its previous significance.
  • Especially preferred compounds of formula (2) are those in which R 3 is phenyl, R 4 is H and M is sodium.
  • One preferred 4,4'-(diphenyl)-stilbene is that having the formula:
  • 4,4'-distyryl-biphenyls used are those of formula: in which R 5 and R 6 , independently, are H, SO 3 M, SO 2 N(C 1 -C 4 -alkyl) 2 , O-(C 1 -C 4 -alkyl), CN, Cl, COO(C 1 -C 4 -alkyl), CON(C 1 -C 4 -alkyl) 2 or O(CH 2 ) 3 N ⁇ (CH 3 ) 2
  • Especially preferred compounds of formula (4) are those in which n is 1 and each R 5 is a 2-SO 3 M group in which M is sodium and each R 6 is H, or each R 5 is O(CH 2 ) 3 N ⁇ (CH 3 ) 2 An ⁇ in which An ⁇ is acetate.
  • Preferred 4-phenyl-4'-benzoxazolyl-stilbenes have the formula: in which R 7 and R 8 , independently, are H, Cl, C 1 -C 4 -alkyl or SO 2 -C 1 -C 4 -alkyl.
  • An especially preferred compound of formulae (5) is that in which R 7 is 4-CH 3 and R 8 is 2-CH 3 .
  • stilbenyl-naphthotriazoles used are those of formula: in which R 9 is H or Cl; R 10 is SO 3 M, SO 2 N(C 1 -C 4 -alkyl) 2 , SO 2 O-phenyl or CN; R 11 is H or SO 3 M; and M has its previous significance.
  • Especially preferred compounds of formula (6) are those in which R 9 and R 11 are H and R 10 is 2-SO 3 M in which M is Na.
  • 4-styryl-stilbenes used are those of formula: in which R 12 and R 13 , independently, are H, SO 3 M, SO 2 N(C 1 -C 4 -alkyl) 2 , O-(C 1 -C 4 -alkyl), CN, Cl, COO(C 1 -C 4 -alkyl), CON(C 1 -C 4 -alkyl) 2 or O(CH 2 ) 3 N ⁇ (CH 3 ) 2
  • Especially preferred compounds of formula (7) are those in which each of R 12 and R 13 is 2-cyano, 2-SO 3 M in which M is sodium or O(CH 2 ) 3 N ⁇ (CH 3 ) 2 An ⁇ in which An ⁇ is acetate.
  • R 14 independently, is H, C(CH 3 ) 3 , C(CH 3 ) 2 -phenyl, C 1 -C 4 -alkyl or COO-C 1 -C 4 -alkyl
  • Preferred coumarines are those of formula: in which R 18 is H, Cl or CH 2 COOH, R 19 is H, phenyl, COO-C 1 -C 4 -alkyl or a group formula: and R 20 is O-C 1 -C 4 -alkyl, N(C 1 -C 4 -alkyl) 2 , NH-CO-C 1 -C 4 -alkyl or a group of formula: or in which R 1 , R 2 , R 3 and R 4 have their previous significance and R 21 is H, C 1 -C 4 -alkyl or phenyl.
  • Especially preferred compounds of formula (10) are those having the formula: or
  • pyrazolines used are those having the formula: in which R 22 is H, CI or N(C 1 -C 4 -alkyl) 2 , R 23 is H, Cl, SO 3 M, SO 2 NH 2 , SO 2 NH-(C 1 -C 4 -alkyl), COO-C 1 -C 4 -alkyl, SO 2 -C 1 -C 4 -alkyl, SO 2 NHCH 2 CH 2 CH 2 N ⁇ (CH 3 ) 3 or SO 2 CH 2 CH 2 N ⁇ H(C 1 -C 4 -alkyl) 2
  • An ⁇ , R 24 and R 25 are the same or different and each is H, C 1 -C 4 -alkyl or phenyl and R 26 is H or Cl; and An ⁇ and M have their previous significance.
  • Especially preferred compounds of formula (13) are those in which R 22 is Cl, R 23 is SO 2 CH 2 CH 2 N ⁇ H(C 1 -C 4 -alkyl) 2 An ⁇ in which An ⁇ is phosphite and R 24 , R 25 and R 26 are each H; or those those having the formula: or
  • Preferred naphthalimides are those of formula: in which R 27 is C 1 -C 4 -alkyl or CH 2 CH 2 CH 2 N ⁇ (CH 3 ) 3 ; R 28 and R 29 , independently, are O-C 1 -C 4 -alkyl, SO 3 M or NH-CO-C 1 -C 4 -alkyl; and M has its previous significance.
  • Especially preferred compounds of formula (16) are those having the formula:
  • Preferred triazinyl-pyrenes used are those of formula: in which each R 30 , independently, is C 1 -C 4 -alkoxy.
  • Especially preferred compounds of formula (19) are those in which each R 30 is methoxy.
  • Preferred 2-styryl-benzoxazole- or -naphthoxazole derivatives are those having the formula: in which R 31 is CN, Cl, COO-C 1 -C 4 -alkyl or phenyl; R 32 and R 33 are the atoms required to form a fused benzene ring or R 33 and R 35 , independently, are H or C 1 -C 4 -alkyl; and R 34 is H, C 1 -C 4 -alkyl or phenyl.
  • Especially preferred compounds of formula (20) are those in which R 31 is a 4-phenyl group and each of R 32 to R 35 is H.
  • Preferred benzimidazole-benzofuran derivatives are those having the formula: in which R 36 is C 1 -C 4 -alkoxy; R 37 and R 38 , independently, are C 1 -C 4 -alkyl; and An ⁇ has its previous significance.
  • a particularly preferred compound of formula (21) is that in which R 36 is methoxy, R 37 and R 38 are each methyl and An(-) is methane sulfonate.
  • Preferred oxanilide derivatives include those having the formula: in which R 39 is C 1 -C 4 alkoxy, R 41 is C 1 -C 4 alkyl, C 1 -C 4 alkyl-SO 3 M or C 1 -C 4 alkoxy-SO 3 M in which M has its previous significance and R 40 and R 42 are the same and each is hydrogen, tert. butyl or SO 3 M in which M has its previous significance.
  • the fluorescent whitening agent when used in a composition which is a textile finishing bath, the fluorescent whitening agent may be in various formulations such as:
  • the C 1 -C 4 -alkyl groups of compounds of formulae (23) to (30) are, e.g., methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl.
  • Aryl groups are naphthyl or, especially, phenyl.
  • preferred fluorescent whitening agents for use in the present invention have a spectrum covering a relatively low wavelength range, that is exhibiting rather reddish shades.
  • fluorescent whitening agents include compounds of formula (23) in which R 43 and R 44 are each non-aromatic substituents.
  • R 43 and R 44 independendy, are NH-C 1 -C 4 -alkyl, O-C 1 -C 4 -alkyl or morpholino; as well as compounds of formula (26) in which n is 1.
  • Preferred compounds of formula (23) are those in which R 43 and R 44 , independently, are O-methyl, O-phenyl, NH 2 , NH-methyl, N(methyl) 2 , N(methyl)(hydroxyethyl), NH-ethyl, N(hydroxyethyl) 2 , NH-phenyl, S-methyl(phenyl), Cl or OH.
  • Preferred examples of compounds of formula (26) are those having the formulae:
  • Preferred examples of compounds of formula (27) are those of formulae:
  • a preferred example of a compound of formula (30) is that having the formula:
  • compositions comprising compound (48)
  • An(-) has its previous significance and is preferably the chloride, bromide, iodide, methosulfate, ethosulfate, benzenesulfonate or p-toluenesulfonate anion when R 58 is C 1 -C 4 -alkyl or
  • An(-) is preferably the formate, acetate, propionate or benzoate anion when R 58 is beta -hydroxy- gamma -chloropropyl, beta -cyanoethyl or C 1 -C 4 -alkoxy-carbonylethyl.
  • Preferred compounds of formula (48) are those in which Y is 1,4-phenylene or 4,4'-diphenylene; R 55 is hydrogen, methyl or cyano; R 56 and R 57 are each methyl or cyano; and R 58 and An(-) have their previously indicated preferred meanings.
  • One particularly preferred compound of formula (48) is that having the formula:
  • the compounds of formula (48) and their production are described in US-A-4 009 193.
  • Preferred compounds of formula (50) are those in which q is 1; R 55 is hydrogen, chlorine, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; Y 1 is (CH 2 ) 2 ; R 59 and R 60 are the same and each is methyl or ethyl; R 61 is methyl or ethyl; p is 1; and An(-) is CH 3 OSO 3 or C 2 H 5 OSO 3 .
  • Preferred cationic bistyrylphenyl fluorescent whitening agents of formula (51) are those in which R 55 is hydrogen, chlorine, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; R 62 and R 63 , independently, are C 1 -C 4 -alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R 64 is hydrogen, C 1 -C 4 -alkyl or C 3 -C 4 -alkenyl or R 62 , R 63 and R 64 , together with the nitrogen atom to which they are attached, form a pyridine ring; and Z is sulfur, -SO 2 -or -SO 2 NH-.
  • Preferred compounds of formula (52) are those in which q is 1;
  • R 55 is hydrogen, chlorine, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy;
  • R 62 and R 63 independently, are C 1 -C 4 -alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring;
  • R 64 is hydrogen, C 1 -C 4 -alkyl or C 3 -C 4 -alkenyl or R 62 , R 63 and R 64 , together with the nitrogen atom to which they are attached, form a pyridine ring.
  • Preferred compounds of formula (53) are those in which Z, is oxygen, a direct bond, -CONH-, -SO 2 NH or -COO-, especially oxygen; q is 1; R 62 is hydrogen, C 1 -C 4 -alkyl, methoxy or chlorine; and R 63 , R 64 , Y 1 and Q have their previous significance.
  • Z 2 is oxygen, -SO 2 - or -SO 2 N(R 69 )- in which R 69 is hydrogen or C 1 -C 4 -alkyl optionally substituted by hydroxyl, halogen or cyano; and R 66 and R 67 , independently, are C 1 -C 4 -alkyl optionally substituted by halogen, cyano, hydroxyl, C 1 -C 4 -alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl or C 2 -C 5 -alkoxycarbonyl.
  • Z 2 is oxygen, sulfur, -SO 2 -, -CON(R 69 )- or -SO 2 N(R 69 )- in which R 69 is hydrogen or C 1 -C 4 -alkyl optionally substituted by hydroxyl, halogen or cyano; and Y 2 is C 1 -C 4 -alkylene.
  • brightener radical B 1 has the formula: or the formula: each optionally substituted by one to four substituents selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -hydroxyalkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -cyanoalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl- C 1 -C 4 -alkyl, carboxy- C 1 -C 4 -alkyl, carb-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkenyl, C 5 -C 8 -cyaoalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkenoxy, C 1 -C 4 -alkoxycarbonyl, carbamoyl, cyano, C 1 -C
  • C 1 -C 4 -alkyl groups are, e.g., methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl.
  • Aryl groups are naphthyl or, especially, phenyl.
  • preferred compounds of formula (56) are those having the formula (31), (32) or (34), each as hereinbefore defined.
  • Preferred examples of compounds of formula (57) are those of formula (43), (44), (45) or (46), each as hereinbefore defined.
  • Preferred examples of compounds of formula (58) are those having the formula (40), (41) or (42), each as hereinbefore defined.
  • the fluorescent whitening agent is applied from a textile finishing composition
  • the co-use of the fluorescent whitening agent with a UV absorber is the co-use of the fluorescent whitening agent with a UV absorber.
  • the UV absorber used may be, e.g., an oxalic anilide, an o-hydroxybenzophenone, an o-hydroxyaryl-1,3,5-triazine, a sulphonated-1,3,5-triazine, an o-hydroxyphenylbenzotriazole, a 2-aryl-2H-benzotriazole, a salicylic acid ester, a substituted acrylonitrile, a substituted arylaminoethylene or a nitrilohydrazone.
  • UV absorbers for use in the: present invention are described, for example, in the US patent specifications 2 777 828, 2 853 521, 3 118 887, 3 259 627, 3 293 247, 3 382 183,3 403 183, 3 423 360, 4 127 586, 4 141903, 4 230 867, 4 675 352 and 4 698 064.
  • Preferred UV absorbers for use in the present invention include those of the benzo-triazine or benzo-triazole class.
  • benzo-triazine UV absorbers having the formula: in which R 82 and R 83 , independently, are hydrogen, hydroxy or C 1 -C 5 alkoxy.
  • a second preferred class of triazine UV absorbers is that having the formula: in which at least one of R 84 , R 85 and R 86 is a radical of formula: in which M has its previous significance; m is 1 or 2; and the remaining substituent(s) R 84 , R 85 and R 86 are, independently, amino, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, mono- or di-C 1 -C 12 alkylamino, phenyl, phenylthio, anilino or N-phenyl-N-C 1 -C 4 alkylamino, preferably N-phenyl-N-methylamino or N-phenyl-N-ethylamino, the respective phenyl substituents being optionally substituted by C 1 -C 12 alkyl or -alkoxy, C 5 -C 8 cycloalkyl or halogen.
  • a third preferred class of triazine UV absorbers is that having the formula: in which R 87 is hydrogen or hydroxy; R 88 , independently, are hydrogen or C 1 -C 4 alkyl; n 1 is 1 or 2; and B is a group of formula: in which n 2 is an integer from 2 to 6 and is preferably 2 or 3; Y 3 and Y 4 , independently, are C 1 -C 4 alkyl optionally substituted by halogen, cyano, hydroxy or C 1 -C 4 alkoxy or Y 3 and Y 4 , together with the nitrogen atom to which they are each attached, form a 5-7 membered heterocyclic ring, preferably a morpholine, pyrrolidine, piperidine or hexamethyleneimine ring; Y 5 is hydrogen, C 3 -C 4 alkenyl or C 1 -C 4 alkyl optionally substituted by cyano, hydroxy or C 1 -C 4 alkoxy or Y 3 , Y 4 and
  • triazole UV absorbers having the formula: in which T 1 is chlorine or, preferably, hydrogen; and T 2 is a random statistical mixture of at least three isomeric branched sec. C 8 -C 30 , preferably C 8- C 16 , especially C 9 -C 12 alkyl groups, each having the formula -CH(E 1 )(E 2 ) in which E 1 is a straight chain C 1 -C 4 alkyl group and E 2 is a straight chain C 4 -C 15 alkyl group, the total number of carbon atoms in E 1 and E 2 being from 7 to 29.
  • a second preferred class of triazole UV absorbers is that having the formula: in which M has its previous significance, but is preferably sodium, and T 3 is hydrogen, C 1 -C 12 alkyl or benzyl.
  • a third preferred class of triazole UV absorbers is that having the formula: in which B has its previous significance.
  • C 1 -C 12 alkyl groups R 84 , R 85 , R 86 and T 3 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.-butyl,n-amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl, methyl and ethyl being preferred, except in the case of T 3 for which isobutyl is preferred.
  • C 8 -C 30 alkyl groups T 2 include sec.octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and triacontyl groups.
  • C 1 -C 5 Alkoxy groups R 82 or R 83 may be, e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy or n-amyloxy, preferably methoxy or ethoxy, especially methoxy.
  • C 1 -C 12 Alkoxy groups R 84 , R 85 and R 86 include those indicated for the C 1 -C 5 alkoxy groups R 82 or R 83 together with, e.g., n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, n-nonoxy, n-decoxy, n-undecoxy and n-dodecoxy, methoxy and ethoxy being preferred.
  • C 1 -C 12 Alkylthio groups R 84 , R 85 and R 86 may be, e.g., methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert.-butylthio, n-amylthio, hexylthio, n-heptylthio, n-octylthio, isooctylthio, n-nonylthio, n-decylthio, n-undecylthio and n-dodecylthio, methylthio and ethylthio being preferred.
  • Mono- or di-alkylamino groups R 84 , R 85 and R 86 include, e.g., mono- or di-methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert.-butylamino, n-amylamino, n-hexylamino, n-heptylamino, n-octylamino, isooctylamino, n-nonylamino, n-decylamino, n-undecylamino and n-dodecylamino, mono- or di-methylamino or ethylamino being preferred.
  • the alkyl radicals in the mono-, di-, tri- or tetra-C 1 -C 4 alkylammonium groups M are preferably methyl.
  • Mono-, di- or tri-C 1 -C 4 hydroxyalkylammonium groups M are preferably those derived from ethanolamine, di-ethanolamine or tri-ethanolamine.
  • M is ammonium that is di- or tri-substituted by a mixture of C 1 -C 4 alkyl and C 1 -C 4 hydroxyalkyl groups, it is preferably N-methyl-N-ethanolamine or N,N-dimethyl-N-ethanolamine.
  • M is preferably, however, hydrogen or sodium.
  • Preferred compounds of formula (59) are those having the formulae:
  • the compounds of formula (59) are known and may be prepared e.g. by the method described in U.S. Patent 3 118 887.
  • Preferred compounds of formula (60) are those having the formula: in which R 89 and R 90 , independently, are C 1 -C 12 alkyl, preferably methyl; m is 1 or 2; M 1 is hydrogen, sodium, potassium, calcium, magnesium, ammonium or tetra-C 1 -C 12 alkylammonium, preferably hydrogen; and n 3 and n 4 , independently, are 0, 1 or 2, preferably 1 or 2.
  • Particularly preferred compounds of formula (73) are:
  • the compounds of formula (60) are known and may be prepared in the manner, e.g., described in US Patent 5 197 991.
  • the compounds of formula (63) are known and may be prepared in the manner, e.g., described in US Patent 4 675 352.
  • the compounds of formula (64) are known and may be prepared in the manner, e.g., described in EP-A-0 314 620.
  • the compounds of formula (65) are known and may be prepared in the manner, e.g., described in EP-A-0 357 545.
  • the use of the present invention is advantageously conducted in an aqueous medium in which the relevant fluorescent whitening agent is present in solution or as a fine dispersion.
  • some of the fluorescent whitening agents or UV absorbers for use in the method according to the present invention may be only sparingly soluble in water and may need to be applied in dispersed or emulsified 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.
  • the method of the present invention which is effected from a textile finishing composition, and depending on the type of fluorescent whitening agent 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 fluorescent whitening agent, or its emulsions in organic solvents may also be used in the method of the present invention.
  • solvent dyeing pad thermofix application
  • exhaust dyeing methods in dyeing machines may be used.
  • the fluorescent whitening agent 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.
  • the fluorescent whitening agent 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.
  • 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.
  • the preferred fluorescent whitening agent for use in the method according to the present invention will vary depending on the fibre from which the treated fabric is composed.
  • a fluorescent whitening agent of formula (1), (2), (4), (6) or (9) is preferably used; for polyester fabrics, a fluorescent whitening agent of formula (4), (5), (6), (7), (8), (10), (12), (19) or (20) is preferably used; for the treatment of polyamide, a fluorescent whitening agent of formula (1), (2), (4), (5), (6), (7), (8), (10), (11) or (20) is preferably used; for the treatment of polyacrylonitrile, a fluorescent whitening agent of formula (6), (9), (10), (11), (12) or (21) is preferably used; for wool or silk, a fluorescent whitening agent of formula (1), (2), (4), (6), (9), (10) or (11) is preferably used; and for polypropylene, a fluorescent whitening agent of formula (8) is preferably used.
  • the use according to the present invention is preferably effected by washing the textile fibre material at least once with the detergent composition, preferably at a temperature ranging from 10 to 100°C., especially from 15 to 60°C.
  • the detergent composition used preferably comprises:
  • the detergent may be formulated as a solid, as an aqueous liquid comprising 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in GB-A-2158454.
  • the anionic surfactant component may be, e.g., a sulphate, sulphonate or carboxylate surfactant, or a mixture of these.
  • Preferred sulphates are alkyl sulphates having 12-22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxy sulphates having 10-20 carbon atoms in the alkyl radical.
  • Preferred sulphonates include alkyl benzene sulphonates having 9-15 carbon atoms in the alkyl radical.
  • the cation is preferably an alkali metal, especially sodium.
  • Preferred carboxylates are alkali metal sarcosinates of formula R-CO(R 1 )CH 2 COOM 1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is C 1 -C 4 alkyl and M 1 is alkali metal.
  • the nonionic surfactant component may be, e.g., a condensate of ethylene oxide with a C 9 -C 15 primary alcohol having 3-8 moles of ethylene oxide per mole.
  • the builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.
  • Preferred silicates are crystalline layered sodium silicates of the formula NaHSi m O 2m+1 ⁇ pH 2 O or Na 2 Si m O 2m+1 ⁇ pH 2 O in which m is a number from 1.9 to 4 and p is 0 to 20.
  • aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.
  • Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
  • Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.
  • Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • any peroxide component may be any organic or inorganic peroxide compound, described in the literature or available on the market, which bleaches textiles at conventional washing temperatures, e.g. temperatures in the range of from 5°C. to 90°C.
  • the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest.
  • inorganic peroxides such as persulphate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides.
  • the peroxides, especially the inorganic peroxides are preferably activated by the inclusion of an activator such as tetraacetyl ethylenediamine or nonoyloxybenzene sulfonate.
  • Bleaching catalysts which may be added include, e.g., enzymatic peroxide precursors and/or metal complexes.
  • Preferred metal complexes are manganese or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A-0 509 787.
  • the detergents used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; enzymes, such as amylases; photobleaching agents; pigments; and/or shading agents.
  • auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; enzymes, such as amylases; photobleaching agents
  • the preferred fluorescent whitening agent for use in the detergent used according to the present invention will vary depending on the fibre from which the treated fabric is composed.
  • a fluorescent whitening agent of formula (28) is preferably used for the treatment of polyester fabrics from a detergent composition.
  • a fluorescent whitening agent of formula (28) is preferably used for the treatment of polyester fabrics from a detergent composition.
  • a fluorescent whitening agent of formula (29), (30) or (34) is preferably used for the treatment of polyamide.
  • a fluorescent whitening agent of formula (29), (30) or (37) is preferably used for wool.
  • the use in the present invention of a fluorescent whitening agent which absorbs radiation in the wavelength range 280-400 nm from a detergent composition has the following advantages: easier application since it exhausts on to the fibre; coloured textile goods can be washed with a detergent composition according to the claimed use (previously it was generally believed that FWAs had no useful role to play in detergents for coloured goods - see, e.g., A.E.Lee "Technology developments in laundry products", Proc. of the 3 rd World Conference on Detergents, Montreux, Sept.
  • the present invention provides, as a further aspect, a stable, concentrated fabric care composition
  • a stable, concentrated fabric care 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 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.
  • cationic fabric softening agents include imidazolines, quaternary ammonium compounds, ester amide amine salts, as well as mixtures thereof.
  • R 91 is hydrogen or methyl;
  • R 92 and An ⁇ have their previous significance
  • R 92 is C 14 -C 18 alkyl or C 14 -C 18 alkenyl
  • R 94 is C 14 -C 18 alkyl, C 14 -C 18 alkenyl, C 1 -C 4 alkyl, C 1 -C 4 halogenoalkyl or C 1 -C 4 hydroxyalkyl
  • Preferred anions An ⁇ 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.
  • One class of preferred quaternary ammonium compounds is that having the formula: in which R 98 is a C 8 -C 30 aliphatic residue, R 99 , R 100 , R 101 , R 102 and R 103 , independently, are hydrogen, C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl, An ⁇ has its previous significance, m 1 is an integer from 1 to 5 and n 2 has its previous significance.
  • Preferred compounds of formula (76) are those in which R 98 is C 12 -C 18 alkyl and R 99 , R 100 , R 101 , R 102 and R 103 , independently, are C 1 -C 4 alkyl, especially methyl.
  • the remaining groups R 104 are C 1 -C 4 alkyl, especially methyl or ethyl, or C 1 -C 4 hydroxyalkyl, especially hydroxymethyl or hydroxyethyl.
  • a preferred compound of formula (78) is: 3-stearoylamidopropyl-2-stearoyloxymethyl-methylamine hydrochloride.
  • the fabric care composition according to the present invention may also contain a minor proportion of one or more adjuvants.
  • 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 yet further aspect, 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.
  • 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 use according the present invention in addition to providing an improvement in the SPF of the treated textile material, may also increase the useful life of the textile material so treated, for example by preserving its tear strength and/or its lightfastness.
  • the present invention is further illustrated by the following Examples.
  • An aqueous textile finishing bath is made up having the composition:
  • the whiteness (GW) of the treated samples is 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 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.
  • samples of poplin (Supraluxe" ex Walser AG; density 0.62 g/cm 3 ; thickness 0.17 mm) are foularded (70 % liquor uptake) with the various finishing baths, at pH 4-5. Drying of the samples of poplin is effected for 3 minutes at 110°C. followed by thermofixing for 4 minutes at 150°C.
  • the whiteness (GW) and SPF of the respective treated samples are measured as before.
  • the respective treated poplin samples are washed ten times and the whiteness (GW) and SPF values are determined after the first, fifth and tenth washes.
  • the washing is conducted at 60°C. over 15 minutes.
  • the swatches are then rinsed under cold running tap water for 30 seconds and dried.
  • Foularding is conducted at alkaline pH.
  • Drying of the treated sample is carried out at 80°C. for 2 minutes.
  • the treated poplin has an SPF rating of above 40, whereas that of the untreated poplin is 4.
  • Foularding is conducted at a pH of 6-7.
  • Drying of the treated sample is carried out at 80°C. for 2 minutes, followed by thermofixing for 4 minutes at 150°C.
  • the treated poplin has an SPF rating of above 30, whereas that of the untreated poplin is 4.
  • the treated poplin is rinsed successively with hot or cold water and dried.
  • the treated poplin has an SPF rating of above 30, whereas that of the untreated poplin is 4.
  • the washing is conducted at 40°C. over 15 minutes.
  • the swatches are then rinsed under cold running tap water for 30 seconds and dried.
  • the wash treatment is repeated three times. After the third wash, the swatches are ironed at 160°C.
  • SPF values are the average of 3 measurements at various points on the swatches.
  • the relative variation of the results lies within a range of from about plus or minus 10%.
  • a bleached, mercerised cotton swatch is dyed by the exhaustion method using 0.95% by weight on the fabric of a commercial blue reactive dye.
  • the dyeing is conducted at a liquor ratio of 20: 1, the temperature is raised from 25° to 100°C. over 40 minutes, and then held for 1 hour at 100°C. with the addition of 15g/l of sodium sulphate, before applying a final cold rinse.
  • the SPF of the dyed goods is then determined by the method described in Examples 24 to 29.
  • the dyed goods are then washed in the manner described in Examples 24 to 29 using the same detergent composition.
  • the FWA compound used in the detergent is the compound of formula (40), at a level of 0.1 weight % of active substance, based on the weight of the detergent.
  • the SPF value of the washed goods and also of goods washed with the same detergent containing no FWA (for control purposes) is determined after 1, 3, 5 and 10 washes. The results are set out in the following Table 4.
  • the following rinse cycle softener base composition is made up:
  • amphoteric fluorescent whitening agent of formula:
  • the following rinse cycle softener base composition is made up:
  • 5g. of cotton fabric are first washed with 4g/l of ECE standard detergent using a liquor ratio of 1:20 at 60°C.
  • 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 5g/l.
  • the liquor ratio is 1:40 using tap water and the treatment is effected at 25°C. for 10 minutes.
  • the softener-treated goods are then spin-dried at 60°C.
  • 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 60°C. without being subjected to a rinse softener treatment.
  • the whiteness and SPF values of the re-washed, dried goods are measured.
  • Example Rinse Composition Conc. FWA Without re-wash With re-wash GW SPF GW SPF - control (no FWA) - 67 3 75 3 33 Rinse of Example 31 0.3 194 9 181 8 0.9 197 15 199 11 2.7 169 24 200 16 34 Rinse of Example 32 0.3 199 14 182 13 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.

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Description

  • The present invention relates to a use of a fluorescent whitening agent in a composition for improving the sun protection factor (SPF) of textile fibre material, wherein said fluorescent whitening agent absorbs radiation in the wavelength range 280-400 nm.
  • US-A-4 460 485 discloses fluorescent whitening agents, which are applied to textile fiber material. US-A-4 339 393 discloses distyrylbiphenyls as fluorescent whitening agents for textiles.
  • 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.
  • 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
  • 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/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 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 treating a textile fibre material with a fluorescent whitening agent which can also serve as a UV (ultra-violet) radiation absorber, namely one which absorbs radiation in the wavelength range 280-400 nm, in a composition, imparts an excellent sun protection factor to the fibre material so treated.
  • Accordingly, the present invention provides a use of a fluorescent whitening agent for improving the sun protection factor (SPF) of textile fibre material, wherein said fluorescent whitening agent absorbs radiation in the wavelength range 280-400 nm, in a composition, which is
  • a) an aqueous textile finishing composition;
    comprising at least one fluorescent whitening agent which is selected from the group consisting of bis-(triazinylamino)-stilbene-2,2'-disulfonic acid, 4,4'-bis-(triazol-2-yl)stilbene-2,2'-disulfonic acid, 4,4'-(diphenyl)-stilbenes, 4,4'-distyryl-biphenyl, 4-phenyl-4'-benzoxazolyl-stilbene, stilbenyl-naphthotriazoles, 4-styryl-stilbene, bis-(benzoxazol-2-yl) derivatives, bis-(benzimidazol-2-yl) derivative, coumarine, pyrazoline, naphthalimide, triazinyl-pyrene, 2-styryl-benzoxazole- or -naphthoxazole derivative, benzimidazole-benzofuran or oxanilide derivative, or
  • b) a detergent composition
    comprising at least one fluorescent whitening agent, which is selected from the group consiting of:
    Figure 00040001
    Figure 00040002
    Figure 00050001
    Figure 00050002
    Figure 00050003
    Figure 00060001
    Figure 00060002
    Figure 00060003
    in which R43 and R44, independently, are OH, NH2, O-C1-C4-alkyl, O-aryl, NH-C1-C4-alkyl, N(C1-C4-alkyl)2, N(C1-C4-alkyl)(C1-C4hydroxyalkyl), N(C1-C4-hydroxyalkyl)2, NH-aryl, morpholino, S-C1-C4-alkyl(aryl), Cl or OH; R45 and R46, independently, are H, C1-C4-alkyl. phenyl or a group of formula:
    Figure 00060004
    R47 is H, Cl or SO3M; R48 is CN, SO3M, S(C1-C4-alkyl)2 or S(aryl)2; R49 is H, SO3M, O-C1-C4-alkyl, CN, Cl, COO-C1-C4-alkyl, or CON(C1-C4-alkyl)2; R50 is H, C1-C4-alkyl, Cl or SO3M; R51 and R52, independently, are H, C1-C4-alkyl, SO3M, Cl or O-C1-C4-alkyl; R53 is H or C1-C4-alkyl; R54 is H, C1-C4-alkyl, CN, Cl, COO-C1-C4-alkyl, CON(C1-C4-alkyl)2, aryl or O-aryl;
    and
    M is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra- C1-C4-alkyl ammonium, mono-, di- or tri-C1-C4-hydroxyalkylammonium or ammonium that is di- or tri-substituted by a mixture of C1-C4-alkyl and C1-C4-hydroxyalkyl groups, and n is 0 or 1;
    or
  • c) a post-wash fabric care composition comprising at least a fluorescent whitening agent, wherein said fluorescent whitening agent is a cationic bistyrylphenyl fluorescent whitening agent of formula:
    Figure 00070001
    • in which Y is arylene, optionally substituted by chloro, methyl or methoxy; q is 1 or 2; R55 is hydrogen, chloro, C1-C4-alkyl, C1-C4-alkoxy, cyano or C1-C4-alkoxycarbonyl; R56 and R57 are C1-C4-alkyl, chloroethyl, methoxyethyl, beta -ethoxyethyl, beta -acetoxyethyl or beta -cyanoethyl, benzyl or phenylethyl; R58 is C1-C4-alkyl, C2-C3-hydroxyalkyl, beta -hydroxy- gamma -chloropropyl, beta - cyanoethyl or C1-C4-alkoxy-carbonylethyl; and An(-) is an anion of an organic or inorganic acid; or, a cationic bistyrylphenyl fluorescent whitening agent of formula:
    Figure 00070002
    in which R55 and q have their previous significance and Y1 is C2-C4-alkylene or hydroxypropylene; R59, is C1-C4-alkyl or, together with R60 and the nitrogen to which they are each attached, R59 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R60 is C1-C4-alkyl or, together with R59 and the nitrogen to which they are each attached, R60 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R61 is hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C1-C4-alkoxycarbonylmethyl, benzyl, C2-C4-hydroxyalkyl, C2-C4-cyanoalkyl or, together with R59 and R60 and the nitrogen atom to which they are each attached, R61 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; p is 0 or 1; and An(-) is an anion of an organic or inorganic acid; or,
    a bistyrylphenyl fluorescent whitening agent of formula:
    Figure 00080001
    in which R55, Y1, p and q have their previous significance and An(-) is an anion of an organic or inorganic acid; and R62 and R63, independently, are C1-C4-alkyl or C2-C3-alkenyl or R62 and R63, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R64 is hydrogen, C1-C4-alkyl or C2-C3-alkenyl or R62, R63 and R64, 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-, or, in which the cationic bistyrylphenyl fluorescent whitening agent has the formula:
    Figure 00080002
    in which R55, R62, R63, R64, Y1, p and q have their previous significance and An(-) is an anion of an organic or inorganic acid; or, a amphoteric styrene fluorescent whitening agent offormula:
    Figure 00080003
    in which R55, R62, R63, Y1 and q have their previous significance and Z, is oxygen, sulfur, a direct bond, -COO-, -CON(R65)- or -SO2N(R65)- in which R65 is hydrogen, C1-C4-alkyl or cyanoethyl and Q is -COO-or -SO3, and,
    in which the amine oxide fluorescent whitening agent has the formula:
    Figure 00090001
    in which q has its previous significance and B is a brightener radical selected from a 4,4'-distyrylbiphenyl, 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, 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-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;Z2 is a direct bond between B and Y2, an oxygen atom, a sulfur atom, -SO2-,-SO2-O-, -COO-, -CON(R68)- or -SO2N(R68)- in which R68 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 R66 and R67, independently, are C5-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, or, a cationic fluorescent whitening agent of formula:
    Figure 00100001
    in which q and Y2 have their previous significance, and B1 is a brightener radical; Z3 is a direct bond, -SO2-C2-C4-alkyleneoxy, -SO2-C2-C4-alkylene-COO-, -SO2-, -COO-, -SO2-C2-C4-alkylene-CON(R75)-or -SO2N(R75)- in which R75 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; R70 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy, or R70 is benzyl, optionally substituted by halogen, C1-C4-alkyl or C1-C4-alkoxy, or R70, together with R71 or Z3, forms a pyrrolidine, piperidine or morpholine radical;R71 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-:alkylcarbonyloxy, or R71 is benzyl, optionally substituted by halogen , C1-C4-alkyl or C1-C4-alkoxy, or R71, together with R70, forms a pyrrolidine, piperidine or morpholine radical; R72 is C1-C4-alkyl; R73 is hydrogen or
    C1-C4-alkyl, optionally substituted by cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy; and R74 is C1-C4-alkyl or,
    wherein said fluorescent whitening agent is a bis(triazinyl)diaminostilbene anionic fluorescent whitening agent of formula:
    Figure 00100002
    or a dibenzofumylbiphenyl anionic fluorescent whitening agent of formula:
    Figure 00110001
    and
    or an anionic bistyrylphenyl fluorescent of formula:
    Figure 00110002
    in which R76 is phenyl optionally substituted by one or two SO3M groups and R77 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; R70 is H, C1-C4-alkyl, CN, CI or SO3M; R79 and R80, independently, are H, C1-C4-alkyl, SO3M, CN, CI or O- C1-C4-alkyl, provided that at least two of R78, R79 and R80 are SO3M and the third group has solubilising character; R81 is H, SO3M, O- C1-C4-alkyl, CN, CI, COO- C1-C4-alkyl, or CON(C1-C4-alkyl)2; and r is 0 or 1, and M has its previous significance.
  • The textile fibre material treated according to the use of the present invention may be composed of a wide variety of natural or synthetic fibres, e.g., wool, polyamide, cotton, polyester, polyacrylic, silk, polypropylene or mixtures thereof, preferably cotton.
  • The textile fibre material may be in the form of endless filaments (stretched or unstretched), staple fibres, flocks, hanks, textile filament yams, threads, nonwovens, felts, waddings, flocked structures or woven textile or bonded textile fabrics or knitted fabrics.
  • The amount of fluorescent whitening agent present in the composition used according to the use of the present invention may vary within a wide range, e.g. from 0.005 to 20 %, based on the weight of the textile fibre material, depending on the particular composition used in the used of the present invention. Thus, when the composition is an aqueous textile finishing composition, the amount of fluorescent whitening agent present in the composition preferably ranges from 0.01 to 3%, especially from 0.05 to 1%, based on the weight of the textile fibre material. When the composition is a detergent composition, the amount of fluorescent whitening agent present in the composition preferably ranges from 0.005 to 2%, especially from 0.01 to 1%, based on the weight of the textile fibre material. When the composition is a post-wash fabric care composition, the amount of fluorescent whitening agent present in the composition preferably ranges from 0.1 to 20%, especially from 1 to 10%, based on the weight of the textile fibre material.
  • With particular reference to the use of a fluorescent whitening agent in a composition which is an aqueous textile finishing composition, preferred 4,4'-bis-(triazinylamino)-stilbene-2,2'-disulfonic acids are those having the formula:
    Figure 00130001
    in which R1 and R2, independently, are phenyl, mono- or disulfonated phenyl, phenylamino, mono- or disulfonated phenylamino, morpholino, N(CH2CH2OH)2, -N(CH3)(CH2CH2OH), -NH2, -N(C1-C4alkyl)2, -OCH3, -Cl, -NH-CH2CH2SO3H or NH-CH2CH2OH; and M is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra- C1-C4-alkylammonium, mono-, di- or tri- C1-C4-hydroayalkylarnmonium or ammonium that is di- or tri-substituted with by a mixture of C1-C4-alkyl and C1-C4-hydroxyalkyl groups.
  • Especially preferred compounds of formula (1) are those in which each R1 is 2,5-disulfophenyl and each R2 is morpholino; or each R1 is 2,5-disulfophenyl and each R2 is N(CH2CH2); or each R1 is 3-sulfophenyl and each R2 is NH(CH2CH2OH) or N(CH2CH2OH)2; or each R1 is 4-sulfophenyl and each R2 is N(CH2CH2OH)2; and, in each case, the sulfo group is SO3M in which M is sodium.
  • Preferred 4,4'-bis-(triazol-2-yl)stilbene-2,2'-disulfonic acids are those having the formula:
    Figure 00130002
    in which R3 and R4, independently, are H, C1-C4-alkyl, phenyl or monosulfonated phenyl; and M has its previous significance.
  • Especially preferred compounds of formula (2) are those in which R3 is phenyl, R4 is H and M is sodium.
  • One preferred 4,4'-(diphenyl)-stilbene is that having the formula:
    Figure 00140001
  • Preferably, 4,4'-distyryl-biphenyls used are those of formula:
    Figure 00140002
    in which R5 and R6, independently, are H, SO3M, SO2N(C1-C4-alkyl)2, O-(C1-C4-alkyl), CN, Cl, COO(C1-C4-alkyl), CON(C1-C4-alkyl)2 or O(CH2)3N⊕(CH3)2An⊖ in which An⊖ is an anion of an organic or inorganic acid, in particular a formate, acetate, propionate, glycolate, lactate, acrylate, methanephosphonate, phosphite, dimethyl or diethyl phosphite anion , or a mixture thereof; and n is 0 or 1.
  • Especially preferred compounds of formula (4) are those in which n is 1 and each R5 is a 2-SO3M group in which M is sodium and each R6 is H, or each R5 is O(CH2)3N⊕(CH3)2An⊖ in which An⊖ is acetate.
  • Preferred 4-phenyl-4'-benzoxazolyl-stilbenes have the formula:
    Figure 00140003
    in which R7 and R8, independently, are H, Cl, C1-C4-alkyl or SO2-C1-C4-alkyl.
  • An especially preferred compound of formulae (5) is that in which R7 is 4-CH3 and R8 is 2-CH3.
  • Preferably, stilbenyl-naphthotriazoles used are those of formula:
    Figure 00150001
    in which R9 is H or Cl; R10 is SO3M, SO2N(C1-C4-alkyl)2, SO2O-phenyl or CN; R11 is H or SO3M; and M has its previous significance.
  • Especially preferred compounds of formula (6) are those in which R9 and R11 are H and R10 is 2-SO3M in which M is Na.
  • Preferably, 4-styryl-stilbenes used are those of formula:
    Figure 00150002
    in which R12 and R13, independently, are H, SO3M, SO2N(C1-C4-alkyl)2, O-(C1-C4-alkyl), CN, Cl, COO(C1-C4-alkyl), CON(C1-C4-alkyl)2 or O(CH2)3N⊕(CH3)2An⊖ in which An⊖ is an anion of an organic or inorganic acid, in particular a formate, acetate, propionate, glcolate, lactate, acrylate, methanephosphonate, phosphite, dimethyl or diethyl phosphite anion, or a mixture thereof.
  • Especially preferred compounds of formula (7) are those in which each of R12 and R13 is 2-cyano, 2-SO3M in which M is sodium or O(CH2)3N⊕(CH3)2An⊖ in which An⊖ is acetate.
  • Preferred bis-(benzoxazol-2-yl) derivatives are those of formula:
    Figure 00160001
    in which R14, independently, is H, C(CH3)3, C(CH3)2-phenyl, C1-C4-alkyl or COO-C1-C4-alkyl, and X is -CH=CH- or a group of formula:
    Figure 00160002
    Figure 00160003
    Especially preferred compounds of formula (8) are those in which each R14 is H and X is
    Figure 00160004
    or one group R14 in each ring is 2-methyl and the other R14 is H and X is -CH=CH-; or one group R14 in each ring is 2-C(CH3)3 and the other R14 is H and X is
    Figure 00160005
  • Preferred bis-(benzimidazol-2-yl) derivatives are those of formula:
    Figure 00160006
    in which R15 and R16, independently, are H, C1-C4-alkyl or CH2CH2OH; R17 is H or SO3M; X1 is -CH=CH- or a group of formula:
    Figure 00170001
    and M has its previous significance.
  • Especially preferred compounds of formula (9) are those in which R15 and R16 are each H, R17 is SO3M in which M is sodium and X1 is -CH=CH-.
  • Preferred coumarines are those of formula:
    Figure 00170002
    in which R18 is H, Cl or CH2COOH, R19 is H, phenyl, COO-C1-C4-alkyl or a group formula:
    Figure 00170003
    and R20 is O-C1-C4-alkyl, N(C1-C4-alkyl)2, NH-CO-C1-C4-alkyl or a group of formula:
    Figure 00170004
    or
    Figure 00170005
    in which R1, R2, R3 and R4 have their previous significance and R21 is H, C1-C4-alkyl or phenyl.
  • Especially preferred compounds of formula (10) are those having the formula:
    Figure 00180001
    or
    Figure 00180002
  • Preferably, pyrazolines used are those having the formula:
    Figure 00180003
    in which R22 is H, CI or N(C1-C4-alkyl)2, R23 is H, Cl, SO3M, SO2NH2, SO2NH-(C1-C4-alkyl), COO-C1-C4-alkyl, SO2-C1-C4-alkyl, SO2NHCH2CH2CH2N⊕(CH3)3 or SO2CH2CH2N⊕H(C1-C4-alkyl)2 An⊖, R24 and R25 are the same or different and each is H, C1-C4-alkyl or phenyl and R26 is H or Cl; and An⊖ and M have their previous significance.
  • Especially preferred compounds of formula (13) are those in which R22 is Cl, R23 is SO2CH2CH2N⊕H(C1-C4-alkyl)2 An⊖ in which An⊖ is phosphite and R24, R25 and R26 are each H; or those those having the formula:
    Figure 00190001
    or
    Figure 00190002
  • Preferred naphthalimides are those of formula:
    Figure 00190003
    in which R27 is C1-C4-alkyl or CH2CH2CH2N⊕(CH3)3; R28 and R29, independently, are O-C1-C4-alkyl, SO3M or NH-CO-C1-C4-alkyl; and M has its previous significance.
  • Especially preferred compounds of formula (16) are those having the formula:
    Figure 00190004
    Figure 00190005
  • Preferred triazinyl-pyrenes used are those of formula:
    Figure 00200001
    in which each R30, independently, is C1-C4-alkoxy.
  • Especially preferred compounds of formula (19) are those in which each R30 is methoxy.
  • Preferred 2-styryl-benzoxazole- or -naphthoxazole derivatives are those having the formula:
    Figure 00200002
    in which R31 is CN, Cl, COO-C1-C4-alkyl or phenyl; R32 and R33 are the atoms required to form a fused benzene ring or R33 and R35, independently, are H or C1-C4-alkyl; and R34 is H, C1-C4-alkyl or phenyl.
  • Especially preferred compounds of formula (20) are those in which R31 is a 4-phenyl group and each of R32 to R35 is H.
  • Preferred benzimidazole-benzofuran derivatives are those having the formula:
    Figure 00200003
    in which R36 is C1-C4-alkoxy; R37 and R38, independently, are C1-C4-alkyl; and An⊖ has its previous significance.
  • A particularly preferred compound of formula (21) is that in which R36 is methoxy, R37 and R38 are each methyl and An(-) is methane sulfonate.
  • Preferred oxanilide derivatives include those having the formula:
    Figure 00210001
    in which R39 is C1-C4alkoxy, R41 is C1-C4alkyl, C1-C4alkyl-SO3M or C1-C4alkoxy-SO3M in which M has its previous significance and R40 and R42 are the same and each is hydrogen, tert. butyl or SO3M in which M has its previous significance.
  • When a fluorescent whitening agent is used in a composition which is a textile finishing bath, the fluorescent whitening agent may be in various formulations such as:
  • a) in mixtures with dyes (shading) or pigments, especially white pigments;
  • b) in mixtures with carriers, wetting agents, antioxidants, e.g., sterically hindered amines, UV absorbers and/or chemical bleaching agents; or
  • c) in admixture with crosslinking or finishing agents (such as starch or synthetic finishes), and in combination with a wide variety of textile finishing processes, especially synthetic resin finishes, e.g. creaseproof finishes (wash-and-wear, permanent press or non-iron), as well as flameproof finishes, soft handle finishes, antisoiling finishes, antistatic finishes or antimicrobial finishes.
  • With refernce to the use of a fluorescent whitening agent in a detergent composition the C1-C4-alkyl groups of compounds of formulae (23) to (30) are, e.g., methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl. Aryl groups are naphthyl or, especially, phenyl.
  • It will be appreciated that the protection afforded to the wearer of the textile material, washed according to this detergent composition aspect of the use of the invention, will last longer when a fluorescent whitening agent is used which has a high lightfastness.
  • Furthermore, preferred fluorescent whitening agents for use in the present invention have a spectrum covering a relatively low wavelength range, that is exhibiting rather reddish shades. Examples of such fluorescent whitening agents include compounds of formula (23) in which R43 and R44are each non-aromatic substituents. such as compounds of formula (23) in which R43 and R44, independendy, are NH-C1-C4-alkyl, O-C1-C4-alkyl or morpholino; as well as compounds of formula (26) in which n is 1.
  • Preferred compounds of formula (23) are those in which R43 and R44, independently, are O-methyl, O-phenyl, NH2, NH-methyl, N(methyl)2, N(methyl)(hydroxyethyl), NH-ethyl, N(hydroxyethyl)2, NH-phenyl, S-methyl(phenyl), Cl or OH.
  • Specific examples of preferred compounds of formula (23) are those having the formulae:
    Figure 00230001
    Figure 00230002
    Figure 00230003
    Figure 00240001
    Figure 00240002
    Figure 00240003
  • Specific preferred examples of compounds of formula (24) are those of formulae:
    Figure 00240004
    Figure 00250001
    Figure 00250002
    in which n has its previous significance.
  • Preferred examples of compounds of formula (26) are those having the formulae:
    Figure 00250003
    Figure 00250004
    Figure 00250005
  • Preferred examples of compounds of formula (27) are those of formulae:
    Figure 00260001
    Figure 00260002
    Figure 00260003
    Figure 00260004
  • A preferred example of a compound of formula (30) is that having the formula:
    Figure 00260005
  • The compounds of formulae (23) to (30) are known and may be obtained by known methods.
  • In the post-wash care compositions comprising compound (48) An(-) has its previous significance and is preferably the chloride, bromide, iodide, methosulfate, ethosulfate, benzenesulfonate or p-toluenesulfonate anion when R58 is C1-C4-alkyl or An(-) is preferably the formate, acetate, propionate or benzoate anion when R58 is beta -hydroxy- gamma -chloropropyl, beta -cyanoethyl or C1-C4-alkoxy-carbonylethyl.
  • Preferred compounds of formula (48) are those in which Y is 1,4-phenylene or 4,4'-diphenylene; R55 is hydrogen, methyl or cyano; R56 and R57 are each methyl or cyano; and R58 and An(-) have their previously indicated preferred meanings.
  • One particularly preferred compound of formula (48) is that having the formula: The compounds of formula (48) and their production are described in US-A-4 009 193.
    Figure 00280001
  • Preferred compounds of formula (50) are those in which q is 1; R55 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; Y1 is (CH2)2; R59 and R60 are the same and each is methyl or ethyl; R61 is methyl or ethyl; p is 1; and An(-) is CH3OSO3 or C2H5OSO3.
  • The compounds of formula (50) and their production are described in US-A-4 339 393.
  • Preferred cationic bistyrylphenyl fluorescent whitening agents of formula (51) are those in which R55 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; R62 and R63, independently, are C1-C4-alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R64 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl or R62, R63 and R64, 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 (51) and their production are described in US-A-4 486 352.
  • Preferred compounds of formula (52) are those in which q is 1; R55 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; R62 and R63, independently, are C1-C4-alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R64 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl or R62, R63 and R64, together with the nitrogen atom to which they are attached, form a pyridine ring.
  • The compounds of formula (52) and their production are described in US-A-4 602 087.
  • Preferred compounds of formula (53) are those in which Z, is oxygen, a direct bond, -CONH-, -SO2NH or -COO-, especially oxygen; q is 1; R62 is hydrogen, C1-C4-alkyl, methoxy or chlorine; and R63, R64, Y1 and Q have their previous significance.
  • The compounds of formula (53) and their production are described in US-A-4 478 598.
  • Preferred is compound of formula (53), in which the brightener radicals B are those having the formula:
    Figure 00320001
    in which q has its previous significance and the rings are optionally substituted as indicated above.
  • Preferably Z2 is oxygen, -SO2- or -SO2N(R69)- in which R69 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; and R66 and R67, 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 (52) are those in which Z2 is oxygen, sulfur, -SO2-, -CON(R69)- or -SO2N(R69)- in which R69 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; and Y2 is C1-C4-alkylene.
  • The compounds of formula (54) and their production are described in US-A-4 539 161.
  • Preferably, brightener radical B1 has the formula:
    Figure 00330001
    or the formula:
    Figure 00330002
    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- C1-C4-alkyl, carboxy- C1-C4-alkyl, carb-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkenyl, C5-C8-cyaoalkyl, 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 (55) and their production are described in GB-A-2 023 605.
  • In the compounds of formulae (56) to (58), C1-C4-alkyl groups are, e.g., methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl. Aryl groups are naphthyl or, especially, phenyl.
  • Specific examples of preferred compounds of formula (56) are those having the formula (31), (32) or (34), each as hereinbefore defined.
  • Preferred examples of compounds of formula (57) are those of formula (43), (44), (45) or (46), each as hereinbefore defined.
  • Preferred examples of compounds of formula (58) are those having the formula (40), (41) or (42), each as hereinbefore defined.
  • The compounds of formulae (56) to (58) are known and may be obtained by known methods.
  • With respect to that aspect of the use of the present invention in which the fluorescent whitening agent is applied from a textile finishing composition, of particular interest is the co-use of the fluorescent whitening agent with a UV absorber.
  • The UV absorber used may be any of the wide range of known UV absorbers, that is organic compounds which readily absorb UV light, especially in the range lambda =280 to 400 nm, and which convert the absorbed energy, by a chemical intermediate reaction, into non-interfering, stable compounds or into non-interfering forms of energy. If the textile finishing composition is used in combination with a rinse cycle fabric softener composition, the absorber used should, of course, be compatible with the rinse cycle fabric softener composition. In such instances, 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.
  • The UV absorber used may be, e.g., an oxalic anilide, an o-hydroxybenzophenone, an o-hydroxyaryl-1,3,5-triazine, a sulphonated-1,3,5-triazine, an o-hydroxyphenylbenzotriazole, a 2-aryl-2H-benzotriazole, a salicylic acid ester, a substituted acrylonitrile, a substituted arylaminoethylene or a nitrilohydrazone.
  • Such known UV absorbers for use in the: present invention are described, for example, in the US patent specifications 2 777 828, 2 853 521, 3 118 887, 3 259 627, 3 293 247, 3 382 183,3 403 183, 3 423 360, 4 127 586, 4 141903, 4 230 867, 4 675 352 and 4 698 064.
  • Preferred UV absorbers for use in the present invention include those of the benzo-triazine or benzo-triazole class.
  • One preferred class of benzo-triazine UV absorbers is that having the formula:
    Figure 00360001
    in which R82 and R83, independently, are hydrogen, hydroxy or C1-C5alkoxy.
  • A second preferred class of triazine UV absorbers is that having the formula:
    Figure 00360002
    in which at least one of R84, R85 and R86 is a radical of formula:
    Figure 00360003
    in which M has its previous significance; m is 1 or 2; and the remaining substituent(s) R84, R85 and R86 are, independently, amino, C1-C12alkyl, C1-C12alkoxy, C1-C12alkylthio, mono- or di-C1-C12alkylamino, phenyl, phenylthio, anilino or
    N-phenyl-N-C1-C4alkylamino, preferably N-phenyl-N-methylamino or
    N-phenyl-N-ethylamino, the respective phenyl substituents being optionally substituted by C1-C12alkyl or -alkoxy, C5-C8cycloalkyl or halogen.
  • A third preferred class of triazine UV absorbers is that having the formula:
    Figure 00370001
    in which R87 is hydrogen or hydroxy; R88, independently, are hydrogen or C1-C4alkyl; n1 is 1 or 2; and B is a group of formula:
    Figure 00370002
    in which n2 is an integer from 2 to 6 and is preferably 2 or 3; Y3 and Y4, independently, are C1-C4alkyl optionally substituted by halogen, cyano, hydroxy or C1-C4alkoxy or Y3 and Y4, together with the nitrogen atom to which they are each attached, form a 5-7 membered heterocyclic ring, preferably a morpholine, pyrrolidine, piperidine or hexamethyleneimine ring; Y5 is hydrogen, C3-C4alkenyl or C1-C4alkyl optionally substituted by cyano, hydroxy or C1-C4alkoxy or Y3, Y4 and Y5, together with the nitrogen atom to which they are each attached, form a pyridine or picoline ring; and X1 ⊖ is a colourless anion, preferably CH3OSO3 ⊖ or C2H5OSO3 ⊖.
  • One preferred class of triazole UV absorbers is that having the formula:
    Figure 00370003
    in which T1 is chlorine or, preferably, hydrogen; and T2 is a random statistical mixture of at least three isomeric branched sec. C8-C30, preferably C8-C16, especially C9-C12alkyl groups, each having the formula -CH(E1)(E2) in which E1 is a straight chain C1-C4alkyl group and E2 is a straight chain C4-C15alkyl group, the total number of carbon atoms in E1 and E2 being from 7 to 29.
  • A second preferred class of triazole UV absorbers is that having the formula:
    Figure 00380001
    in which M has its previous significance, but is preferably sodium, and T3 is hydrogen, C1-C12alkyl or benzyl.
  • A third preferred class of triazole UV absorbers is that having the formula:
    Figure 00380002
    in which B has its previous significance.
  • In the compounds of formulae (59) to (65), C1-C12alkyl groups R84, R85, R86 and T3 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.-butyl,n-amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl, methyl and ethyl being preferred, except in the case of T3 for which isobutyl is preferred. C8-C30alkyl groups T2 include sec.octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and triacontyl groups.
  • C1-C5Alkoxy groups R82 or R83 may be, e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy or n-amyloxy, preferably methoxy or ethoxy, especially methoxy. C1-C12Alkoxy groups R84, R85 and R86 include those indicated for the C1-C5alkoxy groups R82 or R83 together with, e.g., n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, n-nonoxy, n-decoxy, n-undecoxy and n-dodecoxy, methoxy and ethoxy being preferred.
  • C1-C12Alkylthio groups R84, R85 and R86 may be, e.g., methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert.-butylthio, n-amylthio, hexylthio, n-heptylthio, n-octylthio, isooctylthio, n-nonylthio, n-decylthio, n-undecylthio and n-dodecylthio, methylthio and ethylthio being preferred.
  • C1-C12Mono- or di-alkylamino groups R84, R85 and R86 include, e.g., mono- or di-methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert.-butylamino, n-amylamino, n-hexylamino, n-heptylamino, n-octylamino, isooctylamino, n-nonylamino, n-decylamino, n-undecylamino and n-dodecylamino, mono- or di-methylamino or ethylamino being preferred.
  • The alkyl radicals in the mono-, di-, tri- or tetra-C1-C4alkylammonium groups M are preferably methyl. Mono-, di- or tri-C1-C4hydroxyalkylammonium groups M are preferably those derived from ethanolamine, di-ethanolamine or tri-ethanolamine. When M is ammonium that is di- or tri-substituted by a mixture of C1-C4alkyl and C1-C4hydroxyalkyl groups, it is preferably N-methyl-N-ethanolamine or N,N-dimethyl-N-ethanolamine. M is preferably, however, hydrogen or sodium.
  • Preferred compounds of formula (59) are those having the formulae:
    Figure 00390001
    Figure 00400001
    Figure 00400002
    Figure 00400003
  • The compounds of formula (59) are known and may be prepared e.g. by the method described in U.S. Patent 3 118 887.
  • Preferred compounds of formula (60) are those having the formula:
    Figure 00410001
    in which R89 and R90, independently, are C1-C12alkyl, preferably methyl; m is 1 or 2; M1 is hydrogen, sodium, potassium, calcium, magnesium, ammonium or tetra-C1-C12alkylammonium, preferably hydrogen; and n3 and n4, independently, are 0, 1 or 2, preferably 1 or 2.
  • Particularly preferred compounds of formula (73) are:
  • 2,4-diphenyl-6-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl]-1,3,5-triazine;
  • 2-phenyl-4,6-bis-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)- phenyl] -1,3,5-triazine;
  • 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl] -1,3,5-triazine; and
  • 2,4-bis(4-methylphenyl)-6-[2-hydroxy-4-(2-hydroxy-3-sulfo propoxy)-phenyl] -1,3,5-triazine.
  • The compounds of formula (60) are known and may be prepared in the manner, e.g., described in US Patent 5 197 991.
  • The compounds of formula (63) are known and may be prepared in the manner, e.g., described in US Patent 4 675 352.
  • The compounds of formula (64) are known and may be prepared in the manner, e.g., described in EP-A-0 314 620.
  • The compounds of formula (65) are known and may be prepared in the manner, e.g., described in EP-A-0 357 545.
  • The use of the present invention is advantageously conducted in an aqueous medium in which the relevant fluorescent whitening agent is present in solution or as a fine dispersion.
  • Although most are readily water-soluble, some of the fluorescent whitening agents or UV absorbers for use in the method according to the present invention may be only sparingly soluble in water and may need to be applied in dispersed or emulsified 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 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 diphenyloxidedisulphonic acid derivatives with formaldehyde.
  • With particular reference to that aspect of the method of the present invention which is effected from a textile finishing composition, and depending on the type of fluorescent whitening agent 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 fluorescent whitening agent, 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.
  • In certain cases, the fluorescent whitening agent 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 fluorescent whitening agent 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.
  • The preferred fluorescent whitening agent for use in the method according to the present invention will vary depending on the fibre from which the treated fabric is composed.
  • Thus, in relation to that aspect of the present invention in which the fluorescent whitening agent is applied from a textile finishing composition, there is preferably used, for the treatment of cotton fabrics, a fluorescent whitening agent of formula (1), (2), (4), (6) or (9) is preferably used; for polyester fabrics, a fluorescent whitening agent of formula (4), (5), (6), (7), (8), (10), (12), (19) or (20) is preferably used; for the treatment of polyamide, a fluorescent whitening agent of formula (1), (2), (4), (5), (6), (7), (8), (10), (11) or (20) is preferably used; for the treatment of polyacrylonitrile, a fluorescent whitening agent of formula (6), (9), (10), (11), (12) or (21) is preferably used; for wool or silk, a fluorescent whitening agent of formula (1), (2), (4), (6), (9), (10) or (11) is preferably used; and for polypropylene, a fluorescent whitening agent of formula (8) is preferably used.
  • In relation to that aspect of the present invention in which the fluorescent whitening agent is applied from a detergent composition, the use according to the present invention is preferably effected by washing the textile fibre material at least once with the detergent composition, preferably at a temperature ranging from 10 to 100°C., especially from 15 to 60°C.
  • The detergent composition used preferably comprises:
  • i) 5-90%, preferably 5-70% of an anionic surfactant and/or a nonionic surfactant;
  • ii) 5-70%, preferably 5-40% of a builder;
  • iii) 0-30%, preferably 1-12% of a peroxide;
  • iv) 0-10%, preferably 1-6% of a peroxide activator and/or 0-1%, preferably 0.1-3% of a bleaching catalyst;
  • v) 0.005-2%, preferably 0.01-1% of at least one fluorescent whitening agent which absorbs radiation in the wavelength range 280-400 nm; and
  • vi) 0.005-10%, preferably 0.1-5% of of one or more auxiliaries, each by weight, based on the total weight of the detergent.
  • The detergent may be formulated as a solid, as an aqueous liquid comprising 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in GB-A-2158454.
  • The anionic surfactant component may be, e.g., a sulphate, sulphonate or carboxylate surfactant, or a mixture of these.
  • Preferred sulphates are alkyl sulphates having 12-22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxy sulphates having 10-20 carbon atoms in the alkyl radical.
  • Preferred sulphonates include alkyl benzene sulphonates having 9-15 carbon atoms in the alkyl radical.
  • In each case, the cation is preferably an alkali metal, especially sodium.
  • Preferred carboxylates are alkali metal sarcosinates of formula R-CO(R1)CH2COOM1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4 alkyl and M1 is alkali metal.
  • The nonionic surfactant component may be, e.g., a condensate of ethylene oxide with a C9-C15 primary alcohol having 3-8 moles of ethylene oxide per mole.
  • The builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.
  • Preferred silicates are crystalline layered sodium silicates of the formula NaHSimO2m+1·pH2O or Na2SimO2m+1·pH2O in which m is a number from 1.9 to 4 and p is 0 to 20.
  • Preferred aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.
  • Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
  • Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.
  • Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • Any peroxide component may be any organic or inorganic peroxide compound, described in the literature or available on the market, which bleaches textiles at conventional washing temperatures, e.g. temperatures in the range of from 5°C. to 90°C. In particular, the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest. It is preferred, however, to employ very active inorganic peroxides, such as persulphate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides. The peroxides, especially the inorganic peroxides, are preferably activated by the inclusion of an activator such as tetraacetyl ethylenediamine or nonoyloxybenzene sulfonate. Bleaching catalysts which may be added include, e.g., enzymatic peroxide precursors and/or metal complexes. Preferred metal complexes are manganese or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A-0 509 787.
  • The detergents used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; enzymes, such as amylases; photobleaching agents; pigments; and/or shading agents. These constituents should, of course, be stable to any bleaching system employed.
  • The preferred fluorescent whitening agent for use in the detergent used according to the present invention will vary depending on the fibre from which the treated fabric is composed.
  • Thus, for the treatment of polyester fabrics from a detergent composition, a fluorescent whitening agent of formula (28) is preferably used. For the treatment of polyamide, a fluorescent whitening agent of formula (29), (30) or (34) is preferably used. For wool, a fluorescent whitening agent of formula (29), (30) or (37) is preferably used
  • Relative to the use of a conventional UV absorber, the use in the present invention of a fluorescent whitening agent which absorbs radiation in the wavelength range 280-400 nm from a detergent composition has the following advantages: easier application since it exhausts on to the fibre; coloured textile goods can be washed with a detergent composition according to the claimed use (previously it was generally believed that FWAs had no useful role to play in detergents for coloured goods - see, e.g., A.E.Lee "Technology developments in laundry products", Proc. of the 3rd World Conference on Detergents, Montreux, Sept. 1994, AOCS Press, p.73, § "Color variants"); the UV protection is regularly renewed on washing; yellowing of the textile material caused by o-hydroxy groups in the UV absorber is avoided; minor amounts of the fluorescent whitening agent provide very high extinction values; the textile material is more wash resistant; and higher SPF values are attainable.
  • With respect to that aspect of the method of the present invention in which the fluorescent whitening agent is applied to the textile fibre material via a post-wash fabric care composition, the present invention provides, as a further aspect, a stable, concentrated fabric care 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 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.
  • 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:
    Figure 00470001
    in which R91 is hydrogen or C1-C4alkyl; R92 is a C8-C30aliphatic residue; R93 is -C2H4-O(C=O)-R92 or -C2H4-NH(C=O)-R92; and An(-) has its previous significance.
  • Preferably R91 is hydrogen or methyl; R92 is C14-C18alkyl or C14-C18alkenyl; and R93 is -C2H4-O(C=O)-C14-C18alkyl or -C14-C18alkenyl, or -C2H4-NH(C=O)-C14-C18alkyl or -C14-C18alkenyl.
  • Other preferred imidazoline cationic fabric softening agents are those having the formula:
    Figure 00480001
    in which R92 and An⊖ have their previous significance; R94 and R95, independently, are a C8-C30aliphatic residue, C1-C4alkyl, C1-C4halogenoalkyl, C1-C4hydroxyalkyl or a group -C2H4-N(R96-C(=O)R97 in which R96 is hydrogen or C8-C30alkyl and R97 is hydrogen or C1-C4alkyl.
  • Preferably R92 is C14-C18alkyl or C14-C18alkenyl; R94 is C14-C18alkyl, C14-C18alkenyl, C1-C4alkyl, C1-C4halogenoalkyl or C1-C4hydroxyalkyl; and R95 is a group -C2H4-N(R96)-C(=O)-R97 in which R96 and R97 have their previous significance.
  • Preferred anions An⊖ 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 (74) include:
  • 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-talow-1-methyl-3-(2-stearoylamidoethyl)-imidazoline sulfate and
  • 2-tallow-1 -methyl-3-(2-stearoylamidoethyl)-imidazoline methosulfate.
  • Specific examples of preferred compounds of formula (75) 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)-imidazolinium-chloride
  • 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:
    Figure 00490001
    in which R98 is a C8-C30aliphatic residue, R99, R100, R101, R102 and R103, independently, are hydrogen, C1-C4alkyl or C1-C4hydroxyalkyl, An⊖ has its previous significance, m1 is an integer from 1 to 5 and n2 has its previous significance.
  • Preferred compounds of formula (76) are those in which R98 is C12-C18alkyl and R99, R100, R101, R102 and R103, independently, are C1-C4alkyl, especially methyl.
  • Specific examples of preferred compounds of formula (76) are:
  • 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-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:
    Figure 00500001
    in which An⊖ has its previous significance and the groups R104 may be the same or different and each is a C1-C30aliphatic residue, C1-C4hydroxyalkyl, C2H4OC(=O)-R92, C2H4NHC(=O)-R92 or CH2CH[OC(=O)-R92][CH2OC(=O)-R92], in which R92 has its previous significance, provided that at least one group R104, and preferably two groups R104 are C14-C30alkyl, C2H4OC(=O)-C14-C30alkyl, C2H4NHC(-O)-C14-C30alkyl or CH2CH[OC(=O)-C14-C30alkyl][CH2OC(=O)-C14-C30alkyl]. Preferably, the remaining groups R104 are C1-C4alkyl, especially methyl or ethyl, or C1-C4hydroxyalkyl, especially hydroxymethyl or hydroxyethyl.
  • Specific examples of preferred compounds of formula (77) are:
  • distearyldimethylammonium chloride
  • dilauryldimethylammonium chloride
  • dihexadecyldimethylammonium chloride
  • distearyldimethylammonium 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:
    Figure 00500002
    in which R104 has its previous significance and An1 ⊖ is an inorganic or organic acid from which an anion An⊖ is derived, wherein An⊖ has its previous significance, provided that at least one group R104, and preferably two groups R104 are C14-C30alkyl, (CH2)nOC(=O)-C14-C30alkyl, (CH2)n2NHC(=O)-C14-C30alkyl or CH2CH[OC(=O)-C14-C30alkyl][CH2OC-C14-C30 alkyl, which n2 has its previous significance. Preferably, the remaining groups R104 are C1-C4alkyl, especially methyl or ethyl, or C1-C4hydroxyalkyl, especially hydroxymethyl or hydroxyethyl.
  • A preferred compound of formula (78) is:
    3-stearoylamidopropyl-2-stearoyloxymethyl-methylamine hydrochloride.
  • In addition to the fluorescent whitening agent, the fabric care 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 yet further aspect, 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 use according the present invention, in addition to providing an improvement in the SPF of the treated textile material, may also increase the useful life of the textile material so treated, for example by preserving its tear strength and/or its lightfastness.
  • The present invention is further illustrated by the following Examples.
    • A) Application of a fluorescent whitening agent from a textile treatment composition. Examples 1 to 10
  • An aqueous textile finishing bath is made up having the composition:
  • 2 g/l acetic acid (40%);
  • 40 g/l of an alkyl-modified dihydroxyethyleneurea/melamine-formaldehyde derivative;
  • 12 g/l MgCl2; and
  • 30 g/l of an emulsion of fatty acid amides.
  • To separate samples of this bath are added, in the amounts shown in the following Table one or more of the following active substances (AS):
    Figure 00530001
    Figure 00530002
    Figure 00540001
  • Separate samples of bleached, mercerised cotton (poplin) of density 0.68 g/cm3 and thickness 0.20 mm, are then foularded (70 % liquor uptake) with the various finishing baths, at pH 4-5. Drying of the samples of cotton is effected for 3 minutes at 110°C. followed by thermofixing for 4 minutes at 150°C.
  • The whiteness (GW) of the treated samples is 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 1.
    Example AS Concentration of AS GW SPF
    g/l in bath % on substrate
    - - - - 62 1.9
    - UVA 10 0.35 57 11.2
    - UVA 20 0.70 53 17.3
    - UVA 30 1.05 34 17.4
    1 UVA 10 0.35 175 15.8
    FWA-1 10 0.13
    2 UVA 20 0.70 171 16.5
    FWA-1 10 0.13
    3 UVA 10 0.35 177 18.0
    FWA-1 20 0.25
    4 UVA 10 0.35 167 18.3
    FWA-2 8 0.14
    5 UVA 20 0.70 134 21.7
    FWA-2 8 0.14
    6 UVA 10 0.35 178 15.9
    FWA-2 16 0.28
    7 FWA-1 10 0.13 227 11.7
    8 FWA-1 20 0.25 229 15.2
    9 FWA-2 8 0.14 223 13.0
    10 FWA-2 16 0.28 215 13.2
  • The results in the Table 1 demonstrate clearly the improvement in the SPF value of a substrate treated according to the method of the present invention.
    • Examples 11 to 20
  • Using the general procedure described in Examples 1 to 10, samples of poplin ("Supraluxe" ex Walser AG; density 0.62 g/cm3; thickness 0.17 mm) are foularded (70 % liquor uptake) with the various finishing baths, at pH 4-5. Drying of the samples of poplin is effected for 3 minutes at 110°C. followed by thermofixing for 4 minutes at 150°C.
  • The whiteness (GW) and SPF of the respective treated samples are measured as before.
  • In order to evaluate the wash permanency of the textile treatment applied, the respective treated poplin samples are washed ten times and the whiteness (GW) and SPF values are determined after the first, fifth and tenth washes.
  • 50g of the poplin swatches are washed in 1 litre of tap water (12° German hardness) containing 4g of a detergent having the following 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
    x% fluorescent whitening agent (FWA) by weight on detergent Water to 100%.
  • The washing is conducted at 60°C. over 15 minutes. The swatches are then rinsed under cold running tap water for 30 seconds and dried.
  • The results are set out in the following Table 2.
    Ex. AS Concentration of AS GW after washing SPF after washing
    g/l in bath % on sub. 0x 1x 5x 10x 0x 1x 5x 10x
    - - - - 63 71 75 76 4 5 5 5
    - UVA 10 0.35 59 70 69 72 25 18 13 11
    - UVA 20 0.70 55 67 68 71 47 31 30 19
    - UVA 30 1.05 58 68 72 72 81 45 47 30
    - UVA 40 1.40 52 65 70 70 99 46 50 37
    11 UVA
    FWA-1    		 10
    10    		 0.35
    0.13    		 176 152 133 133 57 19 13 10
    12 UVA
    FWA-1    		 20
    10    		 0.70
    0.13    		 147 123 109 108 67 39 24 16
    13 UVA
    FWA-1    		 10
    20    		 0.35
    0.25    		 203 193 160 155 51 19 13 13
    14 UVA
    FWA-2    		 10
    8    		 0.35
    0.14    		 178 178 171 166 41 2 17 19
    15 UVA
    FWA-2    		 20
    8    		 0.70
    0.14    		 149 141 138 136 82 62 34 29
    16 UVA
    FWA-2    		 10
    16    		 0.35
    0.28    		 198 210 208 208 59 26 16 18
    17 FWA-1 10 0.13 222 205 197 178 24 9 8 7
    18 FWA-1 20 0.25 236 227 203 209 31 13 6 7
    19 FWA-2 8 0.14 216 215 216 206 31 19 16 10
    20 FWA-2 16 0.28 226 239 233 235 42 19 13 16
  • The results in Table 2 demonstrate clearly the improvement in the SPF value of a substrate treated according to the method of the present invention and, moreover, that the use of a combination of UVA and FWA leads to unexpected synergistic SPF values.
    • Example 21
  • A 5 g. sample of poplin ("Supraluxe" ex Walser AG; density 0.62 g/cm3) is foularded (80% liquor uptake) with an aqueous bath containing:
  • 4 g/l sodium bicarbonate and
  • 12.5 g/l of a fluorescent whitening agent having the formula:
    Figure 00580001
    • to provide a concentration of 1% by weight of active substance on the poplin substrate.
  • Foularding is conducted at alkaline pH.
  • Drying of the treated sample is carried out at 80°C. for 2 minutes.
  • The treated poplin has an SPF rating of above 40, whereas that of the untreated poplin is 4.
    • Example 22
  • A 5 g. sample of poplin ("Supraluxe" ex Walser AG; density 0.62 g/cm3) is foularded (80% liquor uptake) with an aqueous bath containing:
  • 2 g/l acetic acid (40%)
  • 40 g/l of an alkyl-modified dihydroxyethyleneurea/melamine-formaldehyde derivative;
  • 12 g/l MgCl2;
  • 30 g/l of an emulsion of fatty acid amides and
  • 12.5 g/l of a fluorescent whitening agent having the formula:
    Figure 00590001
    to provide a concentration of 1% by weight of active substance on the poplin substrate.
  • Foularding is conducted at a pH of 6-7.
  • Drying of the treated sample is carried out at 80°C. for 2 minutes, followed by thermofixing for 4 minutes at 150°C.
  • The treated poplin has an SPF rating of above 30, whereas that of the untreated poplin is 4.
    • Example 23
  • A 5 g. sample of poplin ("Supraluxe" ex Walser AG; density 0.62 g/cm3) is treated with an aqueous bath containing:
  • 3 g/l anhydrous sodium sulfate
  • 3 g/l caustic soda flake
  • 1.5 g/l nonylphenol ethoxylate (7 mols EO) and
  • 1% by weight of poplin fabric of a fluorescent whitening agent having the formula:
    Figure 00600001
    • the treatment is conducted at 95°C. over 30 minutes and at a liquor ratio of 40:1, using a laboratory dyeing machine.
  • The treated poplin is rinsed successively with hot or cold water and dried.
  • The treated poplin has an SPF rating of above 30, whereas that of the untreated poplin is 4.
    • B) Application of a fluorescent whitening agent from a detergent composition. Examples 24 to 29
  • 50g of bleached, mercerised cotton swatches are washed in 1 litre of tap water (12° German hardness) containing 4g of a detergent having the following 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
    x% fluorescent whitening agent (FWA) by weight on detergent
    Water to 100%.
  • The washing is conducted at 40°C. over 15 minutes. The swatches are then rinsed under cold running tap water for 30 seconds and dried. The wash treatment is repeated three times. After the third wash, the swatches are ironed at 160°C.
  • The results obtained are set out in the following Table 3.
    Example FWA Concentration FWA W SPF
    - - - 79 1.6
    24 Compound (31) 0.2% 211 6.1
    25 Compound (32) 0.2% 202 3.9
    26 Compound (36) 0.2% 200 5.2
    27 Compound (37) 0.1% 207 4.2
    28 Compound (40) 0.1% 201 3.4
    29 Compound (45) 0.1% 208 3.1
  • SPF values are the average of 3 measurements at various points on the swatches. The relative variation of the results lies within a range of from about plus or minus 10%.
  • Compared with the control experiment (no FWA), the SPF values obtained to the invention are 2-4 times higher, after only 3 washes.
    • Example 30
  • A bleached, mercerised cotton swatch is dyed by the exhaustion method using 0.95% by weight on the fabric of a commercial blue reactive dye. The dyeing is conducted at a liquor ratio of 20: 1, the temperature is raised from 25° to 100°C. over 40 minutes, and then held for 1 hour at 100°C. with the addition of 15g/l of sodium sulphate, before applying a final cold rinse.
  • The SPF of the dyed goods is then determined by the method described in Examples 24 to 29.
  • The dyed goods are then washed in the manner described in Examples 24 to 29 using the same detergent composition. The FWA compound used in the detergent is the compound of formula (40), at a level of 0.1 weight % of active substance, based on the weight of the detergent. The SPF value of the washed goods and also of goods washed with the same detergent containing no FWA (for control purposes) is determined after 1, 3, 5 and 10 washes. The results are set out in the following Table 4.
    Example number of washes SPF
    without fwa with fwa
    - control pre-wash 23.7 23.7
    30 one 22.5 23.8
    three 22.0 25.9
    five 20.9 26.9
    ten 19.8 28.7
  • The results in Table 4 demonstrate that the SPF of dyed fabrics can decrease significantly when the fabrics are washed with a detergent which does not contain an FWA. By contrast, washing with a detergent containing a compound of formula (40) not only eliminates this loss of protection against aggressive sunlight radiation, but also actually increases the SPF protection with successive washings.
    • C) Application of a fluorescent whitening agent from a rinse composition. Example 31
  • 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:
    Figure 00630001
    • Example 32
  • 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:
    Figure 00630002
    • Examples 33 and 34
  • 5g. of cotton fabric are first washed with 4g/l of ECE standard detergent using a liquor ratio of 1:20 at 60°C. 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 5g/l. The liquor ratio is 1:40 using tap water and the treatment is effected at 25°C. for 10 minutes. The softener-treated goods are then spin-dried at 60°C.
  • 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 60°C. without being subjected to a rinse softener treatment. The whiteness and SPF values of the re-washed, dried goods are measured.
  • The results are shown in the following Table 5.
    Example Rinse Composition Conc. FWA Without re-wash With re-wash
    GW SPF GW SPF
    - control (no FWA) - 67 3 75 3
    33 Rinse of Example 31 0.3 194 9 181 8
    0.9 197 15 199 11
    2.7 169 24 200 16
    34 Rinse of Example 32 0.3 199 14 182 13
    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 Table 5 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 31 or 32 is replaced by a compound having one of the following formulae:
    Figure 00650001
    Figure 00650002
    Figure 00650003
    Figure 00650004
    Figure 00650005
    Figure 00650006
    Figure 00660001

Claims (9)

  1. Use of a fluorescent whitening agent for improving the sun protection factor (SPF) of textile fibre material, wherein said fluorescent whitening agent absorbs radiation in the wavelength range 280-400 nm, in a composition which is
    a) an aqueous textile finishing composition;
    comprising at least one fluorescent whitening agent which is selected from the group consiting of :4,4'-bis-(triazinylamino)-stilbene-2,2'-disulfonic acid, 4,4'-bis-(triazol-2-yl)stilbene-2,2'-disulfonic acid, 4,4'-(diphenyl)-stilbenes, 4,4'-distyryl-biphenyl, 4-phenyl-4'-benzoxazolyl-stilbene, stilbenyl-naphthotriazoles, 4-styryl-stilbene, bis-(benzoxazol-2-yl) derivatives, bis-(benzimidazol-2-yl) derivative, coumarine, pyrazoline, naphthalimide, triazinyl-pyrene, 2-styryl-benzoxazole- or -naphthoxazole derivative, benzimidazole-benzofuran or oxanilide derivative, or
    b) a detergent composition
    comprising at least one fluorescent whitening agent, which is selected from the group consiting of:
    Figure 00670001
    Figure 00670002
    Figure 00680001
    Figure 00680002
    Figure 00680003
    Figure 00690001
    Figure 00690002
    Figure 00690003
    in which R43 and R44, independently, are OH, NH2, O-C1-C4-alkyl, O-aryl, NH-C1-C4-alkyl, N(C1-C4-alkyl)2, N(C1-C4-alkyl)(C1-C4hydroxyalkyl), N(C1-C4-hydroxyalkyl)2, NH-aryl, morpholino, S-C1-C4-alkyl(aryl), Cl or OH; R45 and R46, independently, are H, C1-C4-alkyl, phenyl or a group of formula:
    Figure 00690004
    R47 is H, Cl or SO3M; R48 is CN, SO3M, S(C1-C4-alkyl)2 or S(aryl)2; R49 is H, SO3M, O-C1-C4-alkyl, CN, Cl, COO-C1-C4-alkyl, or CON(C1-C4-alkyl)2; R50 is H, C1-C4-alkyl, Cl or SO3M; R5, and R52, independently, are H, C1-C4-alkyl, SO3M, Cl or O-C1-C4-alkyl; R53 is H or C1-C4-alkyl; R54 is H, C1-C4-alkyl, CN, Cl, COO-C1-C4-alkyl, CON(C1-C4-alkyl)2, aryl or O-aryl;
    and
    M is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra- C1-C4-alkyl ammonium, mono-, di- or tri- C1-C4-hydroxyalkylammonium or ammonium that is di- or tri-substituted by a mixture of C1-C4-alkyl and C1-C4-hydroxyalkyl groups, and n is 0 or 1;
    or
    c) a post-wash fabric care composition comprising at least a fluorescent whitening agent,
    wherein said fluorescent whitening agent is a cationic bistyrylphenyl fluorescent whitening agent of formula:
    Figure 00700001
    in which Y is arylene, optionally substituted by chloro, methyl or methoxy; q is 1 or 2; R55 is hydrogen, chloro, C1-C4-alkyl, C1-C4-alkoxy, cyano or C1-C4-alkoxycarbonyl; R56 and R57 are C1C4-alkyl, chloroethyl, methoxyethyl, beta -ethoxyethyl, beta -acetoxyethyl or beta - cyanoethyl, benzyl or phenylethyl; R58 is C1-C4-alkyl, C2-C3-hydroxyalkyl, beta -hydroxy- gamma -chloropropyl, beta -cyanoethyl or C1-C4-alkoxy-carbonylethyl; and An(-) is an anion of an organic or anionic acid; or,
    a cationic bistyrylphenyl fluorescent whitening agent of formula:
    Figure 00700002
    in which R55 and q have their previous significance and Y1 is C2-C4-alkylene or hydroxypropylene; R59 is C1-C4-alkyl or, together with R60 and the nitrogen to which they are each attached, R59 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R60 is C1-C4-alkyl or, together with R59 and the nitrogen to which they are each attached, R60 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R61 is hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C1-C4-akoxycarbonylmethyl, benzyl, C2-C4-hydroxyalkyl, C2-C4-cyanoalkyl or, together with R59 and R60 and the nitrogen atom to which they are each attached, R61 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring, and p is 0 or 1 and An(-) is an anioin of an organic or inorganic acid; or,
    a bistyrylphenyl fluorescent whitening agent of formula:
    Figure 00710001
    in which R55, Y1, p and q have their previous significance and An(-) is an anioin of an organic or inorganic acid, and R62 and R63, independently, are C1-C4-alkyl or C2-C3-alkenyl or R62 and R63, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R64 is hydrogen, C1-C4-alkyl or C2-C3-alkenyl or R62. R83 and R64, 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-, or, in which the cationic bistyrylphenyl fluorescent whitening agent has the formula:
    Figure 00710002
    in which R55, R62, R63, R64, Y1, p and q have their previous significance and An(-) is an anioin of an organic or inorganic acid; or, a amphoteric styrene fluorescent whitening agent offormula:
    Figure 00720001
    in which R55, R62, R63, Y1, and q have their previous significance and An(-) is an anioin of an organic or inorganic acid; Z1 is oxygen, sulfur, a direct bond, -COO-, -CON(R65)- or -SO2N(R65)- in which R65 is hydrogen, C1-C4-alkyl or cyanoethyl; and Q is -COO-or -SO3, and, in which the amine oxide fluorescent whitening agent has the formula:
    Figure 00720002
    in which in which q has its previous significance and B is a brightener radical selected from a 4,4'-distyrylbiphenyl, 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, 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-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;Z2 is a direct bond between B and Y2, an oxygen atom, a sulfur atom, -SO2-, -SO2-O-, -COO-, -CON(R68)- or -SO2N(R68)- in which R68 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 R66 and R67, independently, are C5-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, or,
    a cationic fluorescent whitening agent of formula:
    Figure 00730001
    in which Y2 and q have their previous significance and B1 is brightener radical; Z3 is a direct bond, -SO2-C2-C4-alkyleneoxy, -SO2-C2-C4-alkylene-COO-, -SO2, -COO-, -SO2-C2-C4-alkylene-CON(R75)- or -SO2N(R75)- in which R75 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; R70 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy, or R70 is benzyl, optionally substituted by halogen, C1-C4-alkyl or C1-C4-alkoxy, or R70, together with R71 or Z3, forms a pyrrolidine, piperidine or morpholine radical;R71 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy, or R71 is benzyl, optionally substituted by halogen, C1-C4-alkyl or C1-C4-alkoxy, or R71, together with R70, forms a pyrrolidine, piperidine or morpholine radical; R72 is C1-C4-alkyl; R73 is hydrogen or
    C1-C4-alkyl, optionally substituted by cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy; and R74 is C1-C4-alkyl, or,
    wherein said fluorescent whitening agent is a bis(triazinyl)diaminostilbene anionic fluorescent whitening agent of formula:
    Figure 00740001
    or a dibenzofuranylbiphenyl anionic fluorescent whitening agent of formula:
    Figure 00740002
    and or an anionic bistyrylphenyl fluorescent of formula:
    Figure 00740003
    in which R76 is phenyl optionally substituted by one or two SO3M groups and R77 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; R70 is H, C1-C4-alkyl, CN, Cl or SO3M; R79 and R80, independently, are H, C1-C4-alkyl, SO3M, CN, Cl or O- C1-C4-alkyl, provided that at least two of R78, R79 and R80 are SO3M and the third group has solubilising character; R81 is H, SO3M, O- C1-C4-alkyl, CN, Cl, COO- C1-C4-alkyl, or CON(C1-C4-alkyl)2; and r is 0 or 1 and M has its previous significance.
  2. Use according to claim 1, in which the composition is an aqueous textile finishing composition and the amount of fluorescent whitening agent present in the composition ranges from 0.01 to 3%; or the composition is a detergent composition and the amount of fluorescent whitening agent present in the composition ranges from 0.005 to 2%.
  3. Use according to claim 1, in which the composition is an aqueous textile finishing composition and the fluorescent whitening agent used is a the 4,4'-bis-(triazinylamino)-stilbene-2,2'-disulfonic acid is one having the formula:
    Figure 00750001
    in which R1 and R2, independently, are phenyl, mono- or disulfonated phenyl, phenylamino, mono- or disulfonated phenylamino, morpholino, -N(CH2CH2OH)2, -N(CH3)(CH2CH2OH), -NH2, -N(C1-C4-alkyl)2, -OCH3, -Cl, -NH-CH2CH2SO3H or -NH-CH2CH2OH; and M 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-subsiituted with by a mixture of C1-C4-alkyl and C1-C4-hydroxyalkyl groups, and,
    in which the 4,4'-bis-(triazol-2-yl)stilbene-2,2'-disulfonic acid is one having the formula:
    Figure 00750002
    in which R3 and R4, independently, are H, C1-C4-alkylphenyl or monosulfonated phenyl, and, in which the 4,4'-(diphenyl)-stilbene is one having the formula:
    Figure 00750003
    and,
    in which the 4,4'-distyryl-biphenyl used has the formula:
    Figure 00760001
    in which R5 and R6, independently, are H, SO3M, SO2N(C1-C4-alkyl)2, O-(C1-C4-alkyl), CN, Cl, COO(C1-C4-alkyl), CON(C1-C4-alkyl)2 or O(CH2)3N(+)(CH3)2An(-), in which An(-) is an anion of an organic or inorganic acid; and n is 0 or 1, or in which the 4-phenyl-4'-benzoxazolylstilbene has the formula:
    Figure 00760002
    in which R7 and R8, independently, are H, Cl, C1-C4-alkyl or SO2-C1-C4-alkyl, and,
    in which a stilbenyl-naphthotriazole used is one of formula
    Figure 00760003
    in which R9 is H or Cl; R10 is SO3M, SO2N(C1-C4-alkyl)2, SO2O-phenyl or CN; R11 is H or SO3M, and in which a 4-styryl-stilbene used is one of formula:
    Figure 00770001
    in which R12 and R13, independently, are H, SO3M, SO2N(C1-C4-alkyl)2, O-(C1-C4-alkyl), CN, Cl, COO(C1-C4-alkyl), CON(C1-C4-alkyl)2 or O(CH2)3N(+)(CH3)2An(-), and
    in which a bis-(benzoxazol-2-yl) derivative used having the formula:
    Figure 00770002
    in which R14, independently, is H, C(CH3)3, C(CH3)2-phenyl, C1-C4-alkyl or COO-C1-C4-alkyl, and X is -CH=CH- or a group of formula:
    Figure 00770003
    Figure 00770004
    and in which a bis-(benzimidazol-2-yl) derivatives is used of formula:
    Figure 00780001
    in which R15 and H16, independently, are H, C1-C4-alkylor CH2CH2OH, R17 is H or SO3M; X1 is - CH =CH- or a group of formula:
    Figure 00780002
    and in which a coumarine is used of formula:
    Figure 00780003
    in which R18 is H, Cl or CH2COOH, R19 is H, phenyl, COO-C1-C4-alkyl or a group of formula:
    Figure 00780004
    and R20 is O-C1-C4-alkyl, N(C1-C4-alkyl)2, NH-CO-C1-C4-alkyl or a group of formula:
    Figure 00790001
    or
    Figure 00790002
    in which R21 is H, C1-C4-alkyl or phenyl, and,
    in which a pyrazoline used is one having the formula:
    Figure 00790003
    in which R22 is H, Cl or N(C1-C4-alkyl)2, R23 is H, Cl, SO3M, SO2NH2, SO2NH-(C1-C4-alkyl), COO-C1-C4-alkyl, SO2C1-C4-alkyl, SO2NHCH2CH2CH2N(+)(CH3)3 or SO2CH2CH2N(+)H(C1-C4-alkyl)2 An(-), R24 and R25 are the same or different and each is H, C1-C4-alkyl or phenyl and R26 is H or Cl; and
    in which a naphthalimide is used of formula:
    Figure 00790004
    in which R27 is C1-C4-alkyl or CH2CH2CH2N(+)(CH3)3; R28 is O- C1-C4-alkyl, SO3M or NH-CO-C1-C4-alkyl;and,
    in which a triazinyl-pyrene is used of formula:
    Figure 00800001
    in which each R29, independently, is C1-C4-alkoxy, and
    in which a 2-styryl-benzoxazole- or -naphthoxazole derivative is used having the formula:
    Figure 00800002
    in which R31 is CN, Cl, COO-C1-C4-alkyl or phenyl; R32 and R33 are the atoms required to form a fused benzene ring or R33 and R35, independently, are H or C1-C4-alkyl; and R34 is H, C1-C4-alkyl or phenyl, and,
    in which a benzimidazole-benzofuran derivative is used having the formula:
    Figure 00800003
    in which R36 is C1-C4-alkoxy; R37 and R38, independently, are C1-C4-alkyl
    and in which an oxanilide derivative is used having the formula:
    Figure 00810001
    in which R39is C1-C4alkoxy, R41 is C1-C4alkyl, C1-C4alkyl-SO3M or C1-C4alkoxy -SO3M iand R40 and R42 are the same and each is hydrogen, tert. butyl or SO3M.
  4. Use according to any of claim 1, in which the composition is a textile finishing composition and the fluorescent whitening agent is used:
    a) in mixtures with dyes (shading) or pigments;
    b) in mixtures with carriers, wetting agents, antioxidants, UV absorbers and/or chemical bleaching agents; or
    c) in admixture with crosslinking or finishing agents or in combination with a textile finishing process or flameproof finish, soft handle finish, antisoiling finish, antistatic finish or antimicrobial finish.
  5. Use according to claim 1, in which the compound of formula (23) has the formula:
    Figure 00810002
    Figure 00810003
    Figure 00820001
    Figure 00820002
    Figure 00820003
    Figure 00820004
    or
    in which the compound of formula (24) has the formula:
    Figure 00830001
    Figure 00830002
    Figure 00830003
    in which n is as defined in claim 1;
    in which the compound of formula (26) has the formula:
    Figure 00840001
    Figure 00840002
    Figure 00840003
    or
    in which the compound of formula (27) has the formula:
    Figure 00850001
    Figure 00850002
    Figure 00850003
    Figure 00850004
    or
    in which the compound of formula (30) has the formula:
    Figure 00850005
  6. Use according to claim 1, in which the compound of formula (56) has the formula (31), (32) or (34), or in which the compound of formula (57) has the formula (43), (44), (45) or (46), or in which the compound of formula (58) has the formula (40), (41) or (42), each as defined in claim 5.
  7. Use according to claim 1, wherein the used composition is a detergent composition comprising:
    i) 5-90% of an anionic surfactant and/or a nonionic surfactant;
    ii) 5-70% of a builder;
    iii) 0-30% of a peroxide;
    iv) 0-10% of a peroxide activator and/or 0-1% of a bleaching catalyst;
    v) 0.005-2% of at least one fluorescent whitening agent which absorbs radiation in the wavelength range 280-400 nm; and
    vi) 0.005-10% of one or more auxiliaries, each by weight, based on the total weight of the detergent.
  8. A stable, concentrated rinse cycle fabric softener composition comprising 2 to 25 % by weight of a fabric softener agent, and >0.3 to 10 % by weight of a fluorescent whitening agent which is compatible with the fabric softener agent, each based on the total weight of the composition, the remainder being substantially water.
  9. Process 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.
EP95810288A 1994-05-12 1995-05-03 Textile treatment Expired - Lifetime EP0682145B1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB9409466A GB9409466D0 (en) 1994-05-12 1994-05-12 Textile treatment
GB9409465A GB9409465D0 (en) 1994-05-12 1994-05-12 Protective use
GB9409466 1994-05-12
GB9409465 1994-05-12
GB9413270 1994-07-01
GB9413270A GB9413270D0 (en) 1994-07-01 1994-07-01 Textile treatment

Publications (3)

Publication Number Publication Date
EP0682145A2 EP0682145A2 (en) 1995-11-15
EP0682145A3 EP0682145A3 (en) 1998-08-26
EP0682145B1 true EP0682145B1 (en) 2004-08-25

Family

ID=27267181

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95810288A Expired - Lifetime EP0682145B1 (en) 1994-05-12 1995-05-03 Textile treatment

Country Status (5)

Country Link
EP (1) EP0682145B1 (en)
DE (1) DE69533417T2 (en)
ES (1) ES2225833T3 (en)
MX (2) MX201082B (en)
PT (1) PT682145E (en)

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CN104995350A (en) * 2013-04-02 2015-10-21 美津浓株式会社 Fluorescent whitened highly cross-linked polyacrylate fiber, manufacturing method therefor, and fiber structure comprising same

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CN104995350A (en) * 2013-04-02 2015-10-21 美津浓株式会社 Fluorescent whitened highly cross-linked polyacrylate fiber, manufacturing method therefor, and fiber structure comprising same

Also Published As

Publication number Publication date
MX203852B (en) 2001-08-22
MX201082B (en) 2001-03-19
DE69533417D1 (en) 2004-09-30
DE69533417T2 (en) 2005-08-18
ES2225833T3 (en) 2005-03-16
EP0682145A3 (en) 1998-08-26
EP0682145A2 (en) 1995-11-15
PT682145E (en) 2005-01-31

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