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
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German (de)
English (en)
French (fr)
Other versions
EP0682145A2 (en
EP0682145A3 (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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Publication date
Priority claimed from GB9409465A external-priority patent/GB9409465D0/en
Priority claimed from GB9409466A external-priority patent/GB9409466D0/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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EP95810288A 1994-05-12 1995-05-03 Textile treatment Expired - Lifetime EP0682145B1 (en)

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GB9409466 1994-05-12
GB9409465A GB9409465D0 (en) 1994-05-12 1994-05-12 Protective use
GB9409466A GB9409466D0 (en) 1994-05-12 1994-05-12 Textile treatment
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GB9413270A GB9413270D0 (en) 1994-07-01 1994-07-01 Textile treatment
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