Dye Formulation and Process for the Treatment of Fiber Materials

The present invention relates to a formulated dye and to a process for improving the whiteness of polyester, polyamide and polyacrylonitrile fiber materials wherein the fiber materials are treated with a specific dye formulation in a laundry process. Further aspects of the invention are a detergent composition and a softener composition containing the dye formulation.

Often, fiber materials do not show the desired grade of whiteness. It has been found that in many cases the whiteness cannot be increased to the desired grade of whiteness by only applying optical brighteners, for example by laundering with brighteners containing detergents. It is, therefore, still a need to improve the whiteness of such fiber materials. Surprisingly it has been found that the treatment of polyester, polyamide and polyacrylnitrile fibers or fabrics with Disperse Violet 57 or Solvent Violet 13, which have been formulated in a non-ionic surfactant, allows improving the whiteness of such fiber materials in simple laundry processes to a great extent.

In addition, it is known that fiber materials show in the course of time a decrease of the whiteness grade. Surprisingly, the present invention allows also improving the whiteness of such fiber materials again.

In one aspect the present invention pertains to a composition for use in laundry processes comprising

0.1 to 10 parts of the compound of formula (1 ) or (2)

and

99.9 to 90 parts of a non-ionic surfactant.

The compounds of formula (1 ) and (2) (1 ).

(2) are known and commercially available under the name

Disperse Violet 57, CAS Registry Number: 1594-08-7, CA Index Name: 9,10-anthracene- dione, 1-hydroxy-4-[[4-[(methylsulfonyl)oxy]phenyl]amino] and Solvent Violet 013, CAS Registry Number: 81-48-1 , CA Index Name: 9,10-anthracenedione,1-hydroxy-4-[(4- methylphenyl)amino].

Parts are in all cases parts by weight, unless otherwise indicated.

Since the compounds of formula (1 ) and (2) are not soluble in the non-ionic surfactant, the composition is in the form of a dispersion. A dispersion can be prepared in known manner, by mixing the dye and the dispersant in an appropriate device, such as mixers, ball mills and the like.

The composition comprises preferably from 0.5 to 5.0 parts and more preferably from 1 to 2 parts of the compounds of formula (1 ) and (2), the non-ionic surfactant being present in an amount that the sum adds to 100 parts.

Preferred is a composition for use in laundry processes comprising

0.1 to 10 parts of the compound of formula (1 ) ; and

99.9 to 90 parts of a non-ionic surfactant.

Examples of the nonionic surfactant include the followings:

(1 ) a polyoxyalkylene alkyl (or alkenyl) ether obtained by adding 3 to 30 mol in average, preferably 4 to 20 mol and more preferably 5 to 17 mol of alkylene oxide having 2 to 4 carbons to an aliphatic alcohol having 6 to 22 carbons and preferably 8 to 18 carbons. Among these, a polyoxyethylene alkyl (or alkenyl) ether, and a polyoxyethylenepolyoxypropylene alkyl (or alkenyl) ether are preferable. The aliphatic alcohol used here includes a primary alcohol and a secondary alcohol. Its alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable;

(2) a polyoxyethylenealkyl (or alkenyl) phenyl ether;

(3) a fatty acid alkyl ester alkoxylate, for example represented by the following general formula (3) in which alkylene oxide is added between the ester bond of a long chain fatty acid alkyl ester:

R ⁹ CO(OA) _n OR 10 ...(3)

(wherein R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms and preferably 8 to 18 carbon atoms, OA represents the addition unit of alkylene oxide having 2 to 4 carbon atoms and preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide, n represents the average addition molar number of alkylene oxide and is generally a number of 3 to 30 and preferably 5 to 20, and R ¹⁰ is a lower alkyl group, which may have a substituent having 1 to 3 carbons;

(4) a fatty acid ester of polyoxyethylene sorbitan;

(5) a fatty acid ester of polyoxyethylene sorbit;

(6) a fatty acid ester of polyoxyethylene;

(7) a caster oil hardened with polyoxyethylene;

(8) a fatty acid ester of glycerin;

(9) a fatty acid alkanoyl amide;

(10) polyoxyethylenealkylamine;

- A -

(1 1 ) alkylglycoside; and

(12) alkylamine oxide.

Among the above-mentioned nonionic surfactants, there are preferably used polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylenepolyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to fatty acid methyl ester, fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to fatty acid methyl ester, and the like, wherein the melting point is 4O ⁰ C or lower and HLB is 9 to 16. Further, these nonionic surfactants can be suitably used by combining one or two or more.

Further, HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (refer to "New Edition Surfactant Handbook" co-edited by Yoshida, Shindo, Ohgaki and Yamanaka, 1991 , page 234, published by KOGYO-TOSHO, K.K.).

Further, a melting point in the present invention is a value measured by a coagulation point measurement method described in JIS K8001 "General Rule for Reagent Test Method".

The above mentioned non-ionic surfactants are commercially available, for example, under the trade name DOBANOL®

In a particularly preferred embodiment of the invention, the non-ionic surfactant is a polyoxyethylene alkyl (or alkenyl) ether with a HLB value of 9 to 16.

Another aspect of the invention is a process for improving the whiteness of fiber materials selected from the group consisting of polyester, polyamide and polyacrylonitrile, comprising treating the fiber materials with a) a laundry detergent formulation; and b) a composition

comprising 0.1 to 10 parts of the compound of formula (1 ) or (2)

99.9 to 90 parts of a non-ionic surfactant; in a laundry process.

Compound (1 ) is preferred in the process.

Surprisingly it has been found that the degree of whiteness, as measured according to Ganz, can be significantly improved as compared to the addition of the dye of formula (1 ) or (2) without a surfactant or with cationic or anionic surfactants.

The components a) and b) are preferably simultaneously present as in a usual washing process. In specific cases it may be, however, of advantage to apply the components a) and b) subsequently.

Preferably the composition of component b) is present in an amount of from 1 % to 30% more preferably from 5% to 20% by weight based on the weight of the laundry detergent formulation, component a).

Suitable fiber materials are polyester, polyamide and polyacrylonitrile fiber materials as well as corresponding blended fiber materials. Preferred are especially polyester and polyamide. Highly preferred is polyester.

In case of blends, the fiber materials preferably comprise at least 10 % by weight, especially at least 20 % by weight, of polyester, polyamide or polyacrylonitrile.

The fiber material may be blended with other synthetic or natural fiber materials. Examples of such other synthetic fiber materials are polyamide, polyacrylonitrile, polyacryl, polyisoprene and polyurethane. Examples of such natural fiber materials are cotton, viscose, flax, rayon,

linen, wool, mohair, cashmere, angora and silk. As to the blends preference is given to polyester/cotton or polyester/polyamide blends.

In such blends it is preferred that the ratio by weight of polyester, polyamide, polyacrylonitrile to other synthetic or natural fiber material is 80:20 to 20:80, more preferably 70:30 to 30:70.

Preferred is a process wherein the fiber material is polyester or a blend comprising polyester.

Particular preference is given to a process wherein the fiber material is polyester, or a polyester/cotton or polyester/polyamide blend.

The said fiber material may be in any form, such as usual clothes or curtains.

Preferred is an improvement of the whiteness grade by at least 3 whiteness grades according to Ganz, especially at least 5, and more preferably at least 10 whiteness grades, compared to the fiber material before the treatment.

In the general context of the present invention, the process covers all processes carried out in laundering (pre-soaking, washing, and after-treatment like rinsing).

The process can be carried out in a washing machine as well as by hand. The usual washing temperature is between 5°C and 95°C.

The washing or cleaning agents are usually formulated that the washing liquor has pH value of about 6.5 - 11 , preferably 7.5 - 11 during the whole washing procedure.

The liquor ratio in the washing process is usually 1 :2 to 1 :40, preferably 1 :4 to 1 :15, more preferably 1 :4 to 1 :10, especially preferably 1 :5 to 1 :9.

The dyes of formula (1 ) or (2) are usually used in an amount of 0.0001 to 0.1% by weight, preferably 0.0002 to 0.03% by weight, based on the weight of the treated fiber materials.

The washing procedure is usually done in washing machines.

There are various types of washing machines, for example:

top-loader- washing machines with a verticle rotating axis; these machines, which have usually a capacity of about 45 to 83 litres, are used for washing processes at temperatures of 10-50 ⁰ C and washing cycles of about 10-60 minutes. Such types of washing machines are often used in the USA; - front-loader-washing machines with a horizontal rotating axis; these machines, which have usually a capacity of about 8 to 15 litres, are used for washing processes at temperatures of 30-95 ⁰ C and washing cycles of about 10-60 minutes. Such types of washing machines are often used in Europe; top-loader-washing machines with a verticle rotating axis; these machines, which have usually a capacity of about 26 to 52 litres, are used for washing processes at temperatures of 5-25°C and washing cycles of about 8-15 minutes. Such types of washing machines are often used in Japan.

Hand washing is usually carried out at temperatures of 10 to 50 ⁰ C, especially 25 to 40°C. The liquor ratio (fabric to water) is usually 1 to 10. The amount of detergent used for hand washing is, as a rule, 0.1 to 10% by weight, based on the weight of the fabric to be treated. The washing time is preferably 5 to 60 minutes. If desired, a pre-soaking step can be carried out, wherein, before hand washing, the fibre material is left for 0.2-24 hours in a solution or suspension of the detergent without agitation.

The detergents may be in solid, liquid, gel-like or paste-like form. The detergents may also be in the form of powders or (super-)compact powders or granules, in the form of single- or multi-layer tablets (tabs), in the form of washing agent bars, washing agent blocks, washing agent sheets, washing agent pastes or washing agent gels, or in the form of powders, pastes, gels or liquids used in capsules or in pouches (sachets).

Consequently another aspect of the invention is a detergent composition for improving the whiteness of fiber materials selected from the group consisting of polyester, polyamide and polyacrylonitrile comprising a composition for use in laundry processes which comprises

0.1 to 10 parts of the compound of formula (1 ) or (2) (1 ).

99.9 to 90 parts of a non-ionic surfactant.

For example, the detergents comprise:

I) from 5 to 70 wt-% A) of at least one anionic surfactant and/or B) at least one non-ionic surfactant, based on the total weight of the detergent,

II) from 0 to 60 wt-% C) especially from 5 to 60 wt-% of at least one builder substance, based on the total weight of the detergent,

III) from 0 to 30 wt-% D) of at least one peroxide and, optionally, at least one activator and/or at least one catalyst, based on the total weight of the detergent.

The anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxysulfates in which the alkyl radical has from 10 to 20 carbon atoms.

Preferred sulfonates are e.g. alkylbenzenesulfonat.es having from 9 to 15 carbon atoms in the alkyl radical. The cation in the case of anionic surfactants is preferably an alkali metal cation, especially sodium.

The anionic surfactant component may be, e.g., an alkylbenzenesulfonate, an alkylsulfate, an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or

alkenyl ether carboxylate or an α-sulfofatty acid salt or an ester thereof. Preferred are alkylbenzenesulfonat.es having 10 to 20 carbon atoms in the alkyl group, alkylsulfates having 8 to 18 carbon atoms, alkylethersulfates having 8 to 22 carbon atoms, and fatty acid salts being derived from palm oil or tallow and having 8 to 22 carbon atoms. The average molar number of ethylene oxide added in the alkylethersulfate is preferably 1 to 22, preferably 1 to 10. The salts are preferably derived from an alkaline metal like sodium and potassium, especially sodium. Highly preferred carboxylates are alkali metal sarcosinates of formula R _1O g-CO(Ri _I o)CH ₂ COOM ₁ in which R ₁₀₉ is alkyl or alkenyl having 8-20 carbon atoms in the alkyl or alkenyl radical, R ₁₁₀ is C ₁ -C ₄ alkyl and M ₁ is an alkali metal, especially sodium.

Preferred as anionic surfactants are sulfonates, like olefinsulfonates, alkanesulfonates or especially alkylbenzenesulfonat.es having 10 to 20 carbon atoms in the alkyl group, especially C ₁₀ -C ₁₆ alkylbenzenesulfonates and more preferably Cn-Cualkylbenzene- sulfonates. Preferably the alkyl group of the alkylbenzenesulfonate is linear. Especially preferred are the sodium or potassium alkylbenzenesulfonat.es.

Examples for non-ionic surfactants have already been mentioned before, they are also suitable in the detergent formulation.

As builder substance C) there come into consideration, for example, alkali metal phosphates, especially tripolyphosphates, carbonates or hydrogen carbonates, especially their sodium salts, silicates, aluminosilicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds.

Especially suitable silicates are sodium salts of crystalline layered silicates of the formula NaHSitO ₂ t+i.pH ₂ O or Na ₂ Si _t O _2t+1 .pH ₂ O wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.

Among the aluminosilicates, preference is given to those commercially available under the names zeolithe A, B, X and HS, and also to mixtures comprising two or more of those components. Zeolithe A is preferred.

Among the polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates, and acrylates and also copolymers thereof with maleic anhydride. Preferred poly- carboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylene- diamine disuccinate either in racemic form or in the enantiomerically pure (S, S) form.

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1 ,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, hexamethylenediamin N, N, N', N' tetrakis methanphosphonic acid and diethylenetriaminepentamethylenephosphonic acid, as well as the salts therefrom. Also preferred polyphosphonates have the following formula

R ₁ -N- (CH ₂ CH ₂ N) ₀ -R ₁₁₁

I

R ₁₁₁ wherein

Rm is CH ₂ PO ₃ H ₂ or a water soluble salt thereof and d is an integer of the value 0, 1 or 2.

Especially preferred are the polyphosphonates wherein d is an integer of the value of 1.

Suitable peroxide components include, for example, the organic and inorganic peroxides (like sodium peroxides) known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 5 to 95°C.

The amount of the peroxide or the peroxide-forming substance is preferably 0.5-30% by weight, more preferably 1-20% by weight and especially preferably 1-15% by weight.

As the peroxide component D) there comes into consideration every compound which is capable of yielding hydrogen peroxide in aqueous solutions, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C.

The organic peroxides are, for example, mono- or poly-peroxides, urea peroxides, a combination of a Ci-C ₄ alkanol oxidase and Ci-C ₄ alkanol (such as methanol oxidase and

ethanol as described in WO95/07972), alkylhydroxy peroxides, such as cumene

O hydroperoxide and t-butyl hydroperoxide, organic mono peracids of formula ¹¹² wherein

M signifies hydrogen or a cation, Rii ₂ signifies unsubstituted Ci-Ci ₈ alkyl; substituted Ci-Ci ₈ alkyl; unsubstituted aryl; substituted aryl; -(Ci-C ₆ alkylene)-aryl, wherein the alkylene and/or the alkyl group may be substituted; and phthalimidoCi-C ₈ alkylene, wherein the phthalimido and/or the alkylene group may be substituted. Preferred mono organic peroxy acids and their salts are those of

O formula ¹¹ ^ wherein

M signifies hydrogen or an alkali metal, and

R'ii ₂ signifies unsubstituted Ci-C ₄ alkyl; phenyl;-CrC ₂ alkylene-phenyl or phthalimidod-

C ₈ alkylene.

Especially preferred is CH ₃ COOOH and its alkali salts.

Especially preferred is also ε-phthalimido peroxy hexanoic acid and its alkali salts.

Instead of the peroxy acid it is also possible to use organic peroxy acid precursors and H ₂ O ₂ . Such precursors are the corresponding carboxyacid or the corresponding carboxyanhydrid or the corresponding carbonylchlorid, or amides, or esters, which can form the peroxy acids on perhydrolysis. Such reactions are commonly known.

Peroxy acids may also be generated from precursors such as bleach activators, that is to say compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms. Suitable bleach activators include the customary bleach activators, mentioned at the beginning, that carry O- and/or N-acyl groups having the indicated number of carbon atoms and/or unsubstituted or substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU),

acylated triazine derivatives, especially 1 ,5-diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT), compounds of formula:

wherein R ₁₁₃ is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R ₁₁₄ is linear or branched (C ₇ -C ₁₅ )alkyl, especially activators known under the names SNOBS, SLOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use the combinations of conventional bleach activators known from German Patent Application DE-A-44 43 177. Nitrile compounds that form perimine acids with peroxides also come into consideration as bleach activators.

Also suitable are diperoxyacids, for example, 1 ,12-diperoxydodecanedioic acid (DPDA), 1 ,9- diperoxyazelaic acid, diperoxybrassilic acid; diperoxysebasic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1 ,4-diotic acid and 4,4'-sulphonylbisperoxybenzoic acid.

Preferably, however, inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates.

Examples of suitable inorganic peroxides are sodium tetrahydrate or sodium perborated monohydrate, inorganic peroxyacid compounds, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-10 wt-%, preferably from 4-8 wt-%.

All of these peroxy compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst not containing a transition metal. Generally, the composition can be suitably formulated to contain from 2 to 35 wt-% , preferably from 5 to 25 wt-%, of the peroxy bleaching agent.

Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1 ,003,310 and 1 ,519,351 ; German Patent 3,337,921 ; EP-A-0185522; EP-A-0174132; EP-A-0120591 ; and U.S. Pat. Nos. 1 ,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393. Preferred one are those disclosed in WO 01/05925), especially preferred the 1 :1 Mn(III) complexes.

Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Pat. Nos. 4,751 ,015 and 4,397,757, in EP-A-0284292 and EP-A-331 ,229. Examples of peroxyacid bleach precursors of this class are: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride - (SPCC), N-octyl,N,N-dimehyl-N10 -carbophenoxy decyl ammonium chloride - (ODC), 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.

Any one of these peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.

Of the above classes of bleach precursors, the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors.

Examples of said preferred peroxyacid bleach precursors or activators are sodium-4- benzoyloxy benzene sulphonate (SBOBS); N,N,N'N'-tetraacetyl ethylene diamine (TAED); sodium-1 -methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyl-oxybenzene sulphonate (STHOBS).

The precursors may be used in an amount of up to 12%, preferably from 2-10% by weight, of the composition.

It will be understood that mixtures of inorganic and/or organic peroxides can also be used.

The peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.

The detergents may also comprise one or more optical brighteners, for example from the class bis-triazinylamino-stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis- styryl-biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or a pyrazoline derivative.

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; photobleaching agents; pigments; and/or shading agents. These constituents should, of course, be stable to any bleaching system employed. Such auxiliaries can be present in an amount of, for example, 0.1 to 20 wt-%, preferably 0.5 to 10 wt-%, especially 0.5 to 5 wt-%, based on the total weight of the detergent.

Furthermore, the detergent can optionally contain enzymes. Enzymes can be added to detergents for stain removal. The enzymes usually improve the performance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating the roughness to the touch. Examples of enzymes to be used include, but are by no means limited to, the following: proteases as given in US-B-6,242,405, column 14, lines 21 to 32; lipases as given in US-B-6,242,405, column 14, lines 33 to 46 and as given in

WO-A-0060063; amylases as given in US-B-6,242,405, column 14, lines 47 to 56; and cellulases as given in US-B-6,242,405, column 14, lines 57 to 64.

Commercially available detergent proteases, such as Alcalase ^® , Esperase ^® , Everlase ^® , Savinase ^® , Kannase ^® and Durazym ^® , are sold e.g. by NOVOZYMES A/S.

Commercially available detergent amylases, such as Termamyl ^® , Duramyl ^® , Stainzyme ^® , Natalase ^® , Ban ^® and Fungamyl ^® are sold e.g. by NOVOZYMES A/S. Commercially available detergent ellulases, such as Celluzyme ^® , Carezyme ^® and Endolase ^® , are sold e.g. by NOVOZYMES A/S. Commercially available detergent lipases, such as Lipolase ^® , Lipolase Ultra ^® and Lipoprime ^® , are sold e.g. by NOVOZYMES A/S. Suitable mannanases, such as Mannanaway ^® , are sold by NOVOZYMES A/S.

The enzymes can optionally be present in the detergent. When used, the enzymes are usually present in an amount of 0.01-5 wt-%, preferably 0.05-5 wt-% and more preferably 0.1-4 wt-%, based on the total weight of the detergent.

The detergent may also be formulated as an aqueous liquid comprising 5-50, preferably 10- 35 wt-% of water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt-% of water. Non-aqueous liquid detergent compositions can contain other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used. The detergents may contain from 5 wt-% to 90 wt-%, typically 10 wt-% to 50 wt-% of such carriers. The detergents can also be present as the so-called "unit liquid dose" form.

Highly preferred are the following detergent compositions: a) Granular detergent compositions comprising 1-25 wt-% alkylbenzenesulfonat.es having from 9 to 15 carbon, 1-15 wt-% Na ₂ CO3, 1-15 wt-% alkalimetalphosphate, 1-15 wt-% sodium salts of silicates, 5-35 wt-% sodium sulfate and 0-1 wt-% protease; especially granular detergent compositions comprising 10-25 wt-% alkylbenzenesulfonat.es having from 9 to 15 carbon, 8-15 wt-% Na ₂ CO ₃ , 8-15 wt-% alkalimetalphosphate, 5-15 wt-% sodium salts of silicates, 20-35 wt-% sodium sulfate and 0-1 wt-% protease. b) Granular detergent compositions comprising 1-15 wt-% alkylbenzenesulfonat.es, 0-6 wt-% alkylsulphates having 7-19 carbon, 1-8 wt-% non-ionic surfactants based on alkylethylenoxides, 0-5 wt-% of a polymer based on acrylic acid as one of the repeating units, 1-15 wt-% bleaching agent such as sodiumpercarbonate, 1-6 wt-% bleach activator such as

TAED, 0-2 wt-% emzymes such as protease and amlyse and 0-0.5 wt-% of a fluorescent whitening agent; especially granular detergent compositions comprising 5-15 wt-% alkylbenzenesulfonat.es, 0-

6 wt-% alkylsulphates having 7-19 carbon, 2-8 wt-% non-ionic surfactants based on alkylethylenoxides, 0-5 wt-% of a polymer based on acrylic acid as one of the repeating units,

5-15 wt-% bleaching agent such as sodiumpercarbonate, 2-6 wt-% bleach activator such as

TAED, 0-2 wt% emzymes such as protease and amlyse and 0-0.5 wt-% of a fluorescent whitening agent. c) A detergent bar comprising 1-30 wt-% alkylbenzenesulfonat.es, 1-20 wt-% alkalimetalphosphates, 5-40 wt-% Na ₂ CO ₃ and 0-2 wt-% carboxymethylcellulose; especially a detergent bar comprising 5-20 wt-% alkylbenzenesulfonat.es, 5-15 wt-% alkalimetalphosphates, 15-30 wt-% Na ₂ CO ₃ and 0.5-2 wt-% carboxymethylcellulose

It is to be understood that the above detergents can contain further ingredients, like additives or water. Wt-% are based on the total weight of the detergent.

Yet another aspect of the invention is a fabric softening composition for improving the whiteness of fiber materials selected from the group consisting of polyester, polyamide and polyacrylonitrile comprising a composition for use in laundry processes which comprises

0.1 to 10 parts of the compound of formula (1 ) or (2)

99.9 to 90 parts of a non-ionic surfactant.

Compound (1 ) is preferred in the detergent or rinsing compositions.

In a further embodiment of the present invention the fiber materials are treated in the rinse step of a laundry process. In this process it is also possible to add a fabric softener.

Fabric softening compounds, especially hydrocarbon fabric softening compounds, suitable for use herein are selected from the following classes of compounds:

(i) Cationic quaternary ammonium salts. The counter ion of such cationic quaternary ammonium salts may be a halide, such as chloride or bromide, methyl sulphate, or other ions well known in the literature. Preferably the counter ion is methyl sulfate or any alkyl sulfate or any halide.

Examples of cationic quaternary ammonium salts include but are not limited to:

(1 ) Acyclic quaternary ammonium salts having at least two C ₈ to C ₃ o, preferably Ci ₂ to C ₂₂ alkyl or alkenyl chains, such as: ditallowdimethyl ammonium methylsulfate, di(hydrogenated tallow)dimethyl ammonium methylsulfate, di(hydrogenated tallow)dimethyl ammonium methylchloride, distearyldimethyl ammonium methyl-sulfate, dicocodimethyl ammonium methylsulfate and the like. It is especially preferred if the fabric softening compound is a water insoluble quaternary ammonium material which comprises a compound having two Ci ₂ to Ci8 alkyl or alkenyl groups connected to the molecule via at least one ester link. It is more preferred if the quaternary ammonium material has two ester links present. An especially preferred ester-linked quaternary ammonium material for use in the invention can be represented by the formula:

wherein each Ri ₃₆ group is independently selected from Ci to C ₄ alkyl, hydroxyalkyl or C ₂ to C ₄ alkenyl groups; T is either -0-C(O)- or -C(O)-O-, and wherein each Ri ₃₇ group is independently selected from C ₃ to C ₂₃ alkyl or alkenyl groups; and e is an integer from 0 to 5.

A second preferred type of quaternary ammonium material can be represented by the formula:

0-C(O)-R 137

( ^R ₁₃₆ ) ₃ ^N+ — ( ^CH 2) _e -CH

CH ₂ -O-C(O)-R ₁₃₇

wherein R ₁₃₆ , e and Ri ₃₇ are as defined above.

(2) Cyclic quaternary ammonium salts of the imidazolinium type such as di(hydrogenated tallow)dimethyl imidazolinium methylsulfate, 1-ethylene-bis(2-tallow-1 -methyl) imidazolinium methylsulfate and the like;

(3) Diamido quaternary ammonium salts such as: methyl-bis(hydrogenated tallow amidoethyl)-2-hydroxethyl ammonium methyl sulfate, methyl bi(tallowamidoethyl)-2- hydroxypropyl ammonium methylsulfate and the like;

(4) Biodegradable quaternary ammonium salts such as N,N-di(tallowoyl-oxy-ethyl)-N,N- dimethyl ammonium methyl sulfate and N,N-di(tallowoyl-oxy-propyl)-N,N-dimethyl ammonium methyl sulfate. Biodegradable quaternary ammonium salts are described, for example, in U.S. Patents 4,137,180, 4,767,547 and 4,789,491 incorporated by reference herein.

Preferred biodegradable quaternary ammonium salts include the biodegradable cationic diester compounds as described in U.S. Patent 4,137,180, herein incorporated by reference.

(ii) Tertiary fatty amines having at least one and preferably two C ₈ to C ₃₀ , preferably Ci ₂ to C ₂₂ alkyl chains. Examples include hardened tallow-di-methylamine and cyclic amines such as 1-(hydrogenated tallow)amidoethyl-2-(hydrogenated tallow) imidazoline. Cyclic amines, which may be employed for the compositions herein, are described in U.S. Patent 4,806,255 incorporated by reference herein.

(iii) Carboxylic acids having 8 to 30 carbons atoms and one carboxylic group per molecule. The alkyl portion has 8 to 30, preferably 12 to 22 carbon atoms. The alkyl portion may be linear or branched, saturated or unsaturated, with linear saturated alkyl preferred. Stearic acid is a preferred fatty acid for use in the composition herein. Examples of these carboxylic acids are commercial grades of stearic acid and palmitic acid, and mixtures thereof, which may contain small amounts of other acids.

(iv) Esters of polyhydric alcohols such as sorbitan esters or glycerol stearate. Sorbitan esters are the condensation products of sorbitol or iso-sorbitol with fatty acids such as stearic acid. Preferred sorbitan esters are monoalkyl. A common example of sorbitan ester is SPAN ^® 60 (ICI) which is a mixture of sorbitan and isosorbide stearates.

(v) Fatty alcohols, ethoxylated fatty alcohols, alkylphenols, ethoxylated alkylphenols, ethoxylated fatty amines, ethoxylated monoglycerides and ethoxylated diglycerides.

(vi) Mineral oils, and polyols such as polyethylene glycol.

These softening compounds are more definitively described in U.S. Patent 4,134,838 the disclosure of which is incorporated by reference herein. Preferred fabric softening compounds for use herein are acyclic quaternary ammonium salts. Mixtures of the above mentioned fabric softening compounds may also be used.

The fabric softeners preferably comprise about 0.001 - 2.0 wt-%, especially 0.015 - 1.5 wt-% of disperse dyes, based on the total weight of the fabric softener.

The fabric softeners preferably comprise about 0.1 to about 95 wt-% of fabric softening compounds, based on the total weight of the fabric softener. Preferred is an amount of 0.5 to 50 wt-%, especially an amount of 2 to 50 wt-% and most preferably an amount of 2 to 30 wt- %.

The fabric softeners may also comprise additives which are customary for standard commercial fabric softeners, for example alcohols, such as ethanol, n-propanol, i-propanol, polyhydric alcohols, for example glycerol and propylene glycol; amphoteric and nonionic surfactants, for example carboxyl derivatives of imidazole, oxyethylated fatty alcohols, hydrogenated and ethoxylated castor oil, alkyl polyglycosides, for example decyl polyglucose and dodecylpolyglucose, fatty alcohols, fatty acid esters, fatty acids, ethoxylated fatty acid glycerides or fatty acid partial glycerides; also inorganic or organic salts, for example water- soluble potassium, sodium or magnesium salts, non-aqueous solvents, pH buffers, perfumes, dyes, hydrotropic agents, antifoams, anti redeposition agents, enzymes, optical brighteners, antishrink agents, stain removers, germicides, fungicides, dye fixing agents or

dye transfer inhibitors (as described in WO-A-02/02865), antioxidants, corrosion inhibitors, wrinkle recovery or wet soiling reduction agent, such as polyorganosiloxanes. The latter two additives are described in WO0125385.

Such additives are preferably used in an amount of 0 to 30 wt-%, based on the total weight of the fabric softener. Preferred is an amount of 0 to 20 wt-%, especially an amount of 0 to 10 wt-% and most preferably an amount of 0 to 5 wt-%, based on the total weight of the fabric softener.

The fabric softeners are preferably in liquid aqueous form. The fabric softeners preferably contain a water content of 25 to 90 wt-%, based on the total weight of the composition. More preferably the water content is 50 to 90 wt-%, especially 60 to 90 wt-%.

The fabric softeners preferably have a pH value from 2.0 to 9.0, especially 2.0 to 5.0.

These fabric softener compositions are traditionally prepared as dispersions containing for example up to 30 wt-% of active material in water. They usually have a turbid appearance. However, alternative formulations usually containing actives at levels of 5 to 40 wt-% along with solvents can be prepared as microemulsions, which have a clear appearance (as to the solvents and the formulations see for example US-A-5,543,067 und WO-A-98/17757).

Definitions and preferences given above apply equally for all aspects of the invention.

The following examples illustrate the invention

Materials used ECE 77 detergent; Dobanol® 23-6.5;

Compound (1 ) (2);

Comparative example 1a

To 2000 ml tap water 0.8g Dobanol® 23-6.5 and 8g of detergent ECE 77 are added. The detergent mixture is stirred for a while.

To 200 ml of this detergent solution a white polyester fabric is added and washed for 15 minutes at 30° C in a laboratory washing machine, Linitest of Atlas Corp.

The washed fabric is rinsed with tap water, spin dried and finally dried at 60 ⁰ C in the dark.

Comparative Example 1 b

The procedure of comparative example 1 is repeated except that additionally 10mg of the compound of formula (1 ) are added to the initial detergent mixture.

Example 1

To 5g Dobanol® 23-6.5 61.1 mg of the compound of formula (1 ) are added and homogenously mixed. 0.8g of this homogenous mixture and 8 g of detergent ECE 77 are added to 2000 ml tap water. To 200 ml of this detergent solution a white polyester fabric is added and washed for 15 minutes at 30° C in a laboratory washing machine, Linitest of Atlas Corp. The washed fabric is rinsed with tap water, spin dried and finally dried at 60 ⁰ C in the dark.

The three samples are conditioned at room temperature over night and their reflectance spectra are taken using a Datacolor SF 500 spectrophotometer. The whiteness grades calculated with the Ganz formula are given in Table 1.

Table 1

Example 1 exhibits a significant increase in whiteness compared with the comparative examples.

Comparative example 2a

To 2000 ml tap water 0.8g Dobanol® 23-6.5 and 8g of detergent ECE 77 are added. The detergent mixture is stirred for a while.

To 200 ml of this detergent solution a white polyester fabric is added and washed for 15 minutes at 30° C in a laboratory washing machine, Linitest of Atlas Corp.

The washed fabric is rinsed with tap water, spin dried and finally dried at 60 ⁰ C in the dark.

Comparative Example 2b

The procedure of comparative example 2a is repeated except that additionally 9.9 mg of the compound of formula (2) are added to the initial detergent mixture.

Example 2

To 5g Dobanol® 23-6.5 6 1.0 mg of the compound of formula (2) are added and homogenously mixed. 0.79 g of this homogenous mixture and 8 g of detergent ECE 77 are added to 2000 ml tap water. To 200 ml of this detergent solution a white polyester fabric is added and washed for 15 minutes at 30° C in a laboratory washing machine, Linitest of Atlas Corp. The washed fabric is rinsed with tap water, spin dried and finally dried at 60 ⁰ C in the dark.

The three samples are conditioned at room temperature over night and their reflectance spectra are taken using a Datacolor SF 500 spectrophotometer. The whiteness grades calculated with the Ganz formula are given in Table 2.

Table 2

Example 2 exhibits a significant increase in whiteness compared with the comparative examples.