TR201810838T4 - Enzymatic detergent compositions with granules. - Google Patents

Abstract

The invention relates to the prevention of malodour problems by using a granular detergent composition comprising 1 to 30% by weight of an alkyl ester fatty acid sulfonate surfactant and enzyme granules, wherein said composition is substantially free of thiosulfate.

Description

TECHNICAL FIELD This invention relates to granular detergent compositions, especially alkyl ester, especially methyl Granular detergent containing ester fatty acid sulfonate surfactants and enzyme granules relates to their composition.

BACKGROUND TO THE INVENTION Laundry detergent compositions have been ionic, ethoxylated alcohol for many years. anionic sulfonate or sulfate surfactant together with non-surfactants, for example, linear alkylbenzene sulfonate (LAS) or primary alkyl sulfate (PAS). A traditional ethoxylated alcohol used in laundry detergent compositions, typically an average of 3 to 9.1uk among non-ionic surfactants ethoxylated Cio-C1 alcohols having a degree of ethoxylation.

Recently, granular detergent compositions have been designed, where linear alkylbenzene methyl ester fatty acid of the following formula in place of some or all of the sulfonate sulfonate (MES) has been added: Battery( \CI-l3 where Ak= predominantly linear Cl4-16 alkyl chain. For example, the IUPAC nomenclature for the substance also specified as C16 MES is hexadecanoic. acid is 2-sulfo-, 1-methyl ester, sodium salt (Cl7H33NaO5S). Methyl ester sulfonate, e.g. of various renewable oleo-based methyl esters derived from oil (C 1 6-1 8) can be obtained by sulfonation. Besides renewable resource, MES, good biological It is also a special feature due to its degradability, cleaning power and resistance to calcium hardness. has importance.

EP-A-1 surfactants (α-sulfo- fatty acid esters), (bi)carbonate, zeolite and monoethylenically unsaturated mono- and di- high volumetric density containing a polymer containing carboxylic acid units granular detergents are described. and not more than 10 parts of 10% to 30% of at least one nonionic polyalkoxylated surfactant 90 to 70% of the substance selected mainly from α-sulfonated fatty acid derivatives. a surfactant mixture containing an anionic surfactant detergent composition is disclosed, the remainder of the composition is alkaline detergent additives, bleaching agents, optical brighteners, fragrance, anti-redeposition agents and enzymes Contains at least one component selected from among

Although methyl ester fatty acid sulfonate (MES) (partially) replacement of LASin Although it seems like a straightforward, easy process, inventors unexpectedly they encountered a bad odor problem during storage.

Now, surprisingly, 1% to 30% by weight of this malodor problem is an alkyl ester oil. granular detergent according to the invention containing acid sulfonate surfactant and enzyme granules It has been found that the compound in question can be prevented by the composition of thiosulfate. not included.

DESCRIPTION OF THE INVENTION 1 to 30% by weight of an alkyl ester fatty acid sulfonate according to a first aspect of the invention a granular detergent containing surfactant and 01 to 10% by weight enzyme granules composition is provided, wherein said composition does not contain substantially thiosulfate and wherein said detergent composition comprises methyl sulfate.

According to a second aspect of the invention, the pressure of the granular detergent composition according to the invention. A tablet detergent obtained by compression is described.

According to a third aspect of the invention, woven fabrics can be machine or hand washed. A process for a wash containing water in which the detergent composition or tablet detergent dissolves or disperses It includes the step of immersion in the solution, DETAILED DESCRIPTION OF THE INVENTION The granular detergent composition of the invention is 1 to 30% by weight of an alkyl ester fatty acid sulfonate surfactant, preferably inethyl ester fatty acid sulfonate surfactant and enzyme Contains granules, preferably in the amount of α-sulfo-fatty acid esters from 1 to 15% by weight, more preferably 3% to 8% by weight. Methods for the preparation of d-sulfo-fatty acid esters are readily available to those skilled in the art. beef tallow, oil, coconut oil, palm oil, white grease oil, cottonseed oil, rapeseed oil, soybean oil, yellow grease, of which from various sources, including mixtures or partial proportions can be prepared. Among the fatty acids suitable for the preparation of α-sulfo-fatty acid esters, but not limited to caprylic (C8), capric (Cio), lauric (C 12), myristic (Cis), linolenic (Cig), ricinoleic (Cig), aracidic (Czo), gadolic (Czo), behenic (C22), and erucic (sz) fatty acids. D-sulfo- prepared from one or more of these sources fatty acid esters are within the scope of this invention.

Alkyl ester oil prepared in dry powder form by the above-mentioned manufacturing processes acid sulfonate surfactant samples are typically approximately 75% to 85% by weight desirable Contains surfactant. Among other components in a typical production sample A particularly suitable component is sodium methylsulfate, which is typically the result of such an MES. at a level of about 1% -10% by weight (but not limited to this level) The composition may also contain one or more other surfactants. another surface active substance 5% to 40% by weight, preferably 7% by weight, based on the weight of the total composition present in an amount of from 30% to 30%.

Surfactants are well known to those skilled in the art. Many suitable detergent-active in the composite literature, for example by Schwartz and Perry "Surface-Active Agents and Detergents" Volume I and [1 and fully explained. Examples include alkylbenzene sulfonates, dallaninis or linear alkyl benzene sulfonates, primary and secondary alcohol sulfates, especially C8-C1 primary alcohol sulfates; alkyl ether sulfates, olefin sulfonates including alpha olefin sulfonates, alkane sulfonates, alkyl xylene sulfonates, dialkyl sulfosuccinates and alkyl carboxylates. These are sodium, available as potassium, calcium or magnesium salts or mixtures thereof it could be. Generally, sodium salts are preferred.

Another surfactant, preferably a sulfonate or sulfate anionic surfactant or a combination thereof. More preferably anionic surfactant linear alkylbenzene sulfonate or primary alkyl sulfate. Most preferred, other surfactant the substance is linear alkylbenzene sulfonate. linear alkyl benzene sulfonate sodium, available as potassium or alkaline earth inetal salts or mixtures of these salts it could be.

The other surfactant is also a nonionic surfactant, preferably average a degree of ethoxylation in the range of about 3 to 9, preferably about 3 to 7. The ethoxylated alcohol may contain nonionic surfactant. Alcohol natural or synthetic can be derived from the raw material. The preferred alcohol raw materials are coconut and palm The core is predominantly C12-C14 and oxo C1-C15 alcohols.

The nonionic surfactant is suitably weighted, based on the weight of the total composition. present in a preferred amount of 3 to 5 by weight.

Additional surfactants and detergent active compounds alkylpolyglucosides, ionic compounds such as polyhydroxyamides (glucamide), methyl ester ethoxylates, and glycerol monoethers May contain non-surfactants. Also cationic, amphoteric surfactants and/or zwitterionic surfactants may also be present. Preferred cationic surfactants eg general formula R1R2R3R4N+ X.“in quaternary ammonium salts, where R1 is a C2-C14 alkyl group, R2 and R3 are methyl groups, R4 is a 2- is the hydroxyethyl group and X. is a chloride ion. This material is commercially available by weight. can be done.

Preferred amphoteric surfactants are amine oxides, eg coco dimethyl amine oxide. Preferred zwitterionic surfactants are betaines and especially amidobetaines. Preferred betaines are C8 to Cl8 alkyl amidoalkyl betaines, for example coco amido betaine. These are 0% to 10% by weight, based on the weight of the total composition. co-surfactants, preferably present in an amount of 1% to 5% by weight can be included as

enzymes The detergent compositions of this invention may improve cleaning performance, fabric care and/or health. It contains one or more other enzymes that are compatible.

Among the enzymes suitable for inclusion in detergent compositions, preferably protease, lipase, amylase, cellulase, mannanase and oxidase, peroxidase, oxidoreductase, beta-glucanase, pectinase and/or pectate lyase. Most preferably, the compounds contain a proteolytic enzyme or It contains protease.

The appropriate ones of these enzymes are “Enzyme terminology 1992: recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Explained in Academic Press. The most up-to-date information on the terminology of enzymes ExPaSy Available online via Molecular Biology Server (htt z//usex as .or n!). Add additional enzymes mentioned on page 15, line 25 to line 19, line 29. may contain the maltogenic u-amylases described in line 29. commercially available The maltogenic α-amylases available from Novozymes are NovamleM and MaltogenaseTMHir.

The composition is also commercially available under the trade name Novozymesiden LipexTM, T231R. + A lipase variant of Humicola lanuginosa lipase with N233R substitutions or WO- It may include another variant as described in A-00/600633.

The composition also exits Novozymes: MannawayTM, NatalaseTM, RenozymeTM, OvozymeTM, CelluCleanTM, PolarzymeTM, StainzymeTM, CoronaseTM, PectaawayTM, PectawashTM, From Termamyl UltraTM and new enzymes Genencor: FN-3, FN-4, Purafect PrimeTM, Not disclosed in any of the previous descriptions, such as ProperaseTM, more commercially available It may also contain other enzymes.

Enzymes with cleaning properties in granular or particulate detergent compositions about 01 to about 100% by weight, preferably about 02 to about 2% by weight used.

It is important that detergent compositions do not contain thiosulfate to a large extent. has been found. Enzyme granules sometimes contain thiosulfate, so the enzyme does not contain thiosulfate. It has been found that the use of granules is important. The amount of thiosulfate in the compositions can be determined using standard analytical techniques. In the context of this invention, thiosulfate, alkalimetal specifically refers to any salt of thiosulfate such as sodium, but not the same also includes the ammonium, monoethanolamine or triethanolamine salts.

Detergent Makers Compositions of the invention may contain a detergency builder. Preferably, the total detergent builder substance present in an amount of less than 1% to 80% by weight, based on the weight of the composition. More preferably the amount of detergency builder compound is 1% to 603% by weight. detergent maker the compounds are well known to those skilled in the art. Many suitable detergent builder compounds available in the market. Examples of builder compounds zeolites, sodium tripolyphosphate, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, sodium silicate and their are mixtures.

Other optional detergent components The components are surfactants mentioned above to increase performance and properties. optionally more active as well as substances, detergent builder compounds and enzymes. may contain components.

Compositions of the invention, preferably 0 to 85% by weight, based on the weight of the total composition 0% to 60% by weight, preferably 0% to 40% by weight of sodium sulfate, sodium such as sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite. May contain inorganic, non-constructive salt.

Compositions of the invention may include a polycarboxylate polymer. Polycarboxylate polymers homopolymers of acrylic acid, maleic acid and acrylic/maleic acids and copolymers. BASF Aktiengesellschafthn (D-6700 Ludwigshaven, Germany) Organic material useful in his print publication 'Polymeric Dispersing Agents, Sokalan' polymers are described. Polycarboxylate polymer preferably sodium polyacrylate, sodium selected from the group consisting of acrylate maleate and mixtures thereof. Suitable for polymers Examples include polyacrylate Sokalan CP5 from BASF, that is, with a sodium salt maleic acid-acrylic acid copolymer.

Detergent compositions of the invention are soap, peroxyacid and persalt bleaches, bleaching property. exhibit activators, catalysts for bleaching by contact with air, release agents, cellulose ethers and esters, cellulosic polymers, other anti-redeposition agents, sodium bicarbonate, other inorganic salts, fluorescent agents, thermowhitening agents, polyvinyl pyrrolidone, other dye transfer inhibitor polymers, foam suppressants, foam enhancers, citric acid, dirt removing polymers, silicone, fabric softening compounds, one or more selected from perfume and colored dots such as blue dots May contain optional components. This list is not intended to be complete.

Form of Composition Compositions of the invention preferably have an average size of between 200 and 800 micrometers. They are granular detergent compositions in powder form. Alternatively, the compositions are in tablet form. it could be. The compositions are used as detergents for hand washing or as washing machine detergents. can be formulated for use.

Preparation of Compositions Granular compounds of the invention can be prepared by any suitable process. low to medium powders with a bulk density up to the level by spraying a slurry by drying and optionally by subsequent dosing of additional components (dry by mixing) can be prepared. "Concentrated" or "compact" powders for mixing and granulating processing operations, for example using a high speed mixer/granulator or other tower It can be prepared with processes that do not contain

Tablets can be prepared by compressing powders, especially "concentrated" powders.

The choice of the processing route depends on the stability of the surfactants or heat may be according to their sensitivity and the form in which they are present. In any case, all components are separate. can be added separately.

The invention is now described in more detail by way of the following non-limiting Examples. will be explained, parts and percentages are by weight unless otherwise stated in the examples. The following abbreviations are used in the examples, and the compounds have the specified functions. has: Sodium LAS: sodium Cio-Ci3 alkylbenzene sulfonate (anionic surfactant) Non-ionic 7EO: ethoxylated with an average of 7 ethyleneoxide units per molecule C13-C15 fatty alcohol (non-ionic surfactant) MES: sodium CIO'CIS methyl ester sulfonate (approximately 80%-90% pure, sodium salt average molecular weight = 370 - 390 g/mol) (anionic surfactant) STP: Sodium Tri Polyphosphate (complexing agent) Zeolite 4A: Sodium alumino silicate with SizAl ratio of 1 (ion exchange detergent builder) Sodium carbonate (precipitant, detergent and buffer) Calcite (filler) Sodium disilicate (detergent oil and buffer; alkaline silicate) Polymer: acrylic acid/maleic acid type polymer (anti-redeposition agent, anti- ashing agent or auxiliary detergent builder) SCMC: sodium carboxy methyl cellulose (anti-redeposition polymer) Fluorescent substance (optical bleach) Sodium sulfate (filler salt) Sodium chloride (filler salt) Dots: visual cue.

Sodium perborate monohydrate; (hydrogen peroxide) bleach.

MS: Sodium methyl sulfate, Aldrich output chemical Sodium thiosulfate: Chemical substance from BDH Prolabo Polarzyme 120 T: Protease enzyme granule from Novozymes; granule stabilizer Contains sodium thiosulfate.

Savinase : Protease enzyme granule from Novozymes; Contains sodium thiosulfate as granule stabilizer.

Stainzyme 12.0 T: Amylase enzyme granule from Novozymes; granule stabilizer Contains sodium thiosulfate.

Termamyl 60 T: Amylase enzyme granule from Novozymes; granule stabilizer Contains sodium thiosulfate.

Properase IOOOM: Genencor-exited protease enzyme granule; granular sodium Does not contain thiosulfate.

Purafect 3450M: Genencor-exited protease enzyme granule; granular sodium thiosulfate not included.

Lipex 100 T: Novozymes exiting lipase enzyme granule; granular sodium thiosulfate not included.

Savinase pure: Pure protease enzyme powder from Novozymes; coating and sodium does not contain thiosulfate Placebo granule: granule without enzymes and sodium thiosulfate from Novozymes BSA: Bovine Serum Albumin; pattern protein.

The following tables show the composition of the formulations used in examples 3-5: Zeolite-based powder Components Control (MES % miscellaneous not included) with Polarzyme at levels 1A 1B 1C 1D Polymer 1.0 1.0 1.0 1.0 non-lionic 13 1.3 1.3 1.3 sodium disilicate 3.0 3.0 3.0 3.0 Moisture, salt, 2.6 2.6 2.6 2.6 (As noted) Zeolite-based powder Components 10% MES -various types 1% methyl sulfate - miscellaneous with enzyme with enzyme Sodium LAS sodium sulfate Polymer non-ionic fluorescent substance Zeolite 4A sodium carbonate 20.1 sodium disilicate 3.0 Moisture, salt, NDOM 2.6 Polarzyme 12T Savinase 24GTT 0.0 Stainzyme 12T 0.0 MES (specified 11.2 Methyl sulfate 0.0 100.0 Components Control does not include ) Sodium LAS 23.9 Sodium 8.0 disilicate Sodium 15.6 sulfate Sodium 20.1 baking soda Sodium 3.5 Fluorescent 0.1 S T P-based powder 100.0 100.0 types and levels of enzymes Components Control does not include ) Calcite 1.0 Dots 1.5 Moisture, salt, 9.7 Polarzyme 0.1 Savinase 0.0 24.0GTT Properase 0.0 1000M Purafect 0.0 3450M (indicated 100.0 Components Sodium LAS sodium disilicate Polymer sodium sulfate sodium carbonate fluorescent substance sodium perborate dots Moisture, salt, NDOM Polarzyme 12T ST P-based powder types and levels of enzymes 2C 2D 2E 2F 2G 2H Carbonate-based powder Control (no enzymes) 3.2 3.2 6.3 6.3 1.0 1.0 28.9 27.9 39.9 39.9 0.1 0.1 1.0 1.0 0.5 0.5 .0 15.0 4.1 4.1 Carbonate-based powder Components Control (no enzyme) with 1% enzyme 100.0 100.0 Bad odor generated during storage was identified through GC/MS top layer analysis. is a dimethylsulfide (abbr. DMS), predominantly dimethyl-disulfide, dimethyl-trisulfide and dimethyl-tetrasulfide. The severity of malodor due to dimethylsulfides is best can be assessed by sniffing using a density scale DM TS-like' malodor intensity scale 0 No bad smell 1 medium 2 strong 3 severe Samples of various products are in closed glass jars, at room temperature, 37°C/70% 8 weeks at relative humidity and 45°C. At 37°C/70% relative humidity, the products were also stored in closed cardboard packages. MES in combination with thiosulfate-containing proteases in various products Zeoli't-based powder the product is 8 weeks at the following degrees no. bad smell after storage 37°C/70% bond] humidity 45°C (glass) (cardboard) (glass) MES not available (Control) 1A 0 0 0 20% IE replaced with MES 0 0 0 LAS; 0% Polarzyme 12T 20% 1C replaced with MES 0 0 1 LAS;0.2% Polarzyme 12T 20% replaced with MES 1D 0 1 2 LAS;%l Polarzyme 12T S T P-based powder the product is 8 weeks at the following degrees no. bad smell after storage 37°C/70% RH 45°C (glass) (cardboard) (glass) MES not available (Control) 2A 0 0 0 2B 0 0 O replaced with MES 80% replaced with MES 2C 0 O 0 LAS; 0.1% Polarzyme 12T 80% 2D replaced with MES 1 0 1 LAS; %l Polarzyme 12T 80% replaced with MES 2E 0 0 0 LAS; %0.1 Savinase 24GTT 80% 2F 2 0 1 replaced with MES LAS; 1% Savinase 24GTT Carbonate-based powder After the product has been stored for 8 weeks at the following temperatures no. bad smell 37°C/70% RH 45°C (glass) (cardboard) (glass) Enzyme free 3A 0 With the increase of enzyme level in all formulations with various types of detergent builders, It can be concluded that odor formation has increased.

MES or sodium methylsulfate in combination with thiosulfate-containing enzymes.

Zeoli't-based powder product bad after 8 weeks of storage at 45°C no. fragrance (glass) MES not available (Control) 1A 0 Zeolite-based powder product bad after 8 weeks storage at 45°C no. fragrance (glass) 24GTT Polarzyme 12T 24GTT Stainzyme 12T The formation of malodor is caused by the interaction between enzymes and methylsulfate rather than the MES itself. interaction appears to trigger (note: methylsulfate is the mainstay of MES production. one of the by-products).

Comparison of protease enzymes with or without thiosulfate.

S T P-based powder product in the following grades 8 no. week after storage bad smell 37°C/70% relative 45°C moisture (cardboard) (glass) references MES available 2A 0 0 not(Control) Replace with MES 2B 0 0 %SOLAS obtained; 0% protease Replace with MES containing T-iosulfate 2D 1 1 enzymes (% SOLAS with Novozymes; 1% out) Polarzyme 12T Replace with MES 2F 2 1 %SOLAS obtained; %one Savinase 24GTT Replace with MES without T-iosulfate 2G 0 0 enzymes (% SOLAS from Genenco; 1% out) Properase LOOM Replace with MES 2HO 0 obtained 80% LAS; %1EP-1 8000 ST P-based powder product in the following grades 8 no. week after storage bad smell 37°C/70% relative 45°C moisture (cardboard) (glass) Purafect 3450M Root odor in the presence of thiosulfate-free enzymes from Genencor bad odor does not occur with MES/ MS and thiosulfate (enzyme from Novozymes) present in its granules). Mixtures of MES or methylsulphate (1:] of single components with various enzymes) Controls (i.e. single Components) Bad odor after 4 weeks of storage 45°C glass Methyl sulfate Polarzyme 12T Savinase 24GTT Stainzyme 12T Ternamyl 60T Lipex 100T Properase LOOM Purafect 3450M Savinase pure BSA (model protein) Placebo granule (coating only) Sodium thiosulfate (chemical) I:I mixtures with thiosulfate-i-containing enzymes Bad odor after 4 weeks of storage 45°C glass MES/Polarzyme 1 MES/ Savinase 1 MES/ Stainzyme 1 1:] mixtures with thiosulfate-containing enzymes Bad odor after 4 weeks of storage 45°C glass MES/Thermamyl 2 1:] mixtures with enzymes that do not contain thiosulfate-i MES/Lipex MES/Properase MES/Purafect MES/ Savinase pure MES/Placebo 1:] mixtures with thiosulfate (chemical) Bad odor after 4 weeks of storage 45°C glass MES/ thiosulfate 3 Methyl sulfate/thiosulfate 3 Thiosulfate-free enzymes from Genencor, pure Savinase, BSA and Novozyme- Since the granules do not contain thiosulfate enzymes, there is no odor, 1:1 MES/MS and thiosulfate (enzyme from Novozymes) granules) have been shown to be due to the interaction. In addition, During storage of MES/MS containing thiosulfate, a very strong malodor developed.

The foul odor was determined to be DMS by GC/MS top layer analysis.

Claims (16)

REQUESTS l. 1 to 30% by weight of an alkyl ester fatty acid sulfonate surfactant and the composition by weight are substantially free of thiosulfate, wherein said detergent composition contains methyl sulfate. 2. A detergent composition according to claim 1, wherein the alkyl ester fatty acid sulfonate surfactant is the methyl ester fatty acid sulfonate surfactant. 3. A detergent composition according to claim 1, based on the amount of methyl ester fatty acid sulfonate. 4. A detergent composition according to any preceding claim wherein the enzyme is selected from the group consisting of protease, lipase, amylase, cellulase, mannanase and oxidoreductase. 5. A detergent composition according to any one of the preceding claims, further comprising linear 6. A detergent composition according to any preceding claim comprising an ethoxylated alcohol nonionic surfactant. 7. A detergent composition according to claim 6, wherein the ethoxylated alcohol nonionic surfactant has an average degree of ethoxylation n of 3 to 7. 8. A detergent composition according to any one of the preceding claims. to 1% by weight 9. A detergent composition according to claim 8, wherein said builder is selected from the group consisting of zeolite, sodium tripolyphosphate, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, sodium silicate and mixtures thereof. 10. A detergent composition according to any one of the preceding claims, comprising from 2% to 2% by weight. 11. A detergent composition according to claim 9, wherein sodium silicate is from 1% by weight to 12. A detergent composition according to any one of the preceding claims further comprising a cationic surfactant in an amount of 01 to 5% by weight. 13. A detergent composition according to any of the preceding claims, further comprising a polycarboxylate polymer selected from the group consisting of sodium polyacrylate, sodium acrylate maleate and mixtures thereof. 14. A detergent composition according to any of the preceding claims, characterized by soap, peroxyacid and persalt bleaches, activators exhibiting bleaching properties, air-contact bleaching catalysts, separating agents, cellulose ethers and esters, cellulosic polymers, other anti-redeposition agents, fluorescein It also contains one or more optional components selected from among agents, thermowhitening agents, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam suppressors, foam boosters, colorants, citric acid, dirt removing polymers, fabric softening compounds, colored dots and parchment. 15. A tablet detergent obtained by compression of the granular detergent composition according to any one of the preceding claims. 16. A process for hand or machine washing of woven fabrics, characterized in that it includes the step of immersing the fabrics in a washing solution containing water in which a granular detergent composition or tablet detergent as claimed in any one of the above claims is dissolved or dispersed.