JP2008546863A - Organocatalysts with enhanced enzyme compatibility - Google Patents

Abstract

  The present invention relates to a cleaning composition comprising an organic catalyst having enhanced enzyme compatibility and the process of making and using such a cleaning composition. The catalyst is a 3,4-dihydroisoquinoline zwitterionic sulfate derivative.

Description

  The present invention relates to cleaning compositions comprising organic catalysts and methods for making and using such cleaning products.

  Oxygen bleaches, such as hydrogen peroxide, are typically used to facilitate the removal of stains and dirt from clothing and various surfaces. Unfortunately, such agents are extremely temperature rate dependent. As a result, the bleaching action of such solutions is significantly reduced when such reagents are used in lower temperature solutions.

  In order to solve the aforementioned performance problems, a class of materials known in the industry as “bleach activators” has been developed. However, since such materials lose their effectiveness rapidly at solution temperatures below 40 ° C., new organics such as 3,4-dihydro-2- [2- (sulfooxy) decyl] isoquinolinium, inner salts, etc. A catalyst was developed. In general, such current art catalysts are effective in situations where the temperature of water is low, but inactivate certain enzymes. Since most cleaning detergents and cleaning compositions are formulated with enzymes, there can be problems in formulating cleaning products with such catalysts.

  Therefore, there is a need for an inexpensive cleaning composition that includes an organic catalyst that can provide utility that combines flexibility, low water bleaching performance and enzyme compatibility.

  The present invention relates to and relates to cleaning compositions containing organic catalysts having enhanced enzyme compatibility, and methods for their production and use.

Definitions As used herein, the term “cleaning composition”, unless otherwise indicated, is a general purpose or “heavy” cleaning agent in granular or powder form, especially a laundry detergent, liquid, gel or paste form. Detergents, especially so-called heavy liquid types, liquid luxury fabric detergents, hand-washing dishwashing agents, or light dishwashing agents, especially high foaming types, various tablets, granules, liquids and home and business use Machine dishwashing agent including rinse aid for, antibacterial hand wash mold, laundry bar, mouthwash, denture cleaner, car or carpet shampoo, liquid cleaner and disinfectant including bathroom cleaner, hair shampoo and hair rinse, shower Gel and foam baths and metal cleaners, and cleaning aids such as bleach additives and "stain sticks" or pre-treatment molds Including.

  As used herein, the phrase “independently selected from the group consisting of” means that the parts or elements selected from the cited Marcus group are the same, different, or a mixture of any elements It means that there may be.

  Using the test method disclosed in the test method section of this application, the values of the parameters of the invention of the applicants must be determined.

  Unless otherwise stated, all component or composition concentrations relate to the activity level of the component or composition, and impurities, such as residual solvents or byproducts, that may be present in commercial sources. Kinds are excluded.

  All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.

  Any maximum number limitation given throughout this specification should be understood to include any lower numerical limitation as if such lower numerical limitation was expressly written herein. . Every minimum numerical limitation described throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly set forth herein. Any numerical range recited throughout this specification shall be expressly set forth herein in any narrower numerical range that falls within such wider numerical range, as if all such numerical ranges were narrower. Include as if.

  All documents cited are, in relevant part, incorporated herein by reference and the citation of any document should not be construed as an admission that it is prior art with respect to the present invention.

Cleaning composition comprising an organic catalyst Applicants have discovered that the R ¹ portion of the organic catalyst of the present invention is a sensible choice. Without being bound by theory, Applicants believe that this is due to the favorable separation of the catalyst in an aqueous environment as a result of the R ¹ moiety being the wise choice described above.

  In one embodiment of Applicant's invention, Applicant's cleaning composition consists of an organic catalyst having an enzyme compatibility value of 7 or higher, or 80 or higher.

In one aspect of Applicant's invention, Applicant's cleaning composition consists of an organic catalyst having the following Formula 1 or Formula 2 or a mixture thereof.

Here, R ₁ is a branched alkyl group containing 9 to 24 carbons or a linear alkyl group containing 11 to 24 carbons, a branched alkyl group containing 9 to 18 carbons or 11 to 18 carbons. The linear alkyl group containing carbon is 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, Selected from the group consisting of iso-decyl, iso-tridecyl, and iso-pentadecyl, or selected from the group consisting of 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, iso-tridecyl, iso-pentadecyl The

  The balance of any aspect of the cleaning composition described above is maintained with one or more adjuvants.

Methods for Producing Suitable Organic Catalysts Suitable organic catalysts can be produced using a variety of reaction vessels and methods including batch, semi-batch and continuous processes.

  In one aspect of Applicant's invention, the above-described method for producing a catalyst includes a step of reacting a 3,4-dihydroisoquinoline sulfur trioxide complex with an epoxide to produce the organic catalyst.

  In another aspect of Applicant's invention, the process for preparing the catalyst comprises a 3,4-dihydroisoquinoline selected from the group consisting of sulfur trioxide, a substance that provides sulfur trioxide, and mixtures thereof. Reacting to produce a 3,4-dihydroisoquinoline sulfur trioxide complex, and reacting such 3,4-dihydroisoquinoline sulfur trioxide complex with an epoxide to produce the organic catalyst.

  In another aspect of Applicant's invention, the method for producing a catalyst described above comprises the step of reacting 3,4-dihydroisoquinoline with an epoxide sulfur trioxide complex to produce the organic catalyst.

  In another aspect of Applicant's invention, the method of making a catalyst described above comprises reacting an epoxide with a material selected from the group consisting of sulfur trioxide, a material that provides sulfur trioxide, and mixtures thereof. Forming a sulfur trioxide complex, and reacting such an epoxide sulfur trioxide complex with 3,4-dihydroisoquinoline to produce the organic catalyst.

  A variation of the foregoing catalyst containing an oxaziridinium ring can be achieved by contacting the variation of the catalyst containing an iminium ring with an oxygen transfer agent such as peroxycarboxylic acid or peroxymonosulfuric acid, for example, Oxone®. ) Etc. Such species can be formed in situ and can be used without purification.

  One of ordinary skill in the art for treating the teachings herein can readily determine the desired reaction conditions and reactant concentrations, but general reaction parameters for the aforementioned embodiments of Applicants' invention include from about 0 ° C to about 150 ° C. Or a reaction temperature of about 0 ° C. to about 125 ° C., about 0.1 MPa (0.1 atm) to about 10.1 MPa (100 atmospheres), about 0.03 MP (0.3 atmospheres) to about 1.01 MPa (10 atmospheres) or about Reaction pressures from 0.1 MPa (1 atmospheres) to about 1.01 MPa (10 atmospheres); reaction times from 0.1 hours to about 96 hours, from about 1 hour to about 72 hours, or from about 1 hour to about 24 hours. The reaction may be carried out under an inert atmosphere or under anhydrous conditions (for example, use of an anhydrous solvent when a solvent is used).

  Materials used in carrying out Applicant's process include 3,4-dihydroisoquinolines, epoxides and mixtures thereof, sulfur trioxide, sulfur trioxide and sources of mixtures thereof, and solvents.

  When using 3,4-dihydroisoquinoline, the initial reaction mixture generally contains from about 0.5 wt% to about 70 wt%, from about 5 wt% to about 70 wt%, or from about 10 wt% to about 10 wt%. Contains 50% by weight. 3,4-Dihydroisoquinoline can be prepared according to the procedure shown in Example 1.

  When using epoxides, the initial reaction mixture generally comprises from about 0.5% to about 70%, from about 5% to about 70%, or from about 10% to about 50% by weight of such materials. Suitable epoxides include 2-propyl heptyl glycidyl ether, 2-butyl octyl glycidyl ether, 2-pentyl nonyl glycidyl ether, 2-hexyl decyl glycidyl ether, n-dodecyl glycidyl ether, n-tetradecyl glycidyl ether, n- Examples include, but are not limited to, hexadecyl glycidyl ether, n-octadecyl glycidyl ether, isononyl glycidyl ether, iso-decyl glycidyl ether, iso-tridecyl glycidyl ether, and mixtures thereof. These materials may include an oligomeric form of glycidyl ether that may be optionally omitted before being used as a reactant. 2-Propylheptylglycidal ether can be prepared as described in Example 2 herein. The other aforementioned glycidyl ethers can be prepared by the general procedure of Example 2 by substituting 2-propylheptanol with a suitable alcohol. Suitable alcohols include 2-propylheptanol, 2-butyloctanol, 2-pentylnonanol, 2-hexyldecanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, iso -Nonanol, iso-decanol, iso-tridecanol.

  When using sulfur trioxide, a source of sulfur trioxide and mixtures thereof, the initial reaction mixture generally contains from about 0.5% to about 70%, such as from about 5% to about 70% by weight of such materials. %, From about 10% to about 50% by weight. Suitable materials include sulfur trioxide and sulfur trioxide trimethylamine, sulfur trioxide dioxane, sulfur trioxide pyridine, sulfur trioxide N, N-dimethylformamide, sulfur trioxide sulfolane, sulfur trioxide tetrahydrofuran, sulfur trioxide diethyl And sulfur trioxide complexes such as ether and sulfur trioxide 3,4-dihydroisoquinoline, and mixtures thereof.

  The balance of any reaction mixture is generally a solvent. When using a solvent, the initial reaction mixture generally comprises up to 99% by weight solvent, from about 10% to about 90% solvent, or from about 20% to about 80% solvent. Suitable solvents include acetonitrile, dioxane, t-butyl methyl ether, tetrahydrofuran, N, N-dimethylformamide, sulfolane, chlorobenzene, toluene, 1,2 dichloroethane, methylene chloride, chloroform, diethyl ether, hexanes, pentanes, Aprotic, polar and nonpolar solvents such as benzene, xylenes, and mixtures thereof. Suitable solvents can be purchased from Aldrich (P.O. Box 2060, Milwaukee, WI 53201, USA).

Cleaning compositions and cleaning composition additives comprising Applicant's organic catalyst The cleaning compositions of the present invention are for example for laundry applications, hard surface cleaning, automatic dishwashing applications and cosmetics such as dentures, teeth, hair and skin. It can be used advantageously in applications. Due to the unique advantages of both increased effectiveness in cold solutions and excellent enzyme compatibility, the organic catalysts of the present invention are ideally used for bleach-containing detergents or laundry bleach additives. Suitable for laundry applications such as bleaching fabrics. Furthermore, the organic catalyst of the present invention may be used in both granules and liquid compositions.

  The organic catalyst of the present invention may also be used in cleaning additive products. Cleaning additives that include the organic catalysts of the present invention are ideally suitable for inclusion in the cleaning process when additional bleaching effects are desired. Such entities have, but are not limited to, cold solution cleaning applications. The additive product can be Applicant's organocatalyst in its simplest form. Preferably, the additive can be packaged in a dosage form for addition to a cleaning step in which a peroxygen source is used and desiring to increase the bleaching effect. Such single dosage forms may contain pills, tablets, gelcaps or other single dosage units such as premeasured powders or liquids. Filler or carrier materials may be included to increase the volume of such compositions. Suitable filler or carrier materials include, but are not limited to, various salts such as sulfate, carbonate and silicate, as well as talc, clay and the like. The filler or carrier material for the liquid composition may be water or low molecular weight primary and secondary alcohols including polyols and diols. Examples of such alcohols include, but are not limited to methanol, ethanol, propanol and isopropanol. The composition may contain from about 5% to about 90% of such materials. Acidic fillers can be used to lower the pH. Alternatively, the cleaning additive may include an activated peroxide source as defined below, or an adjunct component as fully defined below.

  Applicants 'cleaning compositions and cleaning additives require a catalytically effective amount of Applicants' organic catalyst. The required concentration of such a catalyst can be achieved by adding one or more of Applicant's organic catalysts. In a practical and non-limiting manner, the compositions and cleaning processes of the present invention are at least 0.001 ppm, from about 0.001 ppm to about 500 ppm, about. It can be adjusted to provide the user's organic catalyst on the order of 005 ppm to about 150 ppm, or about 0.05 ppm to about 50 ppm. In order to obtain such concentrations in the cleaning solution, typical compositions herein are from about 0.0002% to about 5% by weight of the cleaning composition, or even from about 0.001% to about May contain 1.5% by weight of organic catalyst.

  If Applicant's organic catalyst is used in a granular composition, Applicant's organic catalyst is in the form of encapsulated particles and is filed during storage from the moisture and / or other components of the granular composition. It may be desirable to protect human organic catalysts. In addition, encapsulation is also a means of controlling the availability of Applicant's organic catalyst during the cleaning process and can enhance the bleaching performance of Applicant's organic catalyst. In this regard, Applicant's organic catalyst can be encapsulated using any encapsulating material known in the art.

  The encapsulating material typically encapsulates at least a portion, preferably all, of Applicant's organic catalyst. Typically, the encapsulating material is water soluble and / or water dispersible. The glass transition temperature (Tg) of the encapsulant may be 0 ° C. or higher.

  The encapsulating material is preferably from the group consisting of carbohydrates, natural or synthetic rubber, chitin and chitosan, cellulose and cellulose derivatives, silicates, phosphates, borates, polyvinyl alcohol, polyethylene glycol, paraffin wax and combinations thereof. Selected. Preferably, the encapsulant is a carbohydrate, typically selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, and combinations thereof. Most preferably, the encapsulant is starch. Preferred starches are described in EP 0 922 499, US Pat. No. 4,977,252, US Pat. No. 5,354,559, US Pat. No. 5,935,826.

  The encapsulating material may be microspheres made from a plastic resin such as thermoplastic, acrylonitrile, methacrylonitrile, polyacrylonitrile, polymethacrylonitrile and mixtures thereof; commercially available microspheres that can be used are Supplied under the trade name Expancel® by Expancel of Stockviksverken, Sweden, as well as PQ (PQ) in Valley Forge, Pennsylvania, USA Corp. under the tradenames PM6545, PM6550, PM7220, PM7228, Extendspheres®, Luxsil®, Q-cel® and Sphericel (Registered trademark) That.

  The cleaning compositions listed herein are preferably formulated so that the cleaning water has a pH between about 6.5 to about 11, or even about 7.5 to about 10.5 during an aqueous cleaning operation. Is done. The liquid dishwashing product formulation may have a pH between about 6.8 and about 9.0. Laundry products typically have a pH between about 9 and about 11. Techniques for controlling the pH to the recommended usage level include the use of buffers, alkalis, acids and the like and are well known in the art.

Auxiliary Substances Although not essential for the purposes of the present invention, the non-limiting list of adjuvants exemplified below is suitable for use in the composition, eg, to assist or improve cleaning performance. In particular embodiments of the present invention, for the treatment of the substrate to be cleaned or to change the aesthetics of the cleaning composition, such as when using fragrances, colorants, dyes, etc. Is desirable. The exact nature of such additional ingredients, and the concentration at which they are incorporated, depends on the physical form of the composition and the nature of the cleaning operation to be used. Suitable adjuvant materials include surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic agents, bleach activators, hydrogen peroxide, hydrogen peroxide sources , Preformed peracids, polymer dispersants, clay soil removal / anti-redeposition agents, brighteners, foam inhibitors, dyes, fragrances, structural stretchers, softeners, carriers, hydrophiles, processing aids Examples include, but are not limited to, agents, solvents, and / or pigments. In addition to the disclosure below, suitable examples and concentrations of such other adjuvants are disclosed in US Pat. No. 5,576,282, US Pat. No. 6,306,812 B1, and US Pat. No. 6,326,348 B1. Which are incorporated herein by reference.

  As mentioned above, the auxiliary ingredients are not essential for the Applicants' compositions. Accordingly, certain embodiments of Applicants' compositions do not contain one or more of the following adjunct materials: surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes, and enzyme stability. Agent, catalyst material, bleach activator, hydrogen peroxide, hydrogen peroxide source, preformed peracids, polymer dispersant, clay soil removal / anti-redeposition agent, whitening agent, foam inhibitor, dye, fragrance, Structural elasticizers, softeners, carriers, hydrophiles, processing aids, solvents and / or pigments. However, where one or more adjuvants are present, the one or more adjuvants may be present as described in detail below.

  Bleach—The cleaning composition of the present invention may comprise one or more bleaches. Suitable bleaching agents other than bleaching catalysts include photobleaching agents, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids and mixtures thereof. In general, when a bleaching agent is used, the composition of the present invention comprises about 0.1% to about 50% or even about 0.1% to about 25% by weight bleaching of the subject cleaning composition. An agent may be included. Examples of suitable bleaching agents include:

(1) Photobleaching agents such as sulfonated zinc phthalocyanine;
(2) Pre-formed peracids: appropriately formed percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfuric acid and salts such as Oxzone®, And peracids such as compounds selected from the group consisting of these and mixtures thereof, but not limited thereto. Formula R— (C═O) O—OM, where R is a branched alkyl group, if desired, 6 to 14 carbon atoms or 8 to 12 carbons when the peracid is hydrophobic When the atom and the peracid are hydrophilic, the hydrophobic and hydrophilic peracids with 6 or fewer carbon atoms or even 4 or fewer carbon atoms, and M with counter ions such as sodium, potassium, and hydrogen. Suitable percarboxylic acids including.
(3) alkali metal salts such as perborate (usually mono- or tetra-hydrate), percarbonate, persulfate, perphosphate, persilicate sodium salts and mixtures thereof. A hydrogen peroxide source (eg, inorganic perhydrate salts). In one aspect of the invention, the inorganic perhydrate salt is selected from the group consisting of perborate, sodium percarbonate, and mixtures thereof. The inorganic perhydrate salt (if used) is typically present in an amount of 0.05 to 40%, or 1 to 30% by weight of the total composition, typically the composition Incorporated as a crystalline solid (optionally coated). Suitable coatings include inorganic salts (such as alkali metal silicates, carbonates or borates or mixtures thereof) or organic materials (such as water soluble or dispersible polymers, waxes, oils or fatty soaps). . and,
(4) Bleach activators having R— (C═O) —L. [Wherein R is an alkyl group which is optionally branched and has 6 to 14 carbon atoms or 8 to 12 carbon atoms when the bleach activator is hydrophobic. When the bleach activator is hydrophilic, it has less than 6 carbon atoms, or even less than 4 carbon atoms, and L is a leaving group. ] Examples of suitable leaving groups are benzoic acid and its derivatives (especially benzenesulfonate). Suitable bleach activators include dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or its salts, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine (TAED) And nonanoyloxybenzene sulfonate (NOBS). Suitable bleach activators are also published in WO 98/17767. In a situation where a suitable bleach activator is used, in one aspect of the invention, the cleaning composition comprises NOBS, TAED, or a mixture thereof.

  The peracid and / or bleach activator (if present) is generally about 0.1 to about 60%, about 0.5 to about 40% or even about 0.6, based on the composition. Present in the composition in an amount of .about.10% by weight. One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracids or precursors thereof.

  The amount of hydrogen peroxide source and peracid or bleach activator is such that the molar ratio of available oxygen (supplied from the peroxide source) to peracid is from 1: 1 to 35: 1, or even 2: You may choose to become 1-10: 1.

  Surfactant—The cleaning composition according to the present invention may comprise a surfactant or a surfactant system, wherein the surfactant is a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric. It can be selected from surfactants, bipolar surfactants, semipolar nonionic surfactants and mixtures thereof. The surfactant (if present) is typically about 0.1% to about 60%, about 1% to about 50% or even about 5% to about 40% by weight of the title composition. % Concentration.

  Builders-The detergent compositions of the present invention may comprise one or more detergent builders or builder systems. When a builder is used, the title composition typically contains at least about 1%, about 5% to about 60%, or even about 10% to about 40% by weight of the builder of the title composition. Including.

  Builders include alkali metal salts of polyphosphates, ammonium and alkanol ammonium salts, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders polycarboxylate compounds, ether hydroxy polycarboxylates, Copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid Various alkali metal salts, ammonium salts and substituted ammonium salts of acetic acid, as well as, for example, mellitic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl Polycarboxylates such as Ruokishikohaku acid, as well as those soluble salts include, but are not limited to.

  Chelating Agent—The cleaning composition herein may contain a chelating agent. Suitable chelating agents include copper, iron and / or manganese chelating agents and mixtures thereof. If a chelating agent is used, the title composition may comprise from about 0.005% to about 15%, or even from about 3.0% to about 10%, by weight of the title composition.

  Dye Transfer Inhibitor—The cleaning composition of the present invention may also include one or more dye transfer inhibitors. Suitable polymeric dye migration inhibitors include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinyl oxazolidones and polyvinyl imidazoles, or mixtures thereof. However, it is not limited to these. When present in the subject composition, the dye transfer inhibitor is about 0.0001% to about 10%, about 0.01% to about 5%, or even about 0.1% by weight of the composition. It may be present at a concentration of ˜about 3% by weight.

  Brighteners-The cleaning compositions of the present invention can also contain additional components (such as fluorescent brighteners) that can also tint the article being cleaned. Suitable optical brightener concentrations include concentrations as low as about 0.01 wt.%, About 0.05 wt.%, About 0.1 wt.%, Or even about 0.2 wt. Furthermore, a high concentration of 0.75% by weight can be mentioned.

  Dispersants—The compositions of the present invention can also include a dispersant. Suitable water-soluble organic materials include homopolymer or copolymer acids or salts thereof, of which the polycarboxylic acids are at least two that are separated from each other by no more than two carbon atoms. Contains carboxyl radicals.

  Enzymes-cleansing compositions can include one or more enzymes that provide cleaning performance and / or fabric care benefits. Examples of suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate triases, keratinases, Reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, maranase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase and amylase, or These mixtures include, but are not limited to. A typical combination is an enzyme reaction mixture that may include, for example, protease and lipase with amylase. When present in the cleaning composition, the enzymes described above may comprise from about 0.00001% to about 2%, from about 0.0001% to about 1%, or even about 0.001% by weight of the composition. It may be present at a concentration of about 0.5% by weight of enzyme protein.

  Enzyme stabilizers—A variety of techniques can stabilize enzymes used in detergents. The enzymes used herein can be stabilized by the presence of a water-soluble source of calcium and / or magnesium ions in the final composition that supplies calcium and / or magnesium ions to the enzyme. In the case of an aqueous composition containing a protease, a reversible protease inhibitor (such as a boron compound) can be added to further improve the stability.

  Catalytic Metal Complex—Applicants' cleaning compositions can include a catalytic metal complex. One type of metal-containing bleach catalyst is a transition metal cation with limited bleach catalyst activity, such as a copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation, a zinc or aluminum cation. Auxiliary metal cations with little or no bleaching catalyst activity, and sequestering agents with limited stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra A catalyst system comprising (methylene phosphonic acid) and their water-soluble salts. Such a catalyst is disclosed in US Pat. No. 4,430,243.

  If desired, the compositions herein can be catalyzed with manganese compounds. Such compounds and concentrations used are well known in the art and include, for example, manganese-based catalysts disclosed in US Pat. No. 5,576,282.

  Cobalt bleach catalysts useful herein are known and described in US Pat. No. 5,597,936, US Pat. No. 5,595,967. Such cobalt catalysts can be readily prepared by known procedures such as, for example, US Pat. No. 5,597,936 and US Pat. No. 5,595,967.

  The compositions herein may suitably comprise a transition metal complex of a ligand such as a macropolycyclic hard ligand abbreviated as bispidones (WO 05/042532 A1) and / or “MRLs”. As a practical matter, and not by way of limitation, the compositions and methods herein typically provide at least about one-tenth of the active MRL family within the water-soluble cleaning medium, and typically Can be adjusted to have from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 pm, and from about 0.1 ppm to about 5 ppm MRL in the cleaning solution.

  Suitable transition metals in the present transition metal bleaching catalyst include, for example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane.

  Suitable transition metal MRLs are readily prepared by known procedures, such as those taught in PCT International Publication No. WO 00/32601, and US Pat. No. 6,225,464.

  Solvent—Suitable solvents include water and other solvents (eg, lipophilic fluids). Examples of suitable lipophilic fluids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerol derivatives such as glycerol ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, Low volatile non-fluorinated organic solvents, diol solvents, other environmentally friendly solvents, and mixtures thereof.

Methods for Producing Cleaning and / or Treatment Compositions The cleaning compositions of the present invention can be formulated in any suitable form, prepared by any method selected by the formulator, and non-limiting examples of methods are described in this application. Examples of humans, as well as US Pat. No. 5,879,584, US Pat. No. 5,691,297, US Pat. No. 5,574,005, US Pat. No. 5,569,645, US Pat. No. 5,565,422, US Pat. No. 5,516,448, US Pat. No. 5,489,392, and US Pat. No. 5,486,303, all of which are incorporated herein by reference. be written.

Method of Use The present invention includes a method for cleaning a situation, particularly a surface or fabric. These methods involve Applicant's cleaning composition embodiments diluted in undiluted form or in a cleaning solution to contact at least a portion of the surface or fabric, and then, optionally, the surface or Including the step of rinsing the fabric. The surface or fabric may be subjected to a washing step prior to the aforementioned rinsing step. For purposes of the present invention, washing includes, but is not limited to, rubbing and mechanical agitation. As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are ideally suited for use in laundry applications. The present invention therefore includes a method for laundering fabrics. The method includes contacting the fabric to be laundered with the laundering wash solution comprising at least one embodiment of the laundering composition of the present application, a lavage additive, or a mixture thereof. The fabric may include almost any fabric that can be washed under normal consumer use conditions. This solution preferably has a pH of about 8 to 10.5. This composition may be used at a concentration in solution of from about 500 ppm to about 15,000 ppm. The water temperature typically ranges from about 5 ° C to about 90 ° C. The water to fabric ratio is typically about 1: 1 to about 30: 1.

Organic Catalyst / Enzyme Compatibility Test In the tests described below, alpha amylase activity is used to measure the effect of an organic catalyst on the enzyme.

  Apparatus @ UV / Vis spectroscopic analyzer capable of measuring 415 nm, 40 ° C. heated magnetic stirrer, 5 mL Luer lock syringe and filter (Acrodisc 0.45 μm), pH meter, balance (four-point analysis).

  Reagents Merck amylase kit (Merck Eurolab, Cat. No. 1.197718.0001); Tris base (Sigma Cat # T-1503 or equivalent); Calcium chloride dihydrate (Sigma Cat # C-5080, Or sodium thiosulfate pentahydrate (Sigma Cat # S-6672 or equivalent); hydrochloric acid (VWR Cat # JT95535-0 or equivalent); Hardness solution (CTC group, 3.00 g / cc) Sodium percarbonate; Peracetic acid (Aldrich, Cat. # 26933-6 or equivalent); Termamyl, Natalase, Duramil (Novozymes, Denmark) amylase enzyme; Enzyme-free granular detergent matrix organic catalyst Or bleach.

1. ) Solution preparation: Prepare the following: a. ) Prepare 1 liter of Tris assay buffer 0.1 M Tris buffer, 0.5% sodium thiosulfate (W / V), 0.11% calcium chloride (W / V), pH 8.3.
b. ) 250 ppm H ₂ O ₂ (0.77 g percarbonate) and 0.5% enzyme and bleach-free granular detergent product in semi-processed detergent solution deionized water (W / V) and Prepare 1 liter of 2.65 g / L (10 gpg) hardness (880 UI hardness).
c. ) Stock of Termamyl, Duramil and Natalase. Make 100633 mL of 0.1633 mg of active Termamyl per mL of Tris buffer, 0.1159 mg of active natalase per mL of Tris buffer, 0.1596 mg of active duramil per mL of Tris buffer.
d. ) Make 500 ppm methanol solution of organic catalyst stock μm.
e. ) Make a 3955 ppm peracetic acid solution in peracetic acid stock deionized water.
f. ) Amylase Reagents In order to prepare the final reagents used in the amylase activity assay, the Merck kit is used to prepare Flacons (containers) 1 and 2 using Flacon 3 followed by a mixture of Flacons 1 and 2. follow orders.

2. Example of analysis a. ) Analysis of sample with enzyme only: Place 100 mL of semi-processed detergent solution into a 150 mL beaker. Place the beaker on a heated stir plate and raise the temperature to 40 ° C. while stirring. YμL of enzyme stock is placed in a beaker containing Duramil Y = 612 μL, Termamyl 306 μL, or Natalase 918 μL. Add only the enzyme of interest. Stir the sample for 1 minute. Start the timer. After 7 minutes 45 seconds, a sample is taken and filtered using a 0.45 μm syringe filter (5 mL syringe). 6 μL of the filtered sample is mixed with 250 μL of amylase reagent in a cuvette and the cuvette is placed in a UV / VIS spectrometer and the change in absorbance at 415 nanometers is observed. The time (t _E ) is measured by rounding off the time until the absorbance of each enzyme reaches 1.0. Step 2. B. ), The following 2. C. ) To use the _{t E} of each enzyme.
b. ) Analysis of samples containing only enzyme and peracetic acid. Step 2. A) ) Except after the addition of enzyme, the solution is stirred for 1 minute, then 127 μL of peracetic acid stock is added before the timer is started. Step 2. A) The sample is pulled out in 7 minutes and 45 seconds in the same manner as in step (b). After mixing the sample and reagent, the absorbance at time t _E is recorded for each enzyme. Such an absorbance _Ab is designated.
c. ) Analysis of samples containing enzymes, peracetic acid and organic catalysts. Step 2. A) ) 1. After the addition of enzyme, stir the solution for 1 minute, then add 127 μL peracetic acid stock and 100 μL organocatalyst stock before starting the timer A) The sample is pulled out in 7 minutes and 45 seconds in the same manner as in step (b). After the sample and reagent are mixed, the absorbance of each enzyme at t _E is recorded. Such an absorbance _Ac is designated.

3. ) Calculate enzyme suitability value (ECV).
a. ) Calculate ECV for Termamyl (ECV _ter ), Duramil (ECV _dur ), Natalase (ECV _nat ), each individual enzyme. The ECV of a particular enzyme is (A _c / A _b ) × 100 for that enzyme, where A _b and _Ac are step 2. B. ) And 2. C. ) Are values determined respectively.
b. ) The ECV for a given organocatalyst is the average ECV for the three enzymes. Therefore, ECV = (ECV _ter ++ ECV _dur ++ ECV _nat ) / 3.

  Unless otherwise indicated, materials are available from Aldrich (Wisconsin, USA (P.O. Box 2060, Milwaukee, WI 53201, USA)). In Examples 1-12, the solvent acetonitrile can be replaced with other solvents including, but not limited to, 1,2-dichloroethane.

Example 1: Preparation of mono- [2- (3,4-hydro-isoquinoline-2-yl) -1- (2-propylheptyloxymethyl) -ethyl] ester sulfate, inner salt of sulfuric acid Preparation of heptyl glycidyl ether: To heat dry, a 500 mL round flask with a funnel filled with epichlorohydrin (15.62 g, 0.17 mol) was added to 2-propylheptanol ( Pfaltz & Bauer (Pfaltz & Bauer, Inc.) Connecticut, USA (172 E. Aurora Street, Waterbury CT, 06708, USA) (20 g, 0.127 mol) and stannic chloride (0.20 g, 0.001) Mole). The reaction is kept under an argon atmosphere and warmed to 90 ° C. using an oil bath. Epichlorohydrin is added dropwise to the stirring solution over 60 minutes, followed by stirring at 90 ° C. for 18 hours. The reaction mass was attached to a vacuum distillation head and 1-chloro-3- (2-propyl-heptyloxy) -propan-2-ol was 26.7 Pa (0.2 mmHg) at a temperature range of 90 ° C. to 95 ° C., weight = Distill at 22.1 g. 1-Chloro-3- (2-propyl-heptyloxy) -propan-2-ol (5.0 g, 0.020 mol) is dissolved in tetrahydrofuran (50 mL) and stirred at room temperature under an argon atmosphere. To the stirring solution is added potassium t-butoxide (2.52 g, 0.022 mol) and the suspension is stirred at room temperature for 18 hours. The reaction is then evaporated to dryness and the residue is dissolved in hexanes and washed with water (100 mL). The phases were separated hexanes, and dried over Na ₂ SO _4, filtered and evaporated to dryness to give the Petit Legris Cedar ether to crude 2-propyl, which can be further purified by vacuum distillation.

Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinoline-2-yl) -1- (2-propylheptyloxymethyl) -ethyl] ester, inner salt: 250 mL heat-dried with condenser A three-necked round bottom flask was charged with dry argon, a magnetic stirring bar, a thermometer, and a heating bath were added, and 3,4-dihydroisoquinoline (0.38 mol, Example of US Pat. No. 5,576,282) 1), 2-propylheptylglycidyl ether (0.38 mol prepared as above), SO ₃ -DMF complex (0.38 mol), acetonitrile (500 mL). The reaction is warmed to 80 ° C. and stirred at temperature for 72 hours. The reaction is cooled to room temperature, dried by evaporation, and the residue is recrystallized from ethyl acetate and / or ethanol to produce the desired product.

Example 2: Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (2-butyl-octyloxymethyl) -ethyl] ester, inner salt The product is prepared according to Example 1, replacing 2-propylheptanol with 2-butyloctanol.

Example 3 Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (2-pentyl-nonyloxymethyl) -ethyl] ester, inner salt The product is prepared according to Example 1 substituting 2-propylheptanol for 2-pentylnonanol (available from Pfaltz & Bauer (Pfaltz & Bauer, Inc.) Connecticut, Wayerbury, CT 06708).

Example 4: Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (2-hexyl-decyloxymethyl) -ethyl] ester, inner salt Desired product Is prepared according to Example 1, replacing 2-propylheptanol with 2-hexidedecanol.

Example 5: Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (dodecyloxymethyl) -ethyl] ester, inner salt The desired product is 1 is prepared by replacing 2-propylheptanol with n-dodecanol.

Example 6: Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (tetradecyloxymethyl) -ethyl] ester, inner salt The desired product was Prepared according to Example 1, replacing 2-propylheptanol with n-tetradecanol.

Example 7: Preparation of sulfate mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (hexadecyloxymethyl) -ethyl] ester, inner salt The desired product was Prepared according to Example 1, substituting 2-propylheptanol for n-hexadecanol.

Example 8: Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (octadecyloxymethyl) -ethyl] ester, inner salt The desired product is 1 is prepared by replacing 2-propylheptanol with n-octadecanol.

Example 9: Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (iso-nonyloxymethyl) -ethyl] ester, inner salt The desired product is According to Example 1, 2-propylheptanol is prepared in place of iso-nonanol (Exxal 9 was obtained from Exxon Mobile Chemical, Houston, Texas USA).

Example 10: Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (iso-decyloxymethyl) -ethyl] ester, inner salt The desired product is According to Example 1, 2-propylheptanol is prepared in place of iso-decanol (obtained from City Chemicals LLC, West Haven, Connecticut USA).

Example 11: Preparation of sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (iso-tridecyloxymethyl) -ethyl] ester, inner salt The desired product is According to Example 1, 2-propylheptanol is prepared in place of iso-tridecanol (BASF (obtained from BASF Corporatio, Mount Olive, New Jersey USA)).

Example 12: Sulfuric acid mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (iso-tridecyloxymethyl) -ethyl] ester, inner salt and sulfuric acid mono- [ Simultaneous preparation of 2- (3,4-dihydro-isoquinolin-2-yl) -1- (iso-pentadecyloxymethyl) -ethyl] ester, inner salt The desired product is 2-propyl according to Example 1 Heptanol is prepared in place of a mixture of isomeric tridecanols and pentadecanols (BASF (obtained from BASF Corporatio, Mount Olive, New Jersey USA)).

＊ 実施例１から１２に従って調製された有機触媒またはそれらの混合物。 (Example 13)
A bleach detergent composition having the form of a granular laundry detergent is exemplified by the following formulation.

* Organic catalyst or mixture thereof prepared according to Examples 1-12.

  All of the above compositions were used in water at 25 ° C. with a concentration of 3500 ppm and a water to fabric ratio of 25: 1. A typical pH is about 10, but can be adjusted by changing the ratio of Na-salt to acid in the form of alkylbenzene sulfonate.

＊ 実施例１から１２またはそれらの混合に従って調製された有機触媒 (Example 14)
A bleach detergent composition having the form of a granular laundry detergent is exemplified by the following formulation.

* Organic catalyst prepared according to Examples 1 to 12 or mixtures thereof

  All of the above compositions are used to wash fabrics at a concentration of 10,000 ppm in water at 20-90 ° C. and a water to fabric ratio of 5: 1. A typical pH is about 10, but can be adjusted by changing the ratio of Na-salt to acid in the form of alkylbenzene sulfonate.

＊ トルエンスルホン酸ナトリウムなどのその他の向水性物質も使用される場合がある。
＊＊ 実施例１から１２またはそれらの混合に従って調製された有機触媒。
＊＊＊ ウルトラマリン青またはアゾ−ＣＭ−セルロースなど（メガザイム（Megazyme）アイルランド（Bray, Co. Wicklow, Ireland））
＊＊＊＊ Ｗ０ ００／０２９９１に従って調製された。 (Example 15)
A bleach detergent composition having the form of a granular laundry detergent is exemplified by the following formulation.

* Other hydrophobic substances such as sodium toluenesulfonate may also be used.
** Organic catalyst prepared according to Examples 1 to 12 or mixtures thereof.
*** Ultramarine blue or azo-CM-cellulose etc. (Megazyme Ireland (Bray, Co. Wicklow, Ireland))
*** Prepared according to W0 00/02991.

  All of the above compositions are used to wash fabrics at a concentration of 500-1500 ppm in water at 5-25 ° C. and a water to fabric ratio of 15: 1-25: 1. A typical pH is about 9.5-10, but can be adjusted by changing the ratio of Na-salt to acid in the form of alkylbenzene sulfonate.

(Example 16)
The organic catalysts listed below were tested according to Applicant's organic catalyst / enzyme compatibility test using [peracetic acid] = 5.0 ppm, [organic catalyst] = 0.5 ppm and gave the following results: It was.

  While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (8)

A cleaning composition comprising:
a. ) Organic catalyst selected from the group consisting of organic catalysts having the formula:
(I)

(Ii)

(Iii) and mixtures thereof;
Wherein each R ¹ is independently a branched alkyl group containing 9 to 24 carbons or a linear alkyl group containing 11 to 24 carbons, preferably each R ¹ is independently 9 to 18 carbons. A branched alkyl group containing carbon or a linear alkyl group containing 11 to 18 carbons, more preferably each R ¹ independently is 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n Selected from the group consisting of -dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, isononyl, iso-decyl, iso-tridecyl, iso-pentadecyl, and b. ) One or more adjuvant ingredients,
A cleaning composition comprising: The cleaning composition of claim 1 is an organic catalyst having the following formula:

Wherein each R ¹ is independently a branched alkyl group containing 9 to 24 carbons or a linear alkyl group containing 11 to 24 carbons, preferably each R ¹ is independently 9 to 18 carbons. A branched alkyl group containing carbon or a linear alkyl group containing 11 to 18 carbons, more preferably each R ¹ is independently 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexidedecyl, A cleaning composition selected from the group consisting of n-dodecyl, n-tetradecyl, n-hexdecyl, n-octadecyl, isononyl, iso-decyl, iso-tridecyl, iso-pentadecyl. An organic catalyst having the formula:

Wherein each R ¹ is independently a branched alkyl group containing 9 to 24 carbons or a linear alkyl group containing 11 to 24 carbons, preferably each R ¹ is independently 9 to 18 carbons. A branched alkyl group containing carbon or a linear alkyl group containing 11 to 18 carbons, more preferably each R ¹ independently is 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexidedecyl, n The cleaning composition according to claim 1, which is selected from the group consisting of -dodecyl, n-tetradecyl, n-hexaiso-decyl, decyl, n-octadecyl, isononyl, iso-tridecyl, iso-pentadecyl.   A cleaning composition comprising an organic catalyst having an enzyme compatibility value of 70 or more and one or more adjuvant components.   The cleaning composition of claim 4 comprising an organic catalyst having an enzyme compatibility value of 80 or greater.   The cleaning composition according to any one of claims 1 to 5, wherein at least one of the one or more adjuvant components is selected from an activated peroxygen source, an enzyme, a surfactant, and a mixture thereof. .   The cleaning composition according to any one of claims 1 to 6, comprising an activated peroxygen source, an enzyme, and a surfactant as the adjuvant component.   A surface comprising the step of contacting said surface or fabric with a cleaning composition according to any one of claims 1 to 7, and then optionally washing and / or rinsing said surface or fabric or How to wash the fabric.