FIELD OF THE INVENTION

The present invention relates to consumer goods products comprising functionalized lignin oligomer.

BACKGROUND OF THE INVENTION

Polyethylene glycol is incorporated into consumer goods products to provide benefits such as hydrophilisation of the treated surface. However, the surface substantivity of polyethylene glycol can be poor, which can lead to poor surface modification performance. The inventors have found that functionalizing lignin with polyethylene glycol in the manner described by the present invention improves the performance of the polyethylene glycol in the consumer goods product. In addition, the lignin provides anti-oxidant properties, this can be especially preferred for consumer goods products of skin applications.

SUMMARY OF THE INVENTION

The present invention relates to a consumer goods product comprising a consumer goods product ingredient and a non-crosslinked functionalised lignin oligomer, wherein the functionalised lignin oligomer: (a) has an average number of lignin monomers of from 3 to 8; (b) comprises a polyethylene glycol functional group; (c) comprises a functionalisation content between 90 and 0.5 % lignin (m/m), wherein the consumer goods product ingredient is an emulsifier, and wherein the lignin oligomer is in the form of an emulsion, and wherein the consumer goods product is in the form of an oral care composition or a detergent composition. DETAILED DESCRIPTION OF THE INVENTION

Consumer goods product: The consumer goods product comprises a consumer goods product ingredient and a functionalised lignin oligomer.

The consumer goods product may comprise an emollient and/or humectant.

The consumer goods product comprises an emulsifier and the lignin oligomer is in the form of an emulsion.

The product may be an oral care composition.

The product may be a detergent composition.

The consumer goods product may comprise chitin and/or chitin derivative. The consumer goods product is typically selected from: hard surface cleaning sheet and/or wipe; and teeth treatment strip.

The consumer goods product is typically selected from: handwash laundry detergent; handwash dishwashing detergent; soap bar; liquid handwash soap; and toothpaste.

Consumer goods product ingredient: The consumer goods product ingredient is an emulsifier. Suitable other ingredients include emmolient, humectants, emulsifiers, and any combination thereof.

Functionalised lignin oligomer: The functionalised lignin oligomer: (a) has an average number of lignin monomers of from 3 to 8 ; (b) comprises a polyethylene glycol functional group; (c) comprises a functionalisation content between 90 and 0.5 % lignin (m/m).

The functionalised lignin oligomer is non-crosslinked and may comprise a functional group having the structure comprising the functional group: lignin_backbone-0-L- 'PEG' wherein 'lignin_backbone' is the lignin structural backbone;

wherein L is a linker; and

wherein 'PEG' is a polyethylene glycol,

wherein L has the chemical structure:

(a) wherein R and R are independently selected from H and linear or branched, saturated or unsaturated, substituted or unsubstituted Ci to Ci ₈ alkyl;

wherein X is independently selected from R ¹ , R ² , hydroxyl, amine, ether and ester;

wherein L' is a linking structural motif selected from linear or branched, saturated or unsaturated, substituted or unsubstituted Q to Q ₈ alkyl;

wherein 'PEG' is a polyethylene glycol; or (b) wherein-C- motif is a connecting motif selected from: -C(=0)-,— OC(=0)-, -C(=0)NR'-, wherein R' is selected from H, or C ₁ -C6 alkyl;

wherein L' is a linking structural motif selected from linear or branched, saturated or unsaturated, substituted or unsubstituted Ci to Qs alkyl;

wherein 'PEG' is a polyethylene glycol.

The functionalised lignin oligomer is non-cross linked and may comprise a functional group being linked via one of the following structural features:

(R ₁ )(Ri')C=C(R ₂ )-N(R ₃ )(R3') wherein Ri, Ri ' and R2 are independently selected from hydrogen or lignin backbone, wherein at least one of R _l5 Rj' and R ₂ is lignin backbone,

wherein R ₃ and R ₃ ' are both independently selected from saturated or unsaturated, linear or branched, substituted or unsubstituted Q-C ₃ 2 alkyl , wherein at least one of R3 or R ₃ ' is bound to the 'PEG' polyethylene glycol; or wherein both Rj and R2 are independently selected from hydrogen or lignin backbone, wherein at least one of Rj or R2 is lignin backbone,

wherein R ₃ is independently selected from saturated or unsaturated, linear or branched, substituted or unsubstituted C ₁ -C ₃ 2 alkyl, wherein R ₃ is bound to the 'PEG' polyethylene glycol.

The lignin oligomer may comprise at least two different linking motifs.

Preferably, the lignin oligomer has a weight average molecular weight ( _w ) in the range of from 800 Da to 5,000 Da.

Preferably, the lignin oligomer has a number average molecular weight (M _n ) in the range of from 800 Da to 1,200 Da. Preferably, the lignin oligomer is essentially free of sulphur.

Preferably, the lignin oligomer has an ester content in the range of from 0.0 mmol/g to 0.1 mmol/g.

Preferably, the lignin oligomer is derived from corn, sugar cane, wheat and any combination thereof.

Polyethylene glycol: Suitable polyethylene glycol (PEG) and derivatives thereof typically have molecular weight ranges from 500 Da to 100,000 Da, preferably from 1,000 Da to 50,000 Da, more preferably from 1,500 Da to 10,000 Da.

Suitable PEGs and derivatives thereof typically have the following structure:

R (OC ₂ H4) _x -OR ₂ wherein:

x is an integer from 36 to about 240;

Ri is selected from the group of moieties comprising glycidyl ether,linear or branched Ci-Ci ₈ alkyl moiety-linked chlorides, bromides, iodides, mesylates, triflates, tosylates, or R ₃ R4N-C ₁ -C18 alkyl;

R2 is selected from H or C¾.

R ₃ and R4 are independently selected from H or linear or branced Q-Qg alkyl groups with at least one of them being H, n-RsR ₆ N-(n-l)-hydroxy-C _n alkyl with n being an integer from 2 to 18; R5 and R6 are independently selected from H or linear or branced Ci-Ci ₈ alkyl groups with at least one of them being H; alkyl residues mentioned in this list can be substituted, or partly or completely exchanged by C2-C18 alkoxy or C2-C18 substituted alkoxy. PEG functionalisation of lignin:

Functionalisation via activated hydroxyl groups: Lignin (500 mg) is dissolved in water containing sodium hydroxide (amount corresponding to lequivalnt (eq.) to total acidic groups in the lignin, i.e., phenolic hydroxyl and carboxylic acid groups. After 1 h of stirring, the suitably terminated PEG-derivative, e.g. , an epoxide-terminated PEG-derivative, is added (depending on the desired technical loading, e.g in the range of from 0.25 to 10.0 eq. to lignin phenolic hydroxyl groups) and the reaction mixture is stirred at 50 °C overnight.

After cooling to room temperature and acidifying to pH 2 using 10% (v/v) aqueous hydrogen chloride solution, the resulting suspension is centrifuged (15 min at 500 rpm) to recover the precipitated lignin. The functionalised lignin is then washed 3 times with 50 mL acidified water (pH 2) followed by renewed isolation via centrifugation (15 min at 500 rpm) each time. The final pellet was subsequently freeze-dried. The freeze-dried material is used for analysis and application without any additional manipulation.

Functionalisation via keto-groups: Lignin, or chemically oxidised lignin, or lignin oxidised biotechnologically using oxidative enzymes, such as, but not exclusively, laccases (EC 1.10.3), polyphenol oxidases (EC 1.14.18) and lipoxygenases (EC 1.13.11) as well as homogenic or heterogenic mixtures thereof, (500 mg) are dissolved or suspended in water or an enzyme- compatible buffer solution in the present of 5% (m/v) of an non-ionic surfactant, the suitably decorated PEG-derivative, e.g., an amine-decorated-PEG-derivative, is added and the mixture is stirred for a maximum of 24 hours. In case the reaction is run in the absence of enzymes, the reaction temperature is at 30 °C. In case the reaction is run in the presence of one or more enzymes, the temperature is chosen according to a performance study on the enzymatic species revealing the optimum temperature for maximum enzyme activity.

After the desired reaction time, at room temperature, the reaction n mixture is acidified to pH 2 using 10% (v/v) aqueous hydrogen chloride solution. The resulting suspension is centrifuged (15 min at 500 rpm) to recover the precipitated lignin. The functionalised lignin is then washed 3 times with 50 mL acidified water (pH 2) followed by renewed isolation via centrifugation (15 min at 500 rpm) each time. The final pellet was subsequently freeze-dried. The freeze-dried material is used for analysis and application without any additional manipulation.

How to measure functionalisation content:

Evaluation of bonding type: For evaluating the presence of covalent bonding between the PEG and the lignin starting materials, gel permeation chromatography studies are performed.

For the starting materials as well as for the PEG-lignin hybrids, M _n and M _w are determined, e.g. as described elsewhere. Covalent bonding is indicated by significant augmentations of the signals obtained by the diode array detector at a wavelength of λ = 280 nm at elution times at which no signal augmentation was observed for the starting lignin, indicating UV-active species exhibiting molecular weights significantly larger than those observed for the starting lignin under identical analysis conditions.

Quantification of PEG/lignin ratios:

Functionalisation via activated hydroxyl groups: Depending on the size of the PEG- derivatives linked to the lignin substrates, functionalisation contents in form of PEG/lignin ratios are estimated on the basis of the hydroxyl group-content as determined via the procedure described above under consideration of the number average moelular weight of the PEGyltated lignin, which in turn is determined via the GPC-based method described above; functionalisation degrees are given in terms of % (m/m) lignin.

Functionalisation via keto-groups: For evaluating the extend of PEG-lignin hybrid formation, an elemental analysis in the form of a CHNS-analysis was performed as described above using a Carlo-Erba NA 1500 analyzer. Ratios between lignin oligomers and PEG polymers were estimated according to the amount of nitrogen found in the sample with respect to the nitrogen content of the polymeric unit of the employed amine group-containing PEG- derivative. PEG/lignin ratios were then estimated based on the formal molecular weights of the species involved under consideration of results obtained in the determination of number average molecular weight; functionalisation degrees are given in terms of % (m/m) lignin.

Method of measuring sulphur content: The chemical composition of a lignin sample in terms of its carbon (C), hydrogen (H), nitrogen (N) and sulphur (S) content can be determined by elemental analysis in form of a CHNS analysis of at least three different representative samples of a given batch of the respective lignin. Typical sample sizes are 2.0 mg of a lignin sample that was oven-dried at 105°C until a steady weight was obtained. The samples are placed in aluminum dishes and analyzed using a Carlo-Erba NA 1500 analyzer, using helium as carrier gas. Carbon (C), hydrogen (H), nitrogen (N) and sulphur (S) were detected in form of carbon dioxide, water, nitrogen, and sulphur dioxide, which are chromatographically separated to exit the instrument in the order of nitrogen, carbon dioxide, water, and sulphur dioxide.

Quantification is achieved against calibrations using typical standard substances used for the calibration of elemental analysers, such as (bis(5-tert-butyl-2-benzo-oxazol-2-yl) thiophene, based on the peak areas of the chromatograms obtained for each lignin sample.

Method of measuring M _n and M _w : The number average molecular weight, M _n , as well as the weight average molecular weight, M _w , can be determined using gel permeation chromatography (GPC). Prior to analysis, representative lignin samples are acetobrominated as reported in archival literature (J. Asikkala, T. Tamminen, D. S. Argyropoulos, J. Agric. Food Chem. 2012, 60, 8968-8973.) to ensure complete solubilisation in tetrahydrofuran (THF). 5mg lignin is suspended in lmL glacial acetic acid/acetyl bromide (9: 1 v/v) for 2 h. The solvent is then removed under reduced pressure, and the residue is dissolved in HPLC-grade THF and filtered over a 0.45 μπι syringe filter prior to injection into a 20 μΕ sample loop. Typical analysis set-ups resemble the following specific example: GPC-analyses are performed using a Shimadzu instrument consisting of a controller unit (CBM-20A), a pumping unit (LC 20AT), a degasser unit (DGU-20A3), a column oven (CTO-20AC), a diode array detector (SPD-M20A), and a refractive index detector (RID- 1 OA); the instrumental set-up is controlled using the Shimadzu LabSolution software package (Version 5.42 SP3). Three analytical GPC columns (each 7.5 x 30 mm) are connected in series for analyses: Agilent PLgel 5 μπι 10000 A, followed by Agilent PLgel 5 μπι 1000 A and Agilent PLgel 5 μπι 500 A. HPLC-grade THF (Chromasolv®, Sigma- Aldrich) is used as eluent (isocratic at 0.75 mL min-1 , at 40 °C). Standard calibration is performed with polystyrene standards (Sigma Aldrich, MW range 162 - 5 x 106 g mol-1), and lower calibration limits are verified / adjusted by the use of synthesized dimeric and trimeric lignin models. Final analyses of each sample is performed using the intensities of the UV signal at λ = 280 nm employing a tailor-made MS Excel-based table calculation, in which the number average molecular weight (M _n ) and the weight average molecular weight ( _w )) is calculated based on the measured absorption (in a.u.) at a given time (min) after corrections for baseline drift and THF-stemming artifacts.

M _n is calculated according to the formula in which M _n is the number average molecular weight

W; is obtained via w,- =— h,-——— with M being molecular weight

^{1 1 1} d(log M) ^{6 6}

hi being the signal intensity of a given logM measurement point

V being the volume of the curve over a given logM interval d(logM).

Mi is a given molecular weight.

The analysis is run in triplicate, and final values are obtained as the standard average.

M _w is calculated according to the formula ,„ =

∑Wi in which M _w is the number average molecular weight

W; is obtained via w,- =— h,-——— with M being the molecular weight

^{1 1 1} d(log M) ^{6 6} hi being the signal intensity of a given logM measurement point

V being the volume of the curve over a given logM interval d(logM).

Mi is a given molecular weight.

The analysis is run in triplicate, and final values are obtained as the standard average.

Eventually necessary adjustment of M _n and M _w with respect to the desired applications is achieved by mechanical breaking of polymeric lignin using a ball mill, by chemically or enzymatically polymerising oligomeric lignin.

Method of measuring aromatic hydroxyl and aliphatic hydroxyl content: Typically, a procedure similar to the one originally published can be used (A. Granata, D. S. Argyropoulos, J. Agric. Food Chem. 1995, 43, 1538-1544). A solvent mixture of pyridine and (CDC13) (1.6: 1 v/v) is prepared under anhydrous conditions. The NMR solvent mixture is stored over molecular sieves (4 A) under an argon atmosphere. Cholesterol is used as internal standard at a

concentration of 0.1 mol/L in the aforementioned NMR solvent mixture. 50 mg of Cr(III) acetyl acetonate are added as relaxation agent to this standard solution.

Ca. 30 mg of the lignin are accurately weighed in a volumetric flask and suspended in 400 μL· of the above prepared solvent solution. One hundred microliters of the internal standard solution are added, followed by 100 μL· of 2-chloro-4,4,5,5-tetramethyl-l,3,2-dioxaphospholane (Cl-TMDP). The flask is tightly closed, and the mixture is stirred for 120 min at ambient temperature. 3 IP NMR spectra are recorded using suitable equipment, similar or identical to the following example: On a Bruker 300 MHz NMR spectrometer, the probe temperature is set to 20 °C. To eliminate NOE effects, the inverse gated decoupling technique is used. Typical spectral parameters for quantitative studies are as follows: 90° pulse width and sweep width of 6600 Hz. The spectra are accumulated with a delay of 15 s between successive pulses. Line broadening of 4 Hz is applied, and a drift correction is performed prior to Fourier transform. Chemical shifts are expressed in parts per million from 85 % H3P04 as an external reference. All chemical shifts reported are relative to the reaction product of water with Cl-TMDP, which has been observed to give a sharp signal in pyridine/CDC13 at 132.2 ppm. To obtain a good resolution of the spectra, a total of 256 scans are acquired. The maximum standard deviation of the reported data is 0.02 mrnol/g, while the maximum standard error is 0.01 mrnol/g. (A. Granata, D. S. Argyropoulos, J. Agric. Food Chem. 1995, 43, 1538-1544). Quantification on the basis of the signal areas at the characteristic shift regions (in ppm, as reported in A. Granata, D. S. Argyropoulos, J. Agric. Food Chem. 1995, 43, 1538-1544) is done using a tailor-made table calculation in which the abundances, given in mmol/g, of the different delineable phosphitylated hydroxyl groups are determined on the basis of the integral obtained for the signal of the internal standard, that is present in the analysis sample at a concentration of 0.1 m, creating a signal at the interval ranging from 144.5 ppm to 145.3 ppm. The area underneath the peak related to the internal standard is set to a value of 1.0 during peak integration within the standard processing of the crude NMR data, allowing for determining abundances using simple rule-of -proportion mathematics under consideration of the accurate weight of the sample used for this analysis. The analysis is run in triplicate, and final values are obtained as the standard average.

Method of measuring hydrolysable ester content: The total ester content of the lignin can be determined by subjecting the lignin to alkaline hydrolysis conditions: Ca. 500 mg of lignin are dissolved in an excess of 1 M sodium hydroxide solution and heated to temperatures of above 70 - 80 °C for 12 h. The lignin is subsequently precipitated by acidifying the reaction mixture, isolated and freeze-dried.

Ca. 30 mg of the lignin are accurately weighed in a volumetric flask and suspended in 400 μL· of the above prepared solvent solution. One hundred microliters of the internal standard solution are added, followed by 100 μΐ. of 2-chloro-4,4,5,5-tetramethyl-l,3,2-dioxaphospholane (Cl-TMDP). The flask is tightly closed, and the mixture is stirred for 120 min at ambient temperature. 31 P NMR spectra are recorded using suitable equipment under the conditions reported above for the determination of aliphatic and aromatic hydroxyl contents. Quantification of the acid content is done on the basis of the signal intensities at the characteristic shift regions (in ppm) using a tailor-made table calculation referring to the signal of the internal standard.

Abundances are typically given in mmol/g. The ester content is obtained as the difference in the abundances of acid groups, aliphatic hydroxyl groups, and aromatic hydroxyl groups found in untreated vs. the lignin treated with sodium hydroxide as outlined above. The analysis is run in triplicate, and final values are obtained as the standard average.

Emollient: Suitable emollients are silicon based emollients. Silicone-based emollients are organo-silicone based polymers with repeating siloxane (Si 0) units. Silicone-based emollients of the present invention are hydrophobic and exist in a wide range of molecular weights. They include linear, cyclic and crosslinked varieties. Silicone oils are generally chemically inert and usually have a high flash point. Due to their low surface tension, silicone oils are easily spreadable and have high surface activity. Examples of silicon oil include: Cyclomethicones, Dimethicones, Phenyl-modified silicones, Alkyl-modified silicones, Silicones resins, Silica. Other emollients useful in the present invention can be unsaturated esters or fatty esters.

Examples of unsaturated esters or fatty esters of the present invention include: Caprylic Capric Triglycerides in combination with Bis-PEG/PPG-1 6/16 PEG/PPG-16/16 Dimethicone and C12- C15 Alkylbenzoate.

The basic reference of the evaluation of surface tension, polarity, viscosity and

spreadability of emollient can be found under Dietz, T., Basic properties of cosmetic oils and their relevance to emulsion preparations. SOFW- Journal, July 1999, pages 1-7.

Humectant: A humectant is a hygroscopic substance used to keep things moist. Typically, it is often a molecule with several hydrophilic groups, most often hydroxyl groups; however, amines and carboxyl groups, sometimes esterified, can be encountered as well (its affinity to form hydrogen bonds with molecules of water is the crucial trait). A humectant typically attracts and retains the moisture in the air nearby via absorption, drawing the water vapour into and/or beneath the organism/object's surface.

Suitable humectants include: Propylene glycol, hexylene glycol, and butylene glycol, Glyceryl triacetate, Neoagarobiose, Sugar alcohols (sugar polyols) such as glycerol, sorbitol, xylitol, maltitol, Polymeric polyols such as polydextrose, Quillaia, Urea, Aloe vera gel, MP diol, Alpha hydroxy acids such as lactic acid, Honey, Lithium chloride

Emulsifier: An emulsifier generally helps disperse and suspend a discontinuous phase within a continuous phase in an oil-in-water emulsion. A wide variety of conventional emulsifiers are suitable for use herein. Suitable emulsifiers include: hydrophobically-modified cross-linked polyacrylate polymers and copolymers, polyacrylamide polymers and copolymers, and polyacryloyldimethyl taurates. More preferred examples of the emulsifiers include:

acrylates/C 10-30 alkyl acrylate cross-polymer having tradenames PemulenTM TR-1,

PemulenTM TR-2 (all available from Lubrizol); acrylates/steareth-20 methacrylate copolymer with tradename ACRYSOLTM 22 (from Rohm and Hass); polyacrylamide with tradename SEPIGEL 305 (from Seppic).

EXAMPLES

Example 1: The following samples were evaluated by the method described below.

Sample A is PEG functionalized lignin oligomer in accordance with the present invention.

Sample B is unfunctionalised lignin mixed with a PEG* (comparative example). Av. # lignin monomers Functionalisation Lignin Content in

Lignin-PEG Hybrid

Lignin oligomer of 3-8 PEG ₅₀₀ linked via ether 22% (m/m)

Sample A bond

Lignin oligomer of 3-8 unfunctionalised 0% (m/m)

Sample B

*Sample B comprises the lignin starting material and the PEG starting material used in the synthesis of the PEG-functionalized lignin oligomer of Sample A as a chemically unreactive derivative (i.e., a derivative in which the functional group used to link it to the lignin has been consumed by activated methanol) (i.e. Sample B is the active PEG-derivative and lignin substrate used to make Sample A).

Lignin sample A is functionalized as following: Lignin (5 g) is dissolved in water containing sodium hydroxide (amount corresponding to lequivalnt (eq.) to total acidic groups in the lignin of choice, i.e. , phenolic hydroxyl and carboxylic acid groups). After 1 h of stirring at 50 °C, the suitably terminated PEG-functional, e.g., an epoxide-terminated PEG-functional, with a number average molecular weight of 500 Da is added (depending on the desired technical loading in ranges from 0.25 to 10.0 eq. to lignin phenolic hydroxyl groups) and the reaction mixture is stirred at 50 °C overnight.

After cooling to room temperature and acidifying to pH 2 using 10% (v/v) aqueous hydrogen chloride solution, the resulting suspension is centrifuged (15 min at 5000 rpm) to recover the PEGylated lignin in solid form. The isolated functionalised lignin is then washed 3 times with 50 mL acidified water (pH 2) followed by renewed isolation via centrifugation (15 min at

5000 rpm) each time. The final pellet was subsequently freeze-dried. The freeze-dried material is used for analysis and application without any additional manipulation.

General structure of lignin sample A:

backbone-O-L-'PEG' wherein the lignin is derived from wheat,

wherein L is a linker having the following structure:

R = R = H

X = OH

L' = CH ₂

and wherein the PEG was PEG500.

Lignin Sample A details:

Lignin Sample B is the same lignin as shown above for lignin sample A except for the PEG functionalisation. Lignin sample B is unfunctionalized.

Preparation of contact angle samples: Weigh out O. lg of PEG functionalised lignin oligomer and disperse in 1 litre of non-ionic surfactant water dispersion where the pH was raised to 10.5 by addition of sodium carbonate and stir it for 15 minutes at 200 rpm at room temperature. Then, glass slides were dipped for 30 minutes and allowed to dry two hours at room temperature. Following this preparatory procedure contact angle of deionized water on the treated surface was measured using First Ten Angstroms 200 equipment.

Contact Angle Data:

Sample A in accordance with the present invention showed superior surface modification properties than the comparison example (Sample B). Example 2, Illustrative examples:

Hand Dishwashing:

Granular laundry detergent compositions designed for front-loading automatic washing machines:

Wt% Wt%

Product I Product II

Linear alkylbenzenesulfonate 8 8

CI 2- 14 Alkylsulfate 1 1

AE7 2.2 2.2

C lo-i 2 Dimethyl

hydroxyethylammonium

chloride 0.75 0.75

Crystalline layered silicate (δ- Na ₂ Si ₂ 0 ₅ ) 4.1 4.1

Zeolite A 5 5

Citric Acid 3 3

Sodium Carbonate 15 15 Silicate 2R (Si0 ₂ :Na ₂ 0 at ratio

2:1) 0.08 0.08

Soil release agent 0.75 0.75

Acrylic Acid Maleic Acid

Copolymer 1.1 1.1

Carboxymethylcellulose 0.15 0.15

Protease - Purafect® (84 mg

active/g) 0.2 0.2

Amylase - Stainzyme Plus® (20

mg active/g) 0.2 0.2

Lipase - Lipex® (18.00 mg

active/g) 0.05 0.05

Amylase - Natalase® (8.65 mg

active/g) 0.1 0.1

TAED 3.6 3.6

Percarbonate 13 13

Na salt of Ethylenediamine- Ν,Ν'-disuccinic acid, (S,S)

isomer (EDDS) 0.2 0.2

Hydroxyethane di phosphonate

(HEDP) 0.2 0.2

MgSC-4 0.42 0.42

Perfume 0.5 0.5

Suds suppressor agglomerate 0.05 0.05

Soap 0.45 0.45

Sulphonated zinc phthalocyanine

(active) 0.0007 0.0007

S-ACMC 0.01 0.01

Lignin 0.01 1.0

Sulfate/ Water & Miscellaneous Balance Balance Automatic Dishwashing Cleaning composition:

such as Alcosperse® 246 or 247, a sulfonated copolymer of acrylic acid from Alco Chemical Co.

linear alcohol ethoxylate from Olin Corporation such as those described above

⁴ a sulfonated polymer such as those described above

⁵ one or more enzymes such as protease, mannaway, natalase, lipase and mixture thereof. The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."