EP0682145B1 - Traitement textile - Google Patents

Traitement textile 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
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German (de)
English (en)
Other versions
EP0682145A3 (fr
EP0682145A2 (fr
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/fr
Publication of EP0682145A3 publication Critical patent/EP0682145A3/fr
Application granted granted Critical
Publication of EP0682145B1 publication Critical patent/EP0682145B1/fr
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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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Claims (9)

  1. Utilisation d'un agent de blanchiment optique permettant d'améliorer l'indice de protection (IP) d'un matériau en fibres textiles, dans laquelle ledit agent de blanchiment optique absorbe le rayonnement dans la plage de longueurs d'onde allant de 280 à 400 nm, dans une composition qui est
    a) une composition aqueuse de finissage textile ;
       comprenant au moins un agent de blanchiment optique qui est choisi dans le groupe constitué par l'acide 4,4'-bis-(triazinylamino)-stilbène-2,2'-disulfonique, l'acide 4,4'-bis-(triazol-2-yl)stilbène-2,2'-disulfonique, des 4,4'-(diphényl)-stilbènes, le 4,4'-distyryl-biphényle, le 4-phényl-4'-benzoxazolylstilbène, des stilbénylnaphtotriazoles, le 4-styryl-stilbène, des dérivés bis-(benzoxazol-2-yle), un dérivé bis-(benzimidazol-2-yle), la coumarine, la pyrazoline, le naphtalimide, le triazinyl-pyrène, un dérivé 2-styryl-benzoxazole ou -naphtoxazole, un dérivé benzimidazole-benzofuranne ou oxanilide, ou
    b) une composition détergente
       comprenant au moins un agent de blanchiment optique, qui est choisi dans le groupe constitué par :
    Figure 01050001
    Figure 01050002
    Figure 01050003
    Figure 01050004
    Figure 01050005
    Figure 01060001
    Figure 01060002
    Figure 01060003
       dans lesquelles R43 et R44, indépendamment, représentent OH, NH2, un groupe O-alkyle en C1-C4, un groupe O-aryle, un groupe NH-alkyle en C1-C4, un groupe N(alkyle en C1-C4)2, un groupe N(alkyle en C1-C4) (hydroxyalkyle en C1-C4) , un groupe. N(hydroxyalkyle en C1-C4) 2, un groupe NH-aryle, un groupe morpholino, un groupe S-alkyl (aryle) en C1-C4, Cl ou OH ; R45 et R46 indépendamment, représentent H, un groupe alkyle en C1-C4, un groupe phényle ou un groupe de formule :
    Figure 01060004
       R47 représente H, Cl ou SO3M ; R48 représente CN, SO3M, un groupe S (alkyle en C1-C4) 2 ou un groupe S(aryle)2 ; R49 représente H, SO3M, un groupe O-alkyle en C1-C4, CN, Cl, un groupe COO-alkyle en C1-C4, ou un groupe CON(alkyle en C1-C4)2 ; R50 représente H, un groupe alkyle en C1-C4, Cl ou SO3M ; R51 et R52, indépendamment, représentent H, un groupe alkyle en C1-C4, SO3M, Cl ou un groupe O-alkyle en C1-C4 ; R53 représente H ou un groupe alkyle en C1-C4; R54 représente H, un groupe alkyle en C1-C4, CN, Cl, un groupe COO-alkyle en C1-C4, un groupe CON(alkyle en C1-C4)2, un groupe aryle ou un groupe O-aryle ;
    et
       M représente H, Na, K, Ca, Mg, un ammonium, un mono-, di-, tri- ou tétra-alkylammonium en C1-C4, un mono-, di- ou tri-hydroxyalkylammonium en C1-C4 ou un ammonium qui est di- ou tri-substitué par un mélange de groupes alkyle en C1-C4 et hydroxyalkyle en C1-C4, et n vaut 0 ou 1 ;
    ou
    c) une composition de traitement de tissu après lavage comprenant au moins un agent de blanchiment optique, dans laquelle ledit agent de blanchiment optique est un agent de blanchiment optique bistyrylphényle cationique de formule :
    Figure 01070001
       dans laquelle Y représente un groupe arylène, éventuellement substitué par un groupe chloro, méthyle ou méthoxy ; q vaut 1 ou 2 ; R55 représente un atome d'hydrogène, un groupe chloro, un groupe alkyle en C1-C4, un groupe alcoxy en C1-C4, un groupe cyano ou un groupe alcoxycarbonyle en C1-C4 ; R56 et R57 représentent un groupe alkyle en C1-C4, un groupe chloroéthyle, un groupe méthoxyéthyle, un groupe bêta-éthoxyéthyle, un groupe bêta-acétoxyéthyle ou bêta-cyanoéthyle, un groupe benzyle ou un groupe phényléthyle ; R58 représente un groupe alkyle en C1-C4, un groupe hydroxyalkyle en C2-C3, un groupe bêta-hydroxy-gamma-chloropropyle, un groupe bêta-cyanoéthyle ou un groupe alcoxy-carbonyléthyle en C1-C4 ; et An (-) représente un anion d'un acide organique ou inorganique ; ou,
       un agent de blanchiment optique bistyrylphényle cationique de formule :
    Figure 01080001
       dans laquelle R55 et q ont la même signification que précédemment et Y1 représente un groupe alkylène en C2-C4 ou un groupe hydroxypropylène ; R59 représente un groupe alkyle en C1-C4 ou, avec R60 et l'atome d'azote auquel ils sont chacun attachés, R59 forme un cycle pyrrolidine, pipéridine, hexaméthylèneimine ou morpholine ; R60 représente un groupe alkyle en C1-C4 ou, conjointement avec R59 et l'atome d'azote auquel ils sont chacun attachés, R60 forme un cycle pyrrolidine, pipéridine, hexaméthylèneimine ou morpholine ; R61 représente un atome d'hydrogène, un groupe alkyle en C1-C4, un groupe alcényle en C3-C4, un groupe alcoxycarbonylméthyle en C1-C4, un groupe benzyle, un groupe hydroxyalkyle en C2-C4, un groupe cyanoalkyle en C2-C4 ou, conjointement avec R59 et R60 et l'atome d'azote auquel ils sont chacun attachés, R61 forme un cycle pyrrolidine, pipéridine, hexaméthylèneimine ou morpholine ; p vaut 0 ou 1 ; et An(-) représente un anion d'un acide organique ou inorganique ; ou,
       un agent de blanchiment optique bistyrylphényle de formule :
    Figure 01090001
       dans laquelle R55, Y1, p et q ont la même signification que précédemment et An(-) représente un anion d'un acide organique ou inorganique ; et R62 et R63 indépendamment, représentent un groupe alkyle en C1-C4 ou un groupe alcényle en C2-C3 ou R62 et R63, conjointement avec l'atome d'azote auquel ils sont attachés, forment un cycle pyrrolidine, pipéridine, hexaméthylèneimine ou morpholine ; R64 représente un atome d'hydrogène, un groupe alkyle en C1-C4 ou un groupe alcényle en C2-C3 ou R62, R63 et R64, conjointement avec l'atome d'azote auquel ils sont attachés, forment un cycle pyridine ou picoline ; et Z représente un atome de soufre, -SO2-, -SO2NH-, un groupe -O-alkylène en C1-C4-COO- ou -OCO-, ou, dans laquelle l'agent de blanchiment optique bistyrylphényle cationique a la formule :
    Figure 01100001
       dans laquelle R55, R62, R63, R64, Y1, p et q ont la même signification que précédemment et An(-) représente un anion d'un acide organique ou inorganique ; ou,
       un agent de blanchiment optique styrène amphotère de formule :
    Figure 01100002
       dans laquelle R55, R62, R63, Y1 et q ont la même signification que précédemment et An(-) représente un anion d'un acide organique ou inorganique ; Z1 représente un atome d'oxygène, un atome de soufre, une liaison directe, -COO-, -CON(R65)- ou -SO2N (R65) - où R65 représente un atome d'hydrogène, un groupe alkyle en C1-C4 ou un groupe cyanoéthyle ; et Q représente -COO- ou -SO3, et,
       dans laquelle l'agent de blanchiment optique oxyde d'amine a la formule :
    Figure 01110001
       dans laquelle q a la même signification que précédemment et B représente un radical d'azurant optique choisi parmi un 4,4'-distyrylbiphényle, un 4,4'-divinyl-stilbène, et un 1,4'-distyrylbenzène, chacun étant éventuellement substitué par un à quatre substituants choisis parmi un atome d'halogène, un groupe alkyle en C1-C4, un groupe hydroxyalkyle en C1-C4, un groupe halogénoalkyle en C1-C4, un groupe cyanoalkyle en C1-C4, un groupe alcoxy en C1-C4-alkyle en C1-C4, un groupe phényl-alkyle en C1-C4, un groupe carboxy-alkyle en C1-C4, un groupe carb-alcoxy en -C1-C4-alkyle en C1-C4, un groupe alcényle en C1-C4, un groupe cycloalkyle en C5-C8, un groupe alcoxy en C1-C4, un groupe alcénoxy en C1-C4, un groupe alcoxycarbonyle en C1-C4, un groupe carbamoyle, un groupe cyano, un groupe alkylsulfonyle en C1-C4, un groupe phénylsulfonyle, un groupe alcoxysulfonyle en C1-C4, un groupe sulfamoyle, un groupe hydroxyle, un groupe carboxyle, un groupe sulfo et un groupe trifluorométhyle ; Z2 représente une liaison directe entre B et Y2, un atome d'oxygène, un atome de soufre, -SO2-, -SO2-O-, -COO-, -CON(R68) ou -SO2N(R68)- où R68 représente un atome d'hydrogène ou un groupe alkyle en C1-C4 éventuellement substitué par un atome d'halogène, un groupe cyano, un groupe hydroxyle, un groupe carbalcoxy en C2-C5, un groupe alcoxy en C1-C4, un groupe phényle, un groupe chlorophényle, un groupe méthylphényle, un groupe méthoxyphényle, un groupe carbamoyle ou un groupe sulfamoyle ; Y2 représente un groupe alkylène en C2-C4 ou un groupe alkylénoxy en C2-C4-alkylène en C2-C4, chacun étant éventuellement substitué par un atome d'halogène, un groupe hydroxyle, un groupe carbalcoxy en C2-C5, un groupe alcoxy en C1-C4, un groupe phényle, un groupe chlorophényle, un groupe méthylphényle, un groupe méthoxyphényle, un groupe carbamoyle ou un groupe sulfamoyle ; et R66 et R67, indépendamment, représentent un groupe cycloalkyle en C5-C8, un groupe alkyle en C1-C4 ou un groupe phényle, chacun étant éventuellement substitué par un atome d'halogène, un groupe hydroxyle, un groupe carbalcoxy en C2-C5, un groupe alcoxy en C1-C4, un groupe phényle, un groupe chlorophényle, un groupe méthylphényle, un groupe méthoxyphényle, un groupe carbamoyle ou un groupe sulfamoyle ; où, dans tous les groupes carbamoyle ou sulfamoyle, l'atome d'azote est éventuellement substitué par un ou deux groupes alkyle en C1-C4, hydroxyalkyle en C1-C4, cyanoalkyle en C2-C5, halogénoalkyle en C1-C4, benzyle ou phényle, ou,
       un agent de blanchiment optique cationique de formule :
    Figure 01120001
       dans laquelle Y2 et q ont la même signification que précédemment, et B1 représente un radical d'azurant optique ; Z3 représente une liaison directe, un groupe -SO2-alkylénoxy en C2-C4, un groupe -O2-alkylène en C2-C4-COO-, -SO2-, -COO-, un groupe -SO2-alkylène en C2-C4-CON (R75)- ou -SO2N (R75)- où R75 représente un atome d'hydrogène ou un groupe alkyle en C1-C4 éventuellement substitué par un groupe hydroxyle, un atome d'halogène ou un groupe cyano ; R70 représente un groupe alkyle en C1-C4 ou un groupe alcényle en C1-C4, chacun étant éventuellement substitué par un atome d'halogène, un groupe cyano, un groupe hydroxy, un groupe alcoxycarbonyle en C1-C4 ou un groupe alkylcarbonyloxy en C1-C4, ou R70 représente un groupe benzyle éventuellement substitué par un atome d'halogène, un groupe alkyle en C1-C4 ou un groupe alcoxy en C1-C4, ou R70, conjointement avec R71 ou Z3, forme un radical pyrrolidine, pipéridine ou morpholine ; R71 représente un groupe alkyle en C1-C4 ou un groupe alcényle en C2-C4, chacun étant éventuellement substitué par un atome d'halogène, un groupe cyano, un groupe hydroxy, un groupe alcoxycarbonyle en C1-C4 ou un groupe alkylcarbonyloxy en C1-C4, ou R71 représente un groupe benzyle, éventuellement substitué par un atome d'halogène, un groupe alkyle en C1-C4 ou un groupe alcoxy en C1-C4, ou R71, conjointement avec R70, forme un radical pyrrolidine, pipéridine ou morpholine ; R72 représente un groupe alkyle en C1-C4, R73 représente un atome d'hydrogène ou
    un groupe alkyle en C1-C4, éventuellement substitué par un groupe cyano, un groupe hydroxy, un groupe alcoxycarbonyle en C1-C4 ou un groupe alkylcarbonyloxy en C1-C4 ; et R74 représente un groupe alkyle en C1-C4,
    ou,
       dans laquelle ledit agent de blanchiment optique est un agent de blanchiment optique anionique bis(triazinyl)diaminostilbène de formule :
    Figure 01140001
       ou un agent de blanchiment optique anionique dibenzofuranylbiphényle de formule :
    Figure 01140002
       ou un agent optique bistyrylphényle anionique de formule :
    Figure 01140003
       dans laquelle R76 représente un groupe phényle éventuellement substitué par un ou deux groupes SO3M et R77 représente un groupe NH-alkyle en C1-C4, un groupe N (alkyle en C1-C4)2, un groupe NH-alcoxy en C1-C4, un groupe N (alcoxy en C1-C4) 2, un groupe N (alkyle en C1-C4)(hydroxyalkyle en C1-C4), un groupe N (hydroxyalkyle en C1-C4) 2 ; R70 représente H, un groupe alkyle en C1-C4, CN, Cl ou SO3M ; R79 et R80, indépendamment, représentent H, un groupe alkyle en C1-C4, SO3M, CN, Cl ou un groupe O-alkyle en C1-C4, à condition qu'au moins deux de R78, R79 et R80 représentent SO3M et que le troisième groupe ait un caractère solubilisant ; R81 représente H, SO3M, un groupe O-alkyle en C1-C4, CN, Cl, un groupe COO-alkyle en C1-C4, ou un groupe CON(alkyle en C1-C4) 2 ; et r vaut 0 ou 1, et M a la même signification que précédemment.
  2. Utilisation selon la revendication 1, dans laquelle la composition est une composition aqueuse de finissage textile et la quantité d'agent de blanchiment optique présente dans la composition se situe dans la plage allant de 0,01 à 3 % ; ou la composition est une composition détergente et la quantité d'agent de blanchiment optique présente dans la composition se situe dans la plage allant de 0,005 à 2 %.
  3. Utilisation selon la revendication 1, dans laquelle la composition est une composition aqueuse de finissage textile et l'agent de blanchiment optique utilisé est l'acide 4,4'-bis-(triazinylamino)-stilbène-2,2'-disulfonique, ayant la formule :
    Figure 01150001
       dans laquelle R1 et R2, indépendamment, représentent un groupe phényle, un groupe phényle mono- ou disulfoné, un groupe phénylamino, un groupe phénylamino mono- ou disulfoné, un groupe morpholino, -N (CH2CH2OH)2, -N(CH3) (CH2CH2OH), -NH2, un groupe -N(alkyle en C1-C4)2, -OCH3, -Cl, -NH-CH2CH2SO3H ou -NH-CH2CH2OH ; et M représente H, Na, K, Ca, Mg, un ammonium, un mono-, di-, tri- ou tétra-alkylammonium en C1-C4, un mono-, di- ou tri-hydroxyalkylammonium en C1-C4 ou un ammonium qui est di- ou tri-substitué par un mélange de groupes alkyle en C1-C4 et hydroxyalkyle en C1-C4, et
       dans laquelle l'acide 4,4'-bis-(triazol-2-yl)-stilbène-2,2'-disulfonique est celui ayant la formule :
    Figure 01160001
       dans laquelle R3 et R4, indépendamment, représentent H, un groupe alkyle en C1-C4, un groupe phényle ou un groupe phényle monosulfoné et, dans laquelle le 4,4'-(diphényl)-stilbène est celui ayant la formule :
    Figure 01160002
       et,
       dans laquelle le 4,4'-distyryl-biphényle utilisé a la formule :
    Figure 01160003
       dans laquelle R5 et R6, indépendamment, représentent H, SO3M, un groupe SO2N (alkyle en C1-C4)2, un groupe O-(alkyle en C1-C4), CN, Cl, un groupe COO(alkyle en C1-C4), un groupe CON(alkyle en C1-C4)2 ou O (CH2) 3N (+) (CH3) 2An (-) , où An (-) représente un anion d' un acide organique ou inorganique ; et n vaut 0 ou 1, ou dans laquelle le 4-phényl-4'-benzoxazolyl-stilbène a la formule :
    Figure 01170001
       dans laquelle R7 et R8, indépendamment, représentent H, Cl, un groupe alkyle en C1-C4 ou un groupe SO2-alkyle en C1-C4, et dans laquelle un stilbényl-naphtotriazole utilisé est celui de formule :
    Figure 01170002
       dans laquelle R9 représente H ou Cl; R10 représente SO3M, un groupe SO2N (alkyle en C1-C4)2, ou un groupe SO2O-phényle ou CN ; R11 représente H ou SO3M, et dans laquelle un 4-styryl-stilbène utilisé est celui de formule :
    Figure 01170003
       dans laquelle R12 et R13, indépendamment, représentent H, SO3M, un groupe SO2N (alkyle en C1-C4)2, un groupe O-(alkyle en C1-C4), CN, Cl, un groupe COO(alkyle en C1-C4), un groupe CON(alkyle en C1-C4) 2 ou O(CH2)3N(+)(CH3)2An(-), et dans laquelle un dérivé bis-(benzoxazol-2-yle) utilisé a la formule :
    Figure 01170004
       dans laquelle R14, indépendamment, représente H, C(CH3)3, un groupe C(CH3)2-phényle, un groupe alkyle en C1-C4 ou un groupe COO-alkyle en C1-C4, et X représente -CH=CH- ou un groupe de formule :
    Figure 01180001
       et
       dans laquelle un dérivé bis-(benzimidazol-2-yle) est utilisé de formule :
    Figure 01180002
       dans laquelle R15 et R16, indépendamment, représentent H, un groupe alkyle en C1-C4 ou CH2CH2OH ; R17 représente H ou SO3M ; X1 représente -CH=CH- ou un groupe de formule :
    Figure 01180003
       et dans laquelle une coumarine est utilisée de formule :
    Figure 01190001
       dans laquelle R18 représente H, Cl ou CH2COOH, R19 représente H, un groupe phényle, un groupe COO-alkyle en C1-C4 ou un groupe de formule :
    Figure 01190002
       et R20 représente un groupe O-alkyle en C1-C4, un groupe N(alkyle en C1-C4)2, un groupe NH-CO-alkyle en C1-C4 ou un groupe de formule :
    Figure 01190003
       ou
       dans laquelle R21 représente H, un groupe alkyle en C1-C4 ou un groupe phényle, et
       dans laquelle une pyrazoline utilisée est celle ayant la formule :
    Figure 01190004
       dans laquelle R22 représente H, Cl, ou un groupe N(alkyle en C1-C4) 2, R23 représente H, Cl, SO3M, SO2NH2, un groupe SO2NH-(alkyle en C1-C4), un groupe COO-alkyle en C1-C4, un groupe SO2-alkyle en C1-C4, SO2NHCH2CH2CH2N (+) (CH3) 3 ou un groupe SO2CH2CH2N(+) H (alkyle en C1-C4)2An (-), R24 et R25 sont identiques ou différents et chacun représente H, Cl, un groupe alkyle en C1-C4 ou un groupe phényle et R26 représente H ou Cl ; et
       dans laquelle un naphtalimide est utilisé de formule :
    Figure 01200001
       dans laquelle R27 représente un groupe alkyle en C1-C4 ou CH2CH2CH2N(+) (CH3)3 ; R28 représente un groupe O-alkyle en C1-C4, SO3M ou un groupe NH-CO-alkyle en C1-C4 ; et
       dans laquelle un triazinyl-pyrène est utilisé de formule:
    Figure 01200002
       dans laquelle chaque R29, indépendamment, représente un groupe alcoxy en C1-C4, et
       dans laquelle un dérivé 2-styryl-benzoxazole ou -naphtoxazole est utilisé ayant la formule :
    Figure 01210001
       dans laquelle R31 représente CN, Cl, un groupe COO-alkyle en C1-C4 ou un groupe phényle ; R32 et R33 représentent les atomes requis pour former un cycle benzène condensé ou R33 et R35, indépendamment, représentent H ou un groupe alkyle en C1-C4 ; et R34 représente H, un groupe alkyle en C1-C4 ou un groupe phényle, et,
       dans laquelle un dérivé benzimidazole-benzofuranne est utilisé ayant la formule :
    Figure 01210002
       dans laquelle R36 représente un groupe alcoxy en C1-C4 ; R37 et R38, indépendamment, représentent un groupe alkyle en C1-C4;
       et dans laquelle un dérivé oxanilide est utilisé ayant la formule :
    Figure 01210003
       dans laquelle R39 représente un groupe alcoxy en C1-C4, R41 représente un groupe alkyle en C1-C4, un groupe alkyle en C1-C4-SO3M ou un groupe alcoxy en C1-C4-SO3M et R40 et R42 sont identiques et chacun représente un atome d'hydrogène, un groupe tert-butyle ou SO3M.
  4. Utilisation selon la revendication 1, dans laquelle la composition est une composition de finissage textile et l'agent de blanchiment optique est utilisé :
    a) dans des mélanges avec des colorants (coloration légère) ou des pigments ;
    b) dans des mélange avec des véhicules, des agents mouillants, des antioxydants, des absorbants d'UV et/ou des agents de blanchiment chimique ; ou
    c) en mélange avec des agents de réticulation ou de finissage ou en combinaison avec un procédé de finissage textile ou un apprêt ignifugeant, un apprêt pour la douceur, un apprêt antisalissures, un apprêt antistatique ou un apprêt antimicrobien.
  5. Utilisation selon la revendication 1, dans laquelle le composé de formule (23) a la formule :
    Figure 01230001
    Figure 01230002
    Figure 01230003
    Figure 01240001
    Figure 01240002
    Figure 01240003
    ou
       dans laquelle le composé de formule (24) à la formule :
    Figure 01240004
    Figure 01250001
    Figure 01250002
       dans laquelle n est tel que défini dans la revendication 1 ;
       dans laquelle le composé de formule (26) a la formule :
    Figure 01250003
    Figure 01250004
    Figure 01250005
    ou
       dans laquelle le composé de formule (27) a la formule :
    Figure 01260001
    Figure 01260002
    Figure 01260003
    Figure 01260004
       ou
       dans laquelle le composé de formule (30) a la formule :
    Figure 01260005
  6. Utilisation selon la revendication 1, dans laquelle le composé de formule (56) a la formule (31), (32) ou (34), ou dans laquelle le composé de formule (57) a la formule (43), (44), (45) ou (46) ou dans laquelle le composé de formule (58) a la formule (40), (41), ou (42), chacune étant telle que définie dans la revendication 5.
  7. Utilisation selon la revendication 1, dans laquelle la composition utilisée est une composition détergente comprenant :
    i) de 5 à 90 % d'un tensioactif anionique et/ou d'un tensioactif non ionique ;
    ii) de 5 à 70 % d'un adjuvant ;
    iii) de 0 à 30 % d'un peroxyde ;
    iv) de 0 à 10 % d'un. activateur de peroxyde et/ou de 0 à 1 % d'un catalyseur de blanchiment ;
    v) de 0,005 à 2 % d'au moins un agent de blanchiment optique qui absorbe le rayonnement dans la plage de longueurs d'onde allant de 280 à 400 nm ; et
    vi) de 0,005 à 10 % d'un ou plusieurs auxiliaires, chacun en poids, par rapport au poids total du détergent.
  8. Composition adoucissante de tissu pour cycle de rinçage concentrée et stable comprenant de 2 à 25 % en poids d'un agent adoucissant de tissu, et > 0,3 à 10 % en poids d'un agent de blanchiment optique qui est compatible avec l'agent adoucissant de tissu, chacun par rapport au poids total de la composition, le reste étant essentiellement de l'eau.
  9. Procédé pour le traitement d'un article textile, comprenant une étape d'application, sur un article préalablement lavé, d'une composition de rinçage de tissu comprenant > 0,3 à 10 % en poids d'un agent de blanchiment optique cationique, amphotère ou anionique, par rapport au poids total de la composition, et éventuellement d'un ingrédient de traitement de tissu, le reste étant essentiellement de l'eau.
EP95810288A 1994-05-12 1995-05-03 Traitement textile Expired - Lifetime EP0682145B1 (fr)

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