CN118647704A - Laundry composition - Google Patents

Abstract

The present invention relates to a solid detergent composition, in particular a solid laundry detergent composition having good biodegradability. There is a need to provide a solid detergent composition having good biodegradability and providing good cleaning performance and good whiteness benefits. It is therefore an object of the present invention to provide a laundry detergent composition having good biodegradability whilst providing fabric care benefits and maintaining good cleaning performance. The inventors have surprisingly found that combining cellulases with specific low levels of fluorescers and/or hueing dyes provides a significant improvement in whiteness benefits. The composition was also found to provide good biodegradability.

Description

Laundry composition

Technical Field

The present invention relates to a solid laundry composition, and more particularly to a solid laundry detergent composition having good biodegradability.

Background Art

From a consumer's perspective, graying, dulling and yellowing of fabrics are problems that need to be addressed. One of the reasons for graying or yellowing of fabrics is due to soil redeposition. In order to reduce soil redeposition, polycarboxylate polymers have been included in laundry compositions to act as anti-redeposition agents.

Copolymers of acrylic acid and maleic acid are well known anti-redeposition agents for use in solid laundry detergent compositions. Copolymers of acrylic acid and maleic acid are also known to act as structuring agents in solid laundry detergent compositions, particularly in spray-dried detergent granules. However, a disadvantage of incorporating polycarboxylate polymers in detergent compositions is that these polymers are not readily biodegradable.

Laundry detergent formulators may also add brighteners (such as fluorescent agents) and hueing dyes to the compositions to improve the whiteness of clothes and reduce yellowing with repeated washings, especially on white fabrics. However, a disadvantage of adding fluorescent agents and hueing dyes to detergent compositions is that these brighteners are not readily biodegradable.

WO 2009/154934 A1 (Procter & Gamble Company) discloses a laundry composition having a fluorescent agent and cellulase.

JP2003 105389A (Lion Corp) discloses a detergent composition for controlling bacteria on fabrics to prevent odor, and discloses a detergent composition comprising 0.5 wt% of acrylic acid-maleic acid copolymer (AA/MA ratio 70:30) and 0.2 wt% of cellulase.

WO 2011/109320A1 (P&G) discloses a solid laundry detergent composition that provides good cleaning performance even under low temperature conditions, and discloses a granular dry laundry detergent composition comprising 1.7 wt% STPP, 0.3 wt% polyacrylic acid/sodium maleate copolymer (70:30 ratio), 0.6 wt% carboxymethyl cellulose, 0.5 wt% HEDP, 5 wt% sodium percarbonate and 53 ppm cellulase.

EP 2377914 A1 (P&G, 2011) discloses a solid fabric treatment detergent composition for providing good cold water cleaning performance, and discloses a composition comprising 0.6 wt % STPP, 0.3 wt % polyacrylic acid/sodium maleate copolymer (70:30 ratio), 0.5 wt % hydrophobically modified carboxymethyl cellulose, 0.3 wt % HEDP, 7 wt % sodium percarbonate and 53 ppm cellulase.

WO 99/13040A1 (P&G) discloses a detergent composition for solving the bleach instability problem of chelating agents and providing improved encrustation chelation and improved bleaching performance. The document discloses a composition comprising 0.5 wt% MA/AA (1:4 maleic acid/acrylic acid copolymer), 1 wt% sodium perborate bleach and 0.2 wt% cellulase.

JP 2007/070613 A (Kao) discloses a granular laundry detergent composition which provides excellent softening and prevents redeposition on fibrous products during washing. The document discloses a granular laundry composition comprising 0.1 wt% cellulase, 0.5 wt% CMC and 0.5 wt% acrylic acid maleic acid copolymer.

There is a need to provide detergent compositions which have good biodegradability and which provide good cleaning performance and good whiteness benefits.

Therefore, there remains a need for a solid laundry composition which provides good fabric cleaning performance, a good biodegradability index, good whiteness maintenance and very good powder properties, while preferably having low levels of alkaline builders.

It is therefore an object of the present invention to provide a solid laundry composition having good biodegradability.

It is also an object of the present invention to provide a solid laundry composition having good whiteness benefits.

Another object of the present invention is to provide a solid laundry composition which provides fabric care benefits while maintaining good cleaning performance.

It is a further object of the present invention to provide a solid laundry composition which provides a wash liquor with lower alkalinity compared to conventional laundry detergent compositions, yet still maintains good cleaning performance.

Still another object of the present invention is to provide a solid laundry composition which provides fabric care benefits by comprising lower levels of bleach or no bleach while maintaining good cleaning performance and whiteness performance.

Summary of the invention

The present inventors have surprisingly found that combining cellulase with specific optical brighteners provides a significant improvement in whiteness benefit. It has also been found that the composition provides good biodegradability. It has surprisingly been found that the combination of cellulase and specific optical brighteners in solid laundry compositions provides improved whiteness benefit even at low levels of the specific optical brighteners.

According to a first aspect of the present invention, there is disclosed a solid laundry composition comprising:

(i) cellulase;

(ii) Optical brightener represented by general formula (I)

in:

_R1 are the same or different and are selected from _-NH2 , -NH( _C1 to _C4 alkyl), -N( _C1 to _C4 alkyl) ₂ , -NH( _C2 to _C4 hydroxyalkyl), -N( _C2 to _C4 hydroxyalkyl) ₂ and -N( _C1 to _C4 alkyl)( _C2 to _C4 hydroxyalkyl);

R ₃ is independently selected from hydrogen (-H), C ₁ to C ₄ alkyl, C ₁ to C ₄ hydroxyalkyl;

M is independently selected from hydrogen, an alkali metal atom, ammonium, and a cation formed from an amine.

According to a second aspect of the present invention, there is disclosed a method for washing a textile surface using a solid laundry composition according to the first aspect of the present invention, the method comprising the following steps:

i) preparing an aqueous wash liquor by contacting a solid laundry composition according to the first aspect with a liquid;

ii) soaking the textile surface in a wash liquor for a predetermined period of time; and

iii) optionally rinsing the textile surface.

According to a third aspect of the present invention, there is disclosed the use of the cellulase according to the first aspect and an optical brightener of formula (I) in a solid laundry composition to provide improved cleaning performance.

These and other aspects, features and advantages will become apparent to those of ordinary skill in the art by reading the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be used in any other aspect of the present invention. The word "comprising" is intended to mean "including", but not necessarily "consisting of" or "composed of". In other words, the steps or options listed do not need to be exhaustive. It should be noted that the examples given in the following description are intended to illustrate the present invention and are not intended to limit the present invention to those examples themselves.

Similarly, unless otherwise indicated, all percentages are weight/weight percentages. Except in the operating examples and comparative examples, or where otherwise explicitly indicated, all numbers in this specification representing the amount of material or reaction conditions, the physical properties of the material and/or the use thereof are understood to be modified by the word "about". Numerical ranges expressed in the format of "x to y" are understood to include x and y. When multiple preferred ranges are described in the form of "x to y" for a particular feature, it will be understood that all ranges combining different endpoints are also considered.

DETAILED DESCRIPTION

According to a first aspect of the present invention, a solid laundry composition having cellulase and an optical brightener is disclosed.

Cellulase :

According to a first aspect of the present invention, a solid laundry composition comprising cellulase is disclosed.

The term cellulase refers to an enzyme that hydrolyzes cellulosic materials. Such enzymes include those selected from endoglucanases (e.g., EC 3.2.1.4), cellobiohydrolases, beta-glucosidases, or combinations thereof. The cellulase can, for example, be a single component or a mixture of endo-1,4-beta-glucanases (also referred to as endoglucanases).

Suitable cellulases include those from bacterial origin, fungal origin or its combination. Chemically modified or protein engineered mutants are also contemplated. Suitable cellulases include those from Bacillus, Pseudomonas, Humicola, Myceliophthora, Fusarium, Thielavia, Trichoderma and Acremonium. Exemplary cellulases include those from Humicola insolens (US 4,435,307) or from Trichoderma, such as T. reesei or T. viride. Other suitable cellulases are from Thielavia, e.g., Thielavia terrestris as described in WO 96/29397, or fungal cellulases produced by Myceliophthora thermophila and Fusarium oxysporum as disclosed in US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259 and WO 91/17244. Also relevant are cellulases from Bacillus, as described in WO 02/099091 and JP 2000210081. Suitable cellulases are alkaline or neutral cellulases, preferably those having color care benefits. Examples of cellulases are described in EP 0 495 257, EP 0 531 372, WO 96/11262, WO 96/29397, WO 98/08940. Other examples are cellulase variants, such as those described in WO 94/07998, EP 05/531315, US 5,457,046, US 5,686,593, US 5,763,254, WO 95/24471, WO 98/12307.

Other cellulases are endo-β-1,4-glucanases having a sequence at least 97% identical to the amino acid sequence from position 1 to position 773 of SEQ ID NO: 2 of WO 2002/099091, or Family 44 xyloglucanases having a sequence at least 60% identical to positions 40-559 of SEQ ID NO: 2 of WO 2001/062903.

Commercially available cellulases include Premium, Classic, (Novozymes A/S), Puradax HA and Puradax EG (available from Genencor International Inc.) and KAC-500(B) ^™ (Kao Corporation).

In one embodiment, the cellulase is obtained from Humicola, in particular Humicola insolens. In another embodiment, the cellulase is obtained from Bacillus, in particular Bacillus akibai. In another embodiment, the cellulase is obtained from Paenibacillus, in particular Paenibacillus polmyxa. In yet another embodiment, the cellulase is obtained from Melanocarpus, in particular Melanocarpus albomyces.

Preferably, the cellulase comprises the amino acid sequence of SEQ ID NO: 10, SEQ ID NO: 11, SEQ ID NO: 12 or SEQ ID NO: 13. More preferably, the cellulase comprises an amino acid sequence having at least 60%, such as at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of SEQ ID NO: 10, SEQ ID NO: 10, SEQ ID NO: 11, SEQ ID NO: 12 or SEQ ID NO: 13. In one aspect, the cellulase comprises an amino acid sequence that differs from a cellulase comprising the amino acid sequence of SEQ ID NO: 10, SEQ ID NO: 10, SEQ ID NO: 11, SEQ ID NO: 12, or SEQ ID NO: 13 by up to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) amino acids.

Examples of these cellulase variants are described in WO 2021/058023 A1.

Cellulase is preferably formulated into a solid form, preferably a granular form. Granular forms can be prepared as disclosed in US 4,106,991 and US 4,661,452, and can optionally be coated by methods known in the art. Examples of waxy coating materials are poly(ethylene oxide) products (polyethylene glycol, PEG) having an average molecular weight of 1000 to 20000, ethoxylated nonylphenols with 16 to 50 ethylene oxide units; ethoxylated fatty alcohols, wherein the alcohol contains 12 to 20 carbon atoms and wherein there are 15 to 80 ethylene oxide units; fatty alcohols; fatty acids; and monoglycerides, diglycerides and triglycerides of fatty acids.

Also preferably, the cellulase can be formulated into granules, preferably in combination with one or more other enzymes. Non-limiting examples of other preferred enzymes include proteases, amylases, lipases, cellulases and/or nucleases (e.g., DNA enzymes, RNA enzymes). Each enzyme will then be present in more granules, ensuring that the enzyme is more evenly distributed in the detergent. This also reduces the physical separation of different enzymes caused by different particle sizes. Methods for producing multi-enzyme co-granules for the detergent industry are known to those skilled in the art. Another example of a cellulase in co-granular form is disclosed in WO 2013/188331 A1.

Also preferred are enzymes in the form of granules having a core comprising cellulase and surrounded by one or more coating layers. The coating layers provide improved storage stability, reduced dust formation, or improve the color or appearance of the granules. The coating layers may include salts, polyethylene glycol (PEG), methylhydroxypropylcellulose (MHPC), and polyvinyl alcohol (PVA).

Cellulase can also be formulated in encapsulated form. Cellulase can be encapsulated in a matrix, preferably a water-soluble or water-dispersible matrix (e.g., water-soluble polymer particles), such as described in WO 2016/023685. An example of a water-soluble polymer matrix is a matrix composition comprising polyvinyl alcohol.

Enzymes can also be encapsulated in core-shell microcapsules, for example as described in WO 2015/144784. Such core-shell capsules can be prepared using a variety of techniques known in the art, for example by using interfacial polymerization of water-in-oil or oil-in-water emulsions, where the polymers are cross-linked at the surface of the droplets in the emulsion (the interface between water and oil), thereby forming a wall/membrane around each droplet/capsule.

Preferably, the cellulase may also be present as a multi-enzyme co-granule which, in addition to the cellulase, comprises one or more additional preferred enzymes selected from lipase, catalase, peroxidase, laccase, first wash lipase, protease, mannanase, reductase, oxidase, nuclease, DNase, amylase or a mixture thereof.

Preferably, the level of cellulase in the composition is in the range of 0.0001 wt% to 0.5 wt%. Preferably, the amount of cellulase present in the composition is at least 0.001 wt%, also preferably at least 0.01 wt%, also preferably at least 0.02 wt%, most preferably at least 0.03 wt%, but typically does not exceed 0.3 wt%, also preferably does not exceed 0.25 wt%, most preferably does not exceed 0.2 wt%. The level of enzyme present in the composition preferably relates to the level of enzyme as pure protein.

Brightener

According to a first aspect of the present invention, a solid detergent composition comprising an optical brightener is disclosed.

Optical brighteners:

The disclosed solid laundry compositions comprise an optical brightener, which is preferably present in the composition in an amount ranging from 0.01 wt% to 0.4 wt%, preferably from 0.05 wt% to 0.3 wt%, also preferably from 0.05 wt% to 0.2 wt%.

Optical brighteners are compounds that absorb ultraviolet light and re-emit energy in the form of visible light. Specifically, the optical brighteners useful in the present invention absorb light in the ultraviolet and violet regions between 300nm and 400nm of the electromagnetic spectrum, and re-emit light at a wavelength of 420nm to 450nm. For the purpose of detergent products, light is typically emitted in the visible spectrum, preferably blue or green light. Optical brighteners may also be referred to as fluorescent whitening agents (FWAs), fluorescent brighteners (FBAs), fluorescent agents, fluorescent agents, optical brightening agents (OBAs), and fluorescent dyes.

The disclosed solid laundry composition comprises an optical brightener represented by the general formula (I):

in:

_R1 are the same or different and are selected from _-NH2 , -NH( _C1 to _C4 alkyl), -N( _C1 to _C4 alkyl) ₂ , -NH( _C2 to _C4 hydroxyalkyl), -N( _C2 to _C4 hydroxyalkyl) ₂ and -N( _C1 to _C4 alkyl)( _C2 to _C4 hydroxyalkyl);

R ₃ is independently selected from hydrogen (-H), C ₁ to C ₄ alkyl, C ₁ to C ₄ hydroxyalkyl;

M is independently selected from hydrogen, an alkali metal atom, ammonium, and a cation formed from an amine.

R ₁ is selected from -NH ₂ , -NH (C ₁ to C ₄ alkyl), -N (C ₁ to C ₄ alkyl) ₂ , -NH (C ₂ to C ₄ hydroxyalkyl), -N (C ₂ to C ₄ hydroxyalkyl) ₂ and -N (C ₁ to C ₄ alkyl) (C ₂ to C ₄ hydroxyalkyl). The alkyl group may preferably be branched or unbranched. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, isobutyl. Non-limiting examples of hydroxyalkyl groups include hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl.

More preferably, each R ₁ group is independently selected from -N-mono(1-hydroxyethyl)amine, -N-mono(2-hydroxyethyl)amine, mono-(2-hydroxyethyl)-N-methylamino, di-(2-hydroxyethyl)amino, di-(2-hydroxypropyl)amino and N-(2-hydroxyethyl)-N-methylamino. Preferably, R ₁ are the same or different.

_R3 is independently selected from hydrogen (-H), _C1 to _C4 alkyl and _C1 to _C4 hydroxyalkyl. Preferably, _C1 to _C4 alkyl is a primary, secondary or tertiary alkyl. More preferably, _C1 to _C4 alkyl is a primary alkyl. Preferably, _C1 to _C4 hydroxyalkyl is a primary, secondary or tertiary alkyl.

The alkyl group may be preferably branched or unbranched. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, isobutyl. Non-limiting examples of hydroxyalkyl groups include hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. Preferably, R ₃ is the same or different.

M is independently selected from hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, preferably selected from Na ⁺ and K ⁺ . More preferably, M represents sodium.

Non-limiting examples of optical brighteners of formula (I) include

Disodium 4,4'-bis[4-amino-6-morpholin-1,3,5-triazin-2-yl)amino]stilbene-2,2'-disulfonic acid

Commercially available optical brighteners of formula (I) include Kayaphor B, Kayaphor AB, Mikephor BP, Lemonite RSJ (supplier Khyati Chemical Pvt. Ltd), Megawhite DK (supplier Meghmani Organics Ltd) and Deepwhite MDM powder (supplier Deepak nitrite).

Preferably, the molecular weight of disodium 4,4′-bis[(4-anilino-6-hydroxyethylamino-1,3,5-triazin-2-yl)amino]stilbene-2,2′-disulfonate is 872.84, and the molecular formula is C ₃₆ H ₃₄ N ₁₂ Na ₂ O ₈ S ₂ .

Most preferably, the composition of the invention comprises 0% by weight of Tinopal CBSX. The composition preferably comprises 0% by weight of optical brighteners of the DASCC type, 0% by weight of anilino-substituted bistriazine derivatives of 4,4'-diaminostilbene-2,2'-disulfonic acid based on cyanuric chloride (CC), in particular 0% by weight of disodium 4,4'-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino]stilbene-2,2'-disulfonic acid.

Typically, fluorescent agents are commercially available and used in the form of their alkali metal salts, preferably the sodium salt. The optical brightener may be added in particulate form or as a premix with a suitable solvent (eg, nonionic surfactant, monoethanolamine, propylene glycol).

Solid laundry compositions of the present invention preferably comprise from 0.01 wt% to 0.4 wt% of an optical brightener of general formula (I).

Preferably, the amount of the optical brightener of formula (I) in the composition ranges from 0.05 wt% to 0.3 wt%, more preferably from 0.05 wt% to 0.2 wt% in the composition.

Preferably, the amount of optical brightener in the composition is at least 0.02 wt%, preferably at least 0.025 wt%, preferably at least 0.03 wt%, and most preferably at least 0.05 wt%. However, it is usually not more than 0.4 wt%, preferably not more than 0.35 wt%, preferably not more than 0.3 wt%, and most preferably not more than 0. wt%.

Color dye

In addition to the optical brightener, preferably the solid laundry composition according to the first aspect of the invention may comprise a hueing dye, preferably in an amount ranging from 0.0005 wt% to 0.005 wt%, further preferably from 0.0005 wt% to 0.004 wt%, further more preferably from 0.0005 wt% to 0.002 wt%. More preferably, the solid laundry composition according to the first aspect of the invention is substantially free of hueing dyes.

During the washing or rinsing step of the washing process, the hueing dye is deposited on the fabric, thereby providing a visible hue to the fabric. The hueing dye used in the present invention is preferably blue or purple. In this regard, the hueing dye imparts a blue or purple hue to the white cloth, with a hue angle of 240 to 345, more preferably 260 to 320, and most preferably 270 to 300. The white cloth used is a bleached non-mercerized woven cotton sheet.

The hueing dye preferably has a calculated logP (octanol-water partition coefficient) of 0.5 to 3, more preferably 1.0 to 2.5. The LogP values are based on atoms and are calculated using Molecular Modeling Pro (Chem Version 5.2.2, Most preferably, the dye is uncharged at pH=7.

The hueing dye preferably has a peak absorption wavelength of 550nm to 650nm, preferably 570nm to 630nm. Combinations of dyes that together have a visual effect on the human eye as a single dye with a peak absorption wavelength of 550nm to 650nm, preferably 570nm to 630nm may also be suitable. This can be provided, for example, by mixing red and green-blue dyes to produce a blue or purple hue.

Hueing dyes are colored organic molecules that are soluble in aqueous media containing surfactants. Dyes are described in "Industrial Dyes", Wiley VCH 2002, K. Hunger (ed.).

Dyes are listed in the Color Index International published by the Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists. Many examples of hueing dyes exist in the categories of basic dyes, solvent dyes, acid dyes, direct dyes and disperse dyes. The dye is preferably selected from the categories of basic dyes, acid dyes and direct dyes.

The dye chromophore is preferably selected from the group consisting of: monoazo, triphenylmethane, naptholactam, azine and anthraquinone. Monoazo, azine and anthraquinone are most preferred.

Preferred hueing dyes are:

(a) Acid azine dyes as described in WO 2008/017570, preferably Acid Blue 59, Acid Blue 98 and Acid Violet 50.

(b) Cationic azine dyes, preferably blue or violet cationic phenazine dyes of the following form, which are not covalently bound to negatively charged substituents. Preferably, the cationic phenazine dyes are as described in WO 2011/042372A1. The cationic phenazine may be selected from:

in:

_X1 is selected from _: -F; -N( _CH3 ) ₂ ; -N( _CH2CH3 ) ₂ ; -N(H) _COCH3 ; and -N(H) _COCH2CH3 ; preferably selected from -N( _CH3 ) ₂ and -N(H) _{COCH3 .}

_X2 is selected from: -F; -N( _CH3 ) ₂ ; -N( _CH2CH3 ) ₂ ; -N( _H ) _COCH3 ; and -N(H) _COCH2CH3 ; preferably selected from -F, -N( _CH3 ) ₂ and -N(H) _{COCH3 .}

_X3 is selected from _{: -H; -F; -CH3; -C2H5; -OCH3 ; and -OC2H5 ; preferably} selected from -H; -F; _-CH3 ; and preferably _X3 is in the 4-position.

_X4 is selected from: -H; _{-CH3 ; -C2H5 ; -OCH3} ; _{and -OC2H5} ; preferably _X4 is H.

_Y1 is selected from: -OH; _-OCH2CH2OH ; -CH(OH) _CH2OH ; and preferably _Y1 is _-OH .

_Y2 is selected from: -OH; _-OCH2CH2OH ; -CH(OH) _CH2OH ; -OC( _O ) _CH3 ; and C(O) _OCH3 . Preferably _Y2 is -OH. Preferably, the _Y2 substituents are the same.

Preferably, the phenazine dye has a counterion ^An- due to its positive charge. ^An- can vary widely and is preferably an anion such as ^RCOO- , _BPh4- , ^CLO4- , _BF4- ^{, PF6-} , _RSO3- , _SO42- ^, _NO3- , ^F- , ^{Cl- ,} _Br- or ^I- , wherein R _is hydrogen, an optionally substituted _alkyl or an optionally substituted aryl. Preferably _, ^{An- is} selected _{from CH3SO3-} ^, _CH3CO2- , ^{BF4- , Cl- , F-} , ^Br- and ^{I- .}

Preferably these include:

(c) Cationic azo dyes, preferably cationic monoazo dyes. Cationic azo dyes preferably have a cationic group on the chain. The dye may also have an anionic group.

(d) The following hydrophobic dyes:

(i) Solvent Violet 13 and Disperse Violet 27 and anthraquinone structures having the following anthraquinone structure (I):

wherein R ₁ , R ₄ , R ₅ and R ₈ are independently selected from -H, -OH, -NH ₂ , NHCOCH ₃ and -NO ₂ , such that at most only one -NO ₂ group and at most two -H are present as R ₁ , R ₄ , R ₅ and R ₈ substituents; and R ₂ , R ₃ , R ₆ and R ₇ are selected from -H, F, Br, Cl or -NO ₂ and -O aryl.

(ii) a monoazo dye selected from the group consisting of compounds of the following formula:

Wherein _R3 and _R4 are optionally substituted _C2 to _C12 alkyl chains optionally having ether (-O-) or ester bonds, which are optionally substituted by -Cl, -Br, -CN, _-NO2 and _-SO2CH3 ; and D represents an aromatic or heteroaromatic group. The aromatic ring may further preferably be substituted by -Cl, -Br, -CN, _CH3 , _{C2H5 , -NO2 , -SO2CH3} and _-NHCOR , and R is selected from _{CH3 , C2H5 and CH2Cl} .

The most preferred azo dyes are of the following form:

wherein X and Y are selected from H, CH ₃ , C ₂ H ₅ , -Cl, -Br, -CN, -NO ₂ , -SO ₂ CH ₃ and -NHCOR and R is selected from CH ₃ , C ₂ H ₅ and CH ₂ Cl. Preferably X is NHCOCH ₃ or NHCOCH ₂ Cl.

(e) Direct dyes as described in WO 2009/132870 A1. Preferably, the dye is a disazo or trisazo dye. Most preferred is Direct Violet 9.

(f) Reactive dyes as described in WO 2009/132870 A1. Preferably, the dye is Reactive Blue 19, Reactive Blue 163, Reactive Blue 182, Reactive Blue 96.

The tinting of white garments can be done with any color according to consumer preference. Blue and violet are particularly preferred hues, so the preferred dyes or dye mixtures are those that produce blue or violet hues on white fabrics.

A variety of suitable solvent dyes and disperse dyes are available. However, detailed toxicological studies have shown that many of these dyes are possible carcinogens, such as disperse blue 1. Such dyes are not preferred. Most preferably, the dye used in the present invention is disperse violet 28.

Examples of hueing dyes are described in WO08017570A1 , WO11098356A1 , WO09141172A1 , WO09141173A1 , and are incorporated herein by reference. Hueing dyes are discussed in WO 2005/003274, WO 2006/032327 (Unilever), WO 2006/032397 (Unilever), WO 2006/045275 (Unilever), WO 2006/027086 (Unilever), WO 2008/017570 (Unilever), WO 2008/141880 (Unilever), WO 2009/132870 (Unilever), WO 2009/141173 (Unilever), WO 2010/099997 (Unilever), WO 2010/102861 (Unilever), WO 2010/148624 (Unilever), WO2008/087497 (P&G), WO2011/011799 (P&G), WO2012/054820 (P&G), WO2013/142495 (P&G) and WO2013/142495 (P&G).

The composition according to the invention may further optionally comprise dye-clay conjugates and other organic and inorganic pigments.

Also preferred are solid laundry compositions having a mixture of 0.01 wt% to 0.4 wt% of an optical brightener according to the invention and 0 to 0.005 wt% of a hueing dye.

Replacement of polysaccharides:

According to the first aspect of the present invention, preferably, the composition may comprise a substituted polysaccharide.

Preferably, the substituted polysaccharide has functional groups present on the polysaccharide backbone selected from alkyl, carboxyalkyl, carboxylic acid, alkoxy or salts thereof.

The polysaccharide is chemically modified at one or more available hydroxyl groups of the monosaccharide units to introduce functional groups appropriately by oxidation, grafting, esterification and etherification in an attempt to balance detergent performance and biodegradation.Preferably, the polysaccharide is selected from cellulose, inulin, starch, dextrin and mixtures thereof.

The term dextrin includes a group consisting of dextrin, maltodextrin and cyclodextrin. Preferably, the average degree of polymerization of dextrin is 3 to 200, also preferably 5 to 100, and most preferably 10 to 40. Dextrin is a group of low molecular weight carbohydrates that can be obtained by hydrolyzing starch to form D-glucose units connected by α-(1,4) bonds starting with α-(1,6) glycosidic bonds. Preferably, based on 100% dextrose (glucose), they have a dextrose equivalent of 1% to 30%, preferably 1% to 13%. Dextrose equivalent (DE) is a measure of the amount of reducing sugars present in a sugar product, expressed as a percentage based on dry matter relative to dextrose. Dextrose equivalent gives an indication of the average degree of polymerization (DP) for starch sugars, which is inversely proportional to the molecular weight. The degree of polymerization (DP) is an indicator of the degree of hydrolysis, the DE of unhydrolyzed starch is 0, and the DE value of glucose is 100. Dextrin is produced by starch using enzymes or by drying and heating (thermolysis) under acidic conditions. Maltodextrin consists only of α-(1,4) bonded glucose and has an average degree of polymerization of 10 to 20 and a dextrose equivalent of 3 to 20%, preferably 10 to 20%.

The cyclodextrin can be any known cyclodextrin, such as unsubstituted cyclodextrins containing 6 to 12 glucose monomers, especially α-, β- and γ-cyclodextrins, and/or derivatives thereof, and/or mixtures thereof. α-, β- and γ-cyclodextrins contain 6, 7 and 8 glucose monomer units, respectively, arranged in a donut-shaped ring. Examples of cyclodextrin derivatives suitable for use in the present invention include methyl β-cyclodextrin, hydroxyethyl β-cyclodextrin and hydroxypropyl β-cyclodextrin of different degrees of substitution. Water-soluble cyclodextrin derivatives are preferred cyclodextrin derivatives. Preferably, at least most of the cyclodextrins are α-, β- and/or γ-cyclodextrins, more preferably α- and β-cyclodextrins. A particularly preferred cyclodextrin for use in the present invention is β-cyclodextrin. It is also preferred to use a mixture of cyclodextrins.

Preferably, the level of substituted polysaccharide in the composition is in the range of 0.05 wt% to 5 wt%. Preferably, the amount of substituted polysaccharide present in the composition is at least 0.07 wt%, also preferably at least 0.08 wt%, also preferably at least 0.09 wt%, most preferably at least 0.1 wt%, but usually not more than 4 wt%, also preferably not more than 3 wt%, most preferably not more than 2 wt%.

Alkyl substituted polysaccharides:

Preferably, the substituted polysaccharide is an alkyl substituted polysaccharide. Alkyl substituted polysaccharides include alkyl groups that are typically linear or branched C ₁ to C ₈ alkyl or aralkyl groups. Alkyl substituted polysaccharides are preferably prepared by replacing hydrogen atoms on the hydroxyl groups of the polysaccharide with alkyl and/or aralkyl groups. Preferred alkyl groups are C ₁ to C ₄ alkyl groups, examples being methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Alkyl groups may be substituted by aromatic groups to form arylalkyl groups, for example, such as substituted by phenyl. A preferred arylalkyl group is benzyl. Mixed alkyl substituted polysaccharides may also be used, containing more than one alkyl, aralkyl or functionally substituted alkyl group.

Preferred examples of the alkyl-substituted polysaccharide include methyl cellulose, ethyl cellulose, propyl cellulose or a mixture thereof.

Hydroxyalkyl substituted polysaccharides:

Preferably, the substituted polysaccharide is a hydroxyalkyl substituted polysaccharide. The alkyl and/or aralkyl groups of the alkyl polysaccharide may be further substituted with nonionic, anionic, cationic or nonionic groups. The alkyl or aralkyl groups may be substituted with hydroxy functional groups to form hydroxyalkyl substituted polysaccharides.

Preferred examples of the hydroxyalkyl-substituted polysaccharide include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, ethyl methyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxybutyl cellulose, ethyl hydroxyethyl cellulose or a mixture thereof.

Carboxyalkyl substituted polysaccharides:

Preferably, the substituted polysaccharide is a carboxyalkyl substituted polysaccharide. The alkyl and/or aralkyl groups of the alkyl substituted polysaccharide may be further substituted by nonionic, anionic, cationic or nonionic groups. The alkyl or aralkyl groups may be functionally substituted by carboxyl or carboxylate groups to form carboxyalkyl substituted polysaccharides. When carboxylate groups are present, corresponding counterions are also present, examples being alkali metal ions, such as sodium or potassium, or ammonium ions.

Preferred examples of carboxyalkyl-substituted polysaccharides include carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose. Among carboxymethyl celluloses, preferred examples include sodium carboxymethyl cellulose, cross-linked sodium carboxymethyl cellulose or enzymatically hydrolyzed carboxymethyl cellulose.

Another preferred carboxyl-substituted polysaccharide is a fructan polycarboxylic acid or a salt thereof. Fructan polycarboxylic acid is any oligosaccharide or polysaccharide containing a plurality of defructan units and which has been converted into a polycarboxylic acid. The fructans on which the fructan polycarboxylic acid may be based may have a polydisperse chain length distribution and may have straight or branched chains. Preferably, the fructans contain mainly β-2,1 bonds, as in inulin, but they may also contain β-2,6 bonds, as in levans. Suitable fructans may be derived directly from natural sources, but they may also be modified. Examples of modifications in this case are reactions known per se, which result in an extension or shortening of the chain length. Suitable fructans have an average chain length (degree of polymerization, DP) of at least 2 to about 1000. Preferably, a fructan having a degree of polymerization of at least 3, more preferably at least 6, and most preferably at least 10 up to about 60 is used.

Preferably, the fructan polycarboxylic acid has a degree of substitution of carboxyl groups obtained by oxidation of at least 0.05 per originally dehydrated fructose unit and a degree of substitution of carboxyalkyl or carboxyacyl groups of at least 0.1 per dehydrated fructose unit.

Preferably, the fructan polycarboxylic acid is based on inulin. Inulin is a polysaccharide composed of fructose units in β-2,1 bond, with an α-D-glucopyranose unit at the reducing end of the molecule. The main difference between inulins of different natural sources is the degree of polymerization. Preferably, the degree of polymerization may vary from about 6 to more than 20, more preferably from 6 to 14, and fructan polycarboxylic acids having a degree of polymerization of 9 to 11 are also preferred.

The inulin derivatives used according to the invention are polycarboxylates. Known suitable polycarboxylate derivatives of inulin are, for example, dicarboxy inulin obtained by glycolytic oxidation of inulin, for example 6-carboxy inulin obtained by selective oxidation of the primary hydroxyl groups of inulin (TEMPO oxidation), for example carboxymethyl inulin, carboxyethyl inulin obtained by cyanoethylation followed by hydrolysis. Preferred inulin derivatives used are dicarboxy inulin, carboxymethyl inulin and carboxyethyl inulin.

In addition, it is possible to use fructan polycarboxylic acids containing carboxyl groups obtained by oxidizing the carbon atoms of the part forming the defructose unit in the molecule and the carboxyl groups obtained by connecting carboxyalkyl or carboxylic acid groups to the defructose unit. These double modified fructan polycarboxylic acids can be prepared by oxidizing fructan in a known manner and then carboxyalkylating or carboxyacylating the oxidation product in a known manner. It is also possible to change the order and perform carboxyalkylating or carboxyacylating before oxidation. In the case of fructan polysaccharides, the term carboxylic acid includes free acids and metal salts or ammonium salts of carboxylic acids. The term carboxyalkyl refers to C ₁ to C ₄ alkyl substituted by one or more carboxyl groups, such as carboxymethyl, carboxyethyl, dicarboxymethyl, 1,2-dicarboxyethyl or a mixture thereof. The term carboxyacyl refers to C ₁ to C ₄ acyl substituted by one or more carboxyl groups, particularly C ₁ to C ₄ alkanoyl or alkenoyl, such as carboxyacetyl, β-carboxypropionyl, β-carboxyacryloyl, γ-carboxybutyryl, dicarboxyhydroxybutyryl and a mixture thereof. As for the carboxyalkyl group and the carboxyacyl group, a carboxymethyl group is represented as preferred.

Preferably, the fructan polycarboxylic acid has an average of at least 0.05 carboxyl groups per monosaccharide unit. Depending on the properties of the fructan polycarboxylic acid, the number of carboxyl groups per monosaccharide unit of the fructan polycarboxylic acid can be expressed as the total degree of substitution (DS) or total degree of oxidation (DO) of carboxyl groups.

More preferably, the fructan polycarboxylic acid comprises 0.5 to 3 carboxyl groups per monosaccharide unit.Most preferably, the fructan polycarboxylic acid is carboxymethyl inulin comprising between 0.5 and 3 carboxyl groups per monosaccharide unit.

Carboxylic acid substituted polysaccharides:

Preferably, the substituted polysaccharide is a carboxylic acid substituted polysaccharide. Non-limiting examples of carboxylic acid substituted polysaccharides include acrylic acid substituted polysaccharides, malic acid substituted polysaccharides, succinic acid substituted polysaccharides, and most preferably acrylic acid substituted polysaccharides. A non-limiting example of a carboxylic acid substituted polysaccharide is acrylated starch.

More preferably, the substituted polysaccharide is selected from carboxyalkyl polysaccharides, carboxylic acid polysaccharides or mixtures thereof. Still more preferably, the carboxyalkyl polysaccharide is selected from carboxymethyl cellulose, carboxymethyl inulin or mixtures thereof. Preferably, the carboxylic acid polysaccharide is an acrylic acid substituted polysaccharide or a salt thereof, more preferably an acrylic acid substituted starch or a salt thereof.

Copolymer of acrylic acid and maleic acid

According to a first aspect of the present invention, a solid laundry composition preferably having an acrylic acid maleic acid copolymer is disclosed. The term "maleic acid" as used herein includes maleic acid, maleic anhydride and/or its salts. The term "acrylic acid" as used herein includes acrylic acid, methacrylic acid and/or its salts.

The acrylic acid-maleic acid copolymer preferably contains 10 to 90% by weight of acrylic acid and 10 to 90% by weight of maleic acid and its salts. Also preferred are 60 to 90% by weight of acrylic acid and 10 to 40% by weight of maleic acid.

In a preferred embodiment, the copolymer of acrylic acid and maleic acid comprises 60 to 90 wt % of acrylic acid and 10 to 40 wt % of maleic acid.

In another preferred embodiment, the copolymer of acrylic acid and maleic acid comprises 10% to 50% by weight of acrylic acid and 50% to 90% by weight of maleic acid. Also preferably 10% to 40% by weight of acrylic acid and 60% to 90% by weight of maleic acid. Preferably, the copolymer of acrylic acid and maleic acid or its salt has a weight ratio of acrylic acid segments to maleic acid segments in the range of 1:1 to 1:9. More preferably, the weight ratio of acrylic acid segments to maleic acid segments is in the range of 1:1 to 1:8, also preferably 1:1 to 1:6, and even more preferably 1:1 to 1:5.

Alternatively, the weight ratio of the acrylic acid segment to the maleic acid segment of the copolymer of acrylic acid and maleic acid or its salt is in the range of 1:1.5 to 1:9, more preferably 1:2 to 1:9, further preferably 1:2.5 to 1:9, further preferably 1:3 to 1:9, and further preferably 1:3.5 to 1:9. In yet another embodiment, the weight ratio of the acrylic acid segment to the maleic acid segment of the copolymer of acrylic acid and maleic acid or its salt is in the range of 1:4 to 1:8, more preferably 1:5 to 1:8, and further preferably 1:6 to 1:8.

Preferably, when acrylic acid exists in a higher weight percentage, i.e., a copolymer with 60 to 90 weight percent acrylic acid and 10 to 40 weight percent maleic acid, the weight average molecular weight range of the acrylic acid maleic acid copolymer is 10,000 to 120,000, preferably 50,000 to 100,000, more preferably 60,000 to 100,000, and most preferably 60,000 to 90,000. In order to ensure high water solubility, the acrylic acid maleic acid copolymer should be partially or completely neutralized. Preferably, the copolymer of acrylic acid and maleic acid has 70 weight percent acrylic acid and 30 weight percent maleic acid. A preferred example of the acrylic acid maleic acid copolymer is Sokalan CP5 from BASF.

Preferably, when the copolymer of acrylic acid and maleic acid contains 10 to 50 wt % of acrylic acid and 50 to 90 wt % of maleic acid, the weight average molecular weight ranges from 500 to 7000, more preferably from 500 to 4000, still more preferably from 2000 to 4000.

Water-soluble salts of copolymers of acrylic acid and maleic acid are also preferred for the present invention. Such salts include those selected from non-limiting examples selected from alkali metal salts, ammonium salts and substituted ammonium salts. Preferred are those copolymers having a weight ratio of acrylic acid segments to maleic acid segments ranging from 1:1 to 1:9.

It is highly preferred that the weight average molecular weight of the copolymer is in the range of 500 to 7000 and the weight ratio of acrylic acid segments to maleic acid segments is from 1:1 to 1:9, more preferably from 1:15 to 1:9; it is also preferred that the weight average molecular weight is in the range of 500 to 4000 and the weight ratio of acrylic acid segments to maleic acid segments is from 1:1 to 1:9, more preferably from 1:1.5 to 1:9; and it is still further preferred that the weight average molecular weight is in the range of 2000 to 4000 and the weight ratio of acrylic acid segments to maleic acid segments is from 1:1 to 1:9, more preferably from 1:15 to 1:9.

Preferably, the solid laundry detergent composition comprises a copolymer of acrylic acid and maleic acid, wherein the weight ratio of acrylic acid segments to maleic acid segments is from 1:1 to 1:9, and another copolymer of acrylic acid and maleic acid, wherein the weight ratio of acrylic acid segments to maleic acid segments is from 1.5:1 to 9:1. Preferably, the solid detergent composition has a higher content of the copolymer of acrylic acid and maleic acid having a weight ratio of acrylic acid segments to maleic acid segments of from 1:1 to 1:9.

The solid laundry composition preferably comprises 0.02 wt % to 0.5 wt % of acrylic acid maleic acid copolymer. Preferably, the level of acrylic acid maleic acid copolymer in the composition is in the range of 0.03 wt % to 0.5 wt %. Preferably, the amount of acrylic acid maleic acid copolymer present in the composition is at least 0.022 wt %, also preferably at least 0.025 wt %, also preferably at least 0.028 wt %, most preferably at least 0.03 wt %, but typically no more than 0.45 wt %, also preferably no more than 0.4 wt %, even more preferably no more than 0.35 wt %, most preferably no more than 0.3 wt %.

Solid laundry compositions

Solid laundry compositions according to the present disclosure encompass a variety of spray-dried or granulated forms, including, for example, powders, granules; cast and extruded forms, including, for example, solids, needles, pellets, blocks, sticks and tablets. The term "solid" refers to the state of the laundry composition under the expected storage conditions and use conditions of the solid laundry composition. Generally, it is expected that the solid laundry composition remains solid when provided at a temperature of up to about 37°C, and preferably greater than 50°C.

The composition according to the invention preferably has a pH of 7.0 to 13, preferably 7.0 to 12.5, further preferably 7.0 to 12, further preferably 8.5 to 9, when measured at 1% by weight dilution in deionized water at 25° C. The composition may preferably comprise a buffer.

The laundry composition of the present invention is in solid form. The laundry composition according to the present invention can be prepared by various conventional methods known in the art and including but not limited to mixing (including dry mixing), wet granulation, compaction (such as agglomeration), extrusion, tableting or spray drying of various compounds contained in the detergent components, or a mixture of these technologies, whereby the components herein can also be prepared by, for example, compaction (including extrusion and agglomeration) or spray drying. The laundry composition can be prepared by any conventional method, and particularly preferred are slurry preparation and spray drying or agglomeration techniques.

The composition of the present invention can adopt various physical solid forms, including the form of powder, granule, strip, thin strip, paste, tablet, thin slice, needle, lozenge and rod, and preferably the composition is in the form of powder, granule or tablet, more preferably the composition is in the form of powder. The laundry composition can be in the form of unit dose formulation, delayed delivery formulation, detergent contained on or in porous substrate or nonwoven sheet, and other suitable forms obvious to those skilled in the art in view of the teaching of this paper. The composition according to the present invention can preferably be selected from the form of powder, unit dose or pouch form, tablet, rod or thin slice.

The solid laundry detergent composition according to the present invention is preferably free-flowing. The composition is preferably a fully formulated detergent composition. Solid detergent compositions include, but are not limited to, powders, granules, particulates, agglomerates, thin strips, flakes, tablets, rods, sheets or other solid forms known in the art and combinations thereof.

Preferably, the composition is for washing fabrics using a hand washing method.Preferably, the composition of the present invention is a solid laundry detergent composition in spray dried powder form or in granular free flowing form.

The composition preferably has a density of greater than 350 g/litre, more preferably greater than 450 g/litre or even greater than 570 g/litre.More preferably, the solid laundry composition has a bulk density in the range of 350 g/litre to 800 g/litre.

Surfactants

Solid laundry compositions according to the first aspect of the present invention preferably include a surfactant.

Surfactants include those selected from anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, nonionic surfactants, or combinations thereof.

Examples of anionic surfactants are given in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). Suitable anionic surfactants include those selected from alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl sulfosuccinamates, alkyl amide sulfosuccinates, alkyl carboxylates, alkyl amide ether carboxylates, alkyl succinates, fatty acyl sarcosinates, fatty acyl amino acids, fatty acyl taurates, fatty alkyl sulfoacetates, alkyl phosphates and two or more mixtures thereof. Non-limiting examples of preferred anionic surfactants include linear alkylbenzene sulfonates, primary alkyl sulfates, methyl ester sulfonates or combinations thereof.

Sulfate surfactants:

Suitable sulfate surfactants include _C8 to _C20 alkyl sulfates, preferably _C8 to _C18 alkyl sulfates, also preferably _C12 to _C14 alkyl sulfates, more preferably mainly _C12 alkyl sulfates. The alkyl sulfate surfactants may be linear or branched, substituted or unsubstituted, and may be derived from petrochemical materials or biomaterials. Preferably, the alkyl sulfate surfactant is linear. Also preferably, it is preferred that the alkyl sulfate surfactant is a _C10 to _C14 alkyl sulfate surfactant, most preferably a lauryl sulfate surfactant.

Conventional primary alkyl sulfate surfactants have the general formula: R" _OSO3 ^- M ⁺ , wherein R" is typically a _C8 to _C20 alkyl group, which may be linear or branched, and M is a water-soluble cation. In a specific embodiment, R" is a _C10 to _C15 alkyl group, and M is an alkali metal, more specifically R" is a _C12 to _C14 alkyl group, and M is sodium. Specific non-limiting examples of anionic alkyl sulfate surfactants useful in the present invention include: _C10 to _C20 primary, branched and random alkyl sulfates (AS); or _C10 to _C18 secondary (2,3)-alkyl sulfates, which have the following formula:

wherein M is hydrogen or a cation providing charge neutrality, and all M units can be hydrogen atoms or cations, depending on the isolated form or the relative pH of the system in which the surfactant is used, non-limiting examples of preferred cations include sodium, potassium, ammonium and mixtures thereof, and x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9.

Preferred sulfate surfactants are alkyl alkoxylated sulfates, preferably alkyl ethoxylated sulfates, preferably _C8 to _C18 alkyl alkoxylated sulfates, preferably _C8 to _C18 alkyl ethoxylated sulfates, preferably alkyl alkoxylated sulfates have an average degree of alkoxylation of 0.5 to 20, preferably 0.5 to 10, preferably alkyl alkoxylated sulfates are _C8 to _C18 alkyl ethoxylated sulfates, having an average degree of ethoxylation of 0.5 to 10, preferably 0.5 to 5, more preferably 0.5 to 3, most preferably 0.5 to 1.5. The alkyl alkoxylated sulfate surfactants may be linear or branched, substituted or unsubstituted, and may be derived from petrochemical materials or biomaterials. Preferably, the sulfate surfactant is a linear or branched, substituted or unsubstituted _C8 to _C18 alkyl sulfate surfactant, a _C8 to _C18 alkyl ether sulfate surfactant, or a mixture thereof.

Sulfonate surfactants:

Suitable sulfonate detersive surfactants include methyl ester sulfonates, alpha-olefin sulfonates, alkylbenzene sulfonates, especially alkylbenzene sulfonates, preferably _C10 to _C14 alkylbenzene sulfonates. Suitable alkylbenzene sulfonates (LAS) are available, preferably by sulfonation of commercially available linear alkylbenzenes (LAB); suitable LABs include lower 2-phenyl LABs, other suitable LABs include higher 2-phenyl LABs, such as those available from Sasol under the trade name Sulfonate surfactants can be linear or branched, substituted or unsubstituted, and can be derived from petrochemical materials or biomaterials. Sulfonate surfactants are preferably linear or branched, substituted or unsubstituted _C10 to _C14 alkylbenzene sulfonates. Sulfonate surfactants can also be selected from modified alkylbenzene sulfonates (MLAS), as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonates (MES); and alpha-olefin sulfonates (AOS).

Anionic surfactants can exist in acid form, and the acid form can be neutralized to form surfactant salts. Typical reagents for neutralization include metal counterion bases, such as hydroxides, such as NaOH or KOH. Other reagents for neutralizing anionic surfactants include ammonia, amines or alkanolamines. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine and other straight or branched alkanolamines known in the art, such as 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine or 1-amino-3-propanol.

Preferably, the anionic surfactant is a non-soap anionic surfactant.The term "soap" is used herein in its general sense, ie, an alkali metal or alkanolammonium salt of an aliphatic, alkane or alkene monocarboxylic acid.

Preferably, the anionic surfactant comprises 0 to 20% by weight of alkyl sulfate, preferably 0 to 15% by weight of alkyl sulfate, preferably 0 to 10% by weight of alkyl sulfate, preferably PAS. The anionic surfactant may also comprise 0 to 10% by weight of MES, preferably 0 to 5% by weight of MES.

The detergent composition of the present invention comprises 2 wt % to 50 wt % of anionic detersive surfactant, most preferably 2 wt % to 25 wt % of anionic surfactant. Preferably, the detergent composition comprises at least 4 wt %, also preferably at least 5 wt %, also preferably at least 8 wt %, also preferably at least 10 wt %, also more preferably at least 12 wt % of anionic surfactant, most preferably at least 15 wt % of anionic surfactant, but usually not more than 45 wt %, also preferably not more than 40 wt %, also more preferably not more than 35 wt %, also more preferably not more than 30 wt %, and most preferably not more than 25 wt %, also more preferably not more than 20 wt % of anionic surfactant, based on the weight of the detergent composition.

Nonionic surfactants:

Non-limiting examples of nonionic surfactants include: _C12 to _C18 alkyl ethoxylates, _C6 to _C12 alkylphenol alkoxylates, wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; _C12 to _C18 alcohols and _C6 to _C12 alkylphenol condensates with ethylene oxide/propylene oxide block alkyl polyamine ethoxylates alkyl polysaccharides and ether-terminated poly(alkoxylated) alcohol surfactants.

Cationic surfactants:

Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants which may have up to 26 carbon atoms, including: alkoxylate quaternary ammonium (AQA) surfactants, dimethylhydroxyethyl quaternary ammonium, dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants and cationic ester surfactants.

Zwitterionic surfactants:

Non-limiting examples of zwitterionic or amphoteric surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants include betaines, including alkyl dimethyl betaines and coconut dimethylaminopropyl betaine, _C8 to _C18 (e.g., _C12 to _C18 ) amine oxides, and sulfo and hydroxy betaines, such as N-alkyl-N, N-dimethylammonium-1-propane sulfonate, wherein the alkyl group may be _C8 to _C18 , and in certain embodiments _C10 to _C14 .

The solid laundry composition preferably has a combination of anionic surfactants.Preferably, the anionic surfactant is selected from alkylbenzene sulfonate surfactants, alkyl sulfate surfactants, alkyl ether sulfate surfactants or mixtures thereof.

Preferably, the total amount of alkyl sulfate surfactants and alkyl ether sulfate surfactants in the composition is less than 50% by weight of the total anionic surfactants present in the composition, more preferably, the total amount of alkyl sulfate surfactants and alkyl ether sulfate surfactants in the composition is less than 50% by weight of the total surfactant content present in the composition.

Alternatively, the total amount of alkyl sulfate surfactants and alkyl ether sulfate surfactants in the composition is greater than 50% by weight of the total anionic surfactants present in the composition, more preferably, the total amount of alkyl sulfate surfactants and alkyl ether sulfate surfactants in the composition is greater than 50% by weight of the total surfactant content present in the composition.

Also preferably, the solid laundry composition may include a combination of anionic surfactants and nonionic surfactants. Preferably, the anionic surfactant is one or both of an alkyl sulfate surfactant and an alkyl ether sulfate surfactant. Preferably, the total amount of alkyl sulfate surfactant, alkyl ether sulfate surfactant and nonionic surfactant in the composition is greater than 50% by weight of the total surfactant content present in the composition.

Carbonate Builder

The detergent composition of the present invention preferably comprises a carbonate builder.In addition to a carbonate builder, the composition may also comprise sodium bicarbonate, potassium carbonate, sodium sesquicarbonate or a mixture thereof.

The detergent composition of the present invention comprises 0 wt % to 35 wt %, more preferably 0 wt % to 20 wt % carbonate builder. Preferably, the detergent composition comprises at least 3 wt %, also preferably at least 5 wt %, also preferably at least 8 wt %, most preferably at least 10 wt % carbonate builder, most preferably at least 12 wt % carbonate builder, but usually no more than 30 wt %, also preferably no more than 28 wt %, most preferably no more than 25 wt %, most preferably no more than 22 wt % carbonate builder, based on the weight of the laundry detergent composition. The carbonate builder can include 100 wt % alkali metal carbonate builder, preferably sodium carbonate builder, or can be a combination of alkali metal carbonate, alkali metal bicarbonate, alkali metal sesquicarbonate or a combination thereof.

Silicate

The detergent composition of the present invention preferably comprises a silicate. The silicate is preferably an alkali metal silicate which acts as an alkalinity agent and builder in the solid detergent composition.

Suitable silicates include water soluble sodium silicates having a _SiO2 : _Na2O ratio of 1.0 to 2.8, preferably a ratio of 1.6 to 2.4, most preferably a ratio of 2.0. The silicates may be in the form of anhydrous or hydrated salts. Sodium silicate having _{a SiO2} : _Na2O ratio of 2.0 is the most preferred silicate.

Silicate is preferably present in solid laundry compositions according to the invention at levels ranging from 0wt% to 17wt% by weight of the composition, more preferably from 0wt% to 15wt%, even more preferably from 0wt% to 13wt% of the solid laundry composition.

The composition of the present invention preferably comprises 0 to 17 wt %, further preferably 0 to 15 wt %, more preferably 0 to 8 wt % of silicate, further preferably 0 to 5 wt %, further more preferably 0 to 1 wt % of silicate. Preferably, the composition of the present invention is substantially free of silicate. Substantially free means that no carbonate is intentionally added to the composition.

Inorganic salts:

The solid laundry composition of the present invention preferably comprises an inorganic salt selected from calcite, dolomite, magnesium carbonate or a mixture thereof. The composition of the present invention preferably comprises 0 wt % to 10 wt %, further preferably 0 wt % to 6 wt %, more preferably 0 wt % to 5 wt % of an inorganic salt selected from calcite, dolomite or a mixture thereof.

The solid laundry composition of the present invention preferably comprises a soluble inorganic salt selected from alkali metal sulfate, alkali metal chloride, alkaline earth metal sulfate or a mixture thereof. More preferably, the composition comprises a soluble inorganic salt selected from sodium sulfate, sodium chloride, magnesium sulfate or a mixture thereof. Preferably, the composition of the present invention comprises 10 wt % to 60 wt %, also preferably 15 wt % to 50 wt %, more preferably 15 wt % to 40 wt % of soluble inorganic salt.

Biodegradable Chelating Agents:

Solid laundry composition may preferably comprise a biodegradable chelating agent. Non-limiting examples of biodegradable chelating agents include MGDA, GLDA, gluconate or mixtures thereof. More preferably, the biodegradable chelating agent is a gluconate. Compositions of the present invention preferably comprise 0 wt % to 10 wt %, also preferably 0 wt % to 6 wt %, more preferably 0 wt % to 5 wt %, even more preferably 0 wt % to 3 wt % of a biodegradable chelating agent, more preferably a gluconate.

Bleach and bleach activators:

The solid laundry composition of the present invention may include a bleaching agent. The bleaching agent is preferably selected from percarbonate bleach. More preferably, a bleach activator is present. Examples of bleach activators include TAED, and other known bleach activators may also be used.

The bleaching system typically comprises a bleaching agent and a bleach activator.Preferably, the solid laundry composition comprises from 0 to 6 wt% of bleaching agent, further preferably from 0 to 5 wt% of bleaching agent, still more preferably from 0 to 3 wt% of bleaching agent.

Preferably, the total amount of bleach and bleach activators present in the composition of the present invention is in the range of 0% to 10% by weight, more preferably 0% to 8% by weight, still preferably 0% to 5% by weight and still more preferably 0% to 3% by weight.

Preferably, the solid laundry composition comprises 0 wt% of a boron based bleach.Examples of boron based bleaches include sodium perborate.Preferably, the solid laundry composition comprises 0 wt% of a boron based bleach activator.

Moisture Content:

The solid laundry composition comprises from 1 wt% to 3.5 wt%, also preferably from 1 wt% to 3 wt% water.Preferably, the solid laundry composition is agglomerated or spray-dried.

The solid laundry composition according to the present invention preferably has 0 to 4 wt% of zeolite builder. Preferably, the amount of zeolite builder is less than 3 wt%, also preferably less than 2.5 wt%, more preferably less than 2 wt% in the detergent composition, and most preferably, the detergent composition is substantially free of zeolite builder.

The solid laundry detergent composition according to the present invention preferably has 0% to 2% by weight of phosphorus-containing chemicals. Preferably, the phosphorus-containing chemicals include STPP, HEDP or a mixture thereof. Preferably, the amount of phosphorus-containing chemicals in the solid laundry composition is less than 2% by weight, also preferably less than 1.5% by weight, more preferably less than 1% by weight, and most preferably the solid laundry composition is substantially free of phosphorus-containing chemicals. Preferably, the composition includes 0% to 2% by weight of STPP. Also preferably, the solid laundry composition is substantially free of STPP. Preferably, the composition includes 0% to 2% by weight of HEDP. Also preferably, the solid laundry composition is substantially free of HEDP. Preferably, the composition includes 0% by weight of STPP. Preferably, the composition includes 0% by weight of HEDP.

The term "substantially free" means that the indicated component is in a very small amount and is not intentionally added to the composition to form a part thereof. This is meant to include compositions in which the indicated material is present only as an impurity in one of the other materials intentionally included.

Optional Ingredients

The solid laundry composition of the present invention may preferably include one or more optional ingredients selected from cleaning and care ingredients. Optional ingredients include one or more auxiliary cleaning additives selected from polymers, further enzymes, enzyme stabilizers, brighteners, whitening agents, bleaches, humectants, perfumes, fillers or carriers, alkaline systems, buffers or combinations thereof.

Cleaning and care polymers:

The compositions of the present invention may preferably contain polymers that provide cleaning or conditioning benefits. Cleansing polymers include, but are not limited to, soil release polymers, anti-redeposition polymers, cellulosic polymers, conditioning polymers, amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil suspending polymers or mixtures thereof.

Suitable other carboxylate polymers may preferably include polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of maleic acid and vinyl methyl ether, or mixtures thereof.

The anti-redeposition polymer is designed to suspend or disperse soil. Typically, in addition to those already discussed above, the anti-redeposition polymer may preferably include those selected from polyethylene glycol polymers, polyethylene imine polymers or mixtures thereof.

Soil release polymers are designed to modify the surface of fabrics to promote easy removal of soil. Suitable soil release polymers are available from Clariant as A series of polymers are sold, e.g. SRN240, SRN100, SRN170, SRN300, SRN325, SRA100 and SRA 300. Other suitable soil release polymers are available from Rhodia as A series of polymers are sold, e.g. SF2, SRP6 and Crystal. Preferred polymers are selected from polyester soil release polymers, end-capped and non-end-capped sulfonated PET/POET polymers, end-capped and non-end-capped unsulfonated PET/POET polymers, or combinations thereof.

Preferably, the level of these soil release polymers in the detergent composition ranges from 0 wt % to 5 wt %, at least 0.1 wt %, also preferably at least 0.25 wt %, also preferably at least 0.3 wt %, but typically does not exceed 5 wt %, also preferably does not exceed 3 wt %, also preferably does not exceed 1 wt %, more preferably does not exceed 0.5 wt %.

Suitable conditioning polymers include cationically modified or hydrophobically modified cellulosic polymers. Suitable commercially available dye locking polymers are FDI (Cognis). Preferably, the auxiliary particles comprise 0.01% to 10% by weight, preferably 0.05% to 0.5% by weight, of care polymers.

Examples of suitable chelating polymers are DEQUEST ^(TM) , an organic phosphonate type chelating polymer sold by Monsanto, and alkane hydroxyphosphonates.

The solid laundry composition is preferably substantially free of phosphate based chelating polymers. "Substantially free" herein means that no phosphate based chelating polymers are intentionally added.

Enzymes:

The compositions of the present invention preferably include one or more additional enzymes.Preferred examples of additional enzymes include those which provide cleaning performance and/or fabric care benefits.

Examples of suitable additional enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, xylanases, lipases, xyloglucanases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, g-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases and amylases, or mixtures thereof. A typical combination is an enzyme mixture, which may comprise, for example, a protease and a lipase in combination with one or more of an amylase and a mannanase. When present in a solid laundry composition, the additional enzyme may be present at a level of about 0.00001% to about 2%, about 0.0001% to about 1%, or 0.001% to about 0.5% enzyme protein by weight of the solid laundry composition.

Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases such as subtilisin (EC 3.4.21.62). Suitable commercially available proteases include those marketed under the trade name HYDROGEN(R) by Novozymes A/S (Denmark). Liquanase Savinase and Those sold by Genencor International under the trade name 1. Purafect Purafect 10 and Purafect Those sold by Solvay Enzymes under the trade name and those sold by Optimase.

Suitable α-amylases include those of bacterial or fungal origin. Suitable commercially available α-amylases include TERMAMYL STAINZYME and (Novozymes A/S, Bagsvaerd, Denmark), 15 AT9000Biozym Biotech Trading GmbH Wehlistrasse 27bA-1200Wien Austria, OPTISIZE HT and PURASTAR (Genencor International Inc., Palo Alto, California) and (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include STAINZYME and STAINZYME and mixtures thereof.

In one aspect, such enzymes may be selected from: lipases, including "first cycle lipases". Preferred lipases include those sold under the trade name and Those that are sold.

Other preferred enzymes include those sold under the trade name Pectate lyase is sold under the trade name (both from Novozymes A/S, Bagsvaerd, Denmark) and (Genencor International Inc., Palo Alto, California)

Enzyme stabilization system:

The enzyme-containing compositions described herein may optionally include 0.001% to 10%, in some instances about 0.005% to about 8%, and in other instances about 0.01% to about 6% of an enzyme stabilizing system by weight of the composition. The enzyme stabilizing system may be any stabilizing system compatible with the detersive enzyme. Such stabilizing systems may, for example, include calcium ions, propylene glycol, short chain carboxylic acids, chlorine bleach scavengers, and mixtures thereof, and are designed to address different stabilization issues depending on the type and physical form of the cleaning composition.

Washing method :

According to a second aspect of the present invention, there is disclosed a method for washing a textile surface using a solid laundry composition according to the first aspect of the present invention, the method comprising the following steps:

iv) preparing an aqueous wash liquor by contacting a solid laundry composition according to the first aspect with a liquid;

v) soaking the textile surface in a wash liquor for a predetermined period of time; and

vi) optionally rinsing the textile surface.

The composition is preferably used in a concentration of about 200 ppm to about 15,000 ppm in solution. Preferably, the liquid is water. The water temperature is preferably in the range of 5°C to 100°C.

The machine laundry method herein generally comprises treating the soiled textile fabric in a washing machine with an aqueous wash solution in which an effective amount of a solid laundry composition according to the present invention is dissolved or dispensed. An effective amount of a solid laundry composition refers to 20 g to 300 g of the product dissolved or dispersed in a wash solution having a volume of 5 to 65 liters, such as typical product dosages and wash solution volumes commonly used in conventional machine laundry methods. Also included are hand wash methods, as well as hand wash in combination with a semi-automatic washing machine.

According to a third aspect of the present invention, there is disclosed the use of the cellulase according to the first aspect and an optical brightener represented by general formula (I) in a solid laundry composition to provide improved cleaning performance.

Preferably the improved cleaning performance is compared to a composition having a cellulase and a conventional (well known in laundry compositions) optical brightener selected from Tinopal CBSX and DASCC type optical brighteners.

According to yet another aspect of the present invention, there is disclosed use of the cellulase according to the first aspect and an optical brightener of formula (I) in a solid laundry composition for exhibiting improved biodegradability.

Preferably, the improved biodegradability is compared to a composition with a cellulase and a conventional (well known in laundry compositions) optical brightener selected from Tinopal CBSX and DASCC type optical brighteners.

The present invention will now be more fully described with the aid of the following non-limiting examples. It should be understood that other modifications may be made to the present invention within the technical scope of those skilled in the art without departing from the spirit and scope of the present invention. Unless a specific method is given, all preparations illustrated below are prepared by conventional preparation and mixing methods. Unless otherwise indicated, all parts, percentages and ratios herein are by weight.

Example

Example 1

The spray-dried solid laundry compositions according to the present invention were prepared by spray drying an aqueous slurry in a counter-current spray dryer. The compositions of spray-dried solid laundry detergent compositions according to the present invention (Ex 1) and compositions having higher levels are provided in Table 1 .

Table 1

It was found that the composition according to the present invention comprising a combination of cellulase and a low level of optical brightener (Ex 1) provides good cleaning performance and has good biodegradability.

Example 2

Different spray dried solid laundry compositions as shown in Table 2 were prepared by spray drying an aqueous slurry in a counter current spray dryer. Acrylic acid maleic acid copolymer, cellulase and optical brightener were added to the spray dried powder to form a solid laundry composition.

The spray-dried solid laundry detergent compositions according to the invention (Ex 2, Ex 3, Ex 4) and the comparative composition (Ex B) were then evaluated for their whiteness performance.

Whiteness performance evaluation:

The whiteness performance of each composition provided in Table 2 was evaluated. To this end, a 4 g/L amount of solid laundry composition was added to a tergo-to-meter with 500 mL of water (water hardness 6FH Ca ²⁺ :Mg ²⁺ 2:1) and the device was run for 2 minutes at a speed of 100 rpm and a water temperature of 25°C. Next, 2 types of standard commercially available soil bars were added to the wash liquor and the machine was run for another 2 minutes at a speed of 100 rpm and the water temperature was maintained at 25°C. These soil bars included a 2 g/L amount of SBL soil emulsion and a 1.5 g/L amount of Stanley clay soil. Five woven cotton samples (woven cotton - CN11 type) were then added and washed using a soak, wash and rinse regimen. In this regimen, the soak time was 20 minutes, which was followed by a 15 minute wash cycle and then 2 rinse cycles of 2 minutes each. The swatches were dried and their Ganz WI values were measured using a Xrite CI 7600 spectrophotometer (UV including mode, supplier Advanced Graphic Systems (AGS)) and reported in Table 2 below. The results are the average of all 5 swatches of cloth for each composition. The Ganz whiteness value is measured accurately to +/- 2 units.

Higher positive Ganz WI values indicate that the washed swatches exhibit more bluing or whitening effect. Therefore, compositions providing higher Ganz WI values are preferred.

Table 2

*Sokalan CP5 from BASF, acrylic acid to maleic acid ratio of 70:30 by weight

^& Acrylic acid maleic acid copolymer with a weight ratio of acrylic acid to maleic acid of 50:50

^@Traditional optical brighteners＝ DMS (DASCC type optical brightener) -

^# -Optical brightener having structure A as shown above

The data provided in Table 2 show that the comparative composition with DASCC type optical brightener and cellulase (Ex B) has lower whiteness values than the inventive composition with cellulase and the same level of optical brightener of general formula (I) (Ex 2).

Furthermore, the inventive compositions (Ex 3 and Ex 4) with lower levels of optical brighteners in combination with cellulases according to the invention give much higher whiteness performance compared to the comparative example (Ex B) with twice higher levels of conventional optical brighteners and cellulases. The inventive compositions provide better performance at much lower optical brightener levels and therefore better biodegradability while maintaining good whiteness performance.

Claims (15)

1. A solid laundry composition comprising: (i) cellulase; (ii) an optical brightener represented by the general formula (I): in: _R1 are the same or different and are selected from _-NH2 , -NH( _C1 to _C4 alkyl), -N( _C1 to _C4 alkyl) ₂ , -NH( _C2 to _C4 hydroxyalkyl), -N( _C2 to _C4 hydroxyalkyl) ₂ and -N( _C1 to _C4 alkyl)( _C2 to _C4 hydroxyalkyl); R ₃ is independently selected from hydrogen (-H), C ₁ to C ₄ alkyl, C ₁ to C ₄ hydroxyalkyl; M is independently selected from hydrogen, an alkali metal atom, ammonium, and a cation formed from an amine. 2. The composition of claim 1, wherein the optical brightener is present in an amount ranging from 0.01 wt% to 0.4 wt%. 3. A composition according to claim 1 or 2 comprising a hueing dye, preferably from 0.0005 wt% to 0.005 wt% of a hueing dye. 4. A composition according to claims 1 to 3 comprising a substituted polysaccharide wherein the functional groups are present on the polysaccharide backbone. 5. The composition according to claim 4, wherein the functional group is selected from alkyl, carboxyalkyl, carboxylic acid, alkoxy or salts thereof, and preferably the substituted polysaccharide is a carboxyalkyl substituted polysaccharide, a carboxylic acid substituted polysaccharide or a salt thereof. 6. A composition according to any preceding claim, wherein the composition comprises a copolymer of acrylic acid and maleic acid. 7. The composition of claim 6, wherein the amount of acrylic acid maleic acid copolymer present in the composition is in the range of 0.02 wt% to 0.5 wt%. 8. A composition according to any preceding claim, wherein the composition comprises a biodegradable chelating agent. 9. The composition of claim 8, wherein the biodegradable chelating agent is selected from MGDA, GLDA, gluconate or mixtures thereof. 10. A composition according to any preceding claim, wherein the composition comprises from 0% to 35% by weight carbonate builder. 11. A composition according to any preceding claim, wherein the composition comprises from 0% to 17% by weight of alkali metal silicate. 12. A composition according to any preceding claim, wherein the composition comprises a phosphorus-containing chemical in an amount ranging from 0 wt% to 2 wt%, preferably the phosphorus-containing chemical is selected from STPP, HEDP or a mixture thereof. 13. A composition according to any preceding claim comprising a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants or mixtures thereof. 14. A composition according to any preceding claim, comprising a bleaching system comprising a bleaching agent, preferably together with a bleach activator. 15. Use of cellulase and an optical brightener represented by general formula (I) in a solid laundry composition to provide improved cleaning performance.