JP4624327B2 - Active substance-containing delivery particles - Google Patents

Description

  The present invention relates to active substance-containing delivery particles and cleaning compositions comprising such active substance-containing delivery particles; and methods of making and using such particles and cleaning products.

  Active substances such as catalysts and enzymes are expensive and generally less effective when used at high concentrations in cleaning compositions. As a result, cleaning compositions usually contain very low concentrations of active substance. Unfortunately, when a low concentration of active substance is used in a cleaning composition, it is difficult to uniformly disperse the active substance in the cleaning composition. Therefore, consumers often only get performances that are less than optimal cleaning performance, and may suffer certain cleaning disadvantages such as fabric damage.

  Therefore, there is a need for active agent-containing delivery particles that can uniformly administer low concentrations of active agent in a cleaning composition.

  The present invention relates to active substance-containing delivery particles that are not surfactants, cleaning compositions comprising the particles, and methods of making and using such particles and cleaning compositions.

Definitions As used herein, the term “cleaning composition”, unless otherwise indicated, is a general purpose or “heavy” detergent in the form of granules or powder, in particular a detergent for washing; a universal detergent in the form of a liquid, gel or paste. , Especially so-called heavy liquid type; liquid fine fiber detergent; dishwashing detergent or light dish detergent, especially high foaming type; dishwasher detergent (various tablets, granules, liquids and rinses for home and facility use) Liquid wash and disinfectant (including antibacterial hand wash, solid soap, mouthwash, denture cleaner, car or carpet shampoo, bathroom cleaner); hair shampoo and hair rinse Shower gels and foam baths and metal cleaners; and bleach additives and cleaning aids such as "stain sticks" or pretreatment molds.

  As used herein, the articles “a” and “an” are understood to mean one or more of the claimed or described when used in the claims.

  The test method disclosed in the Test Methods section of this application is used to measure each value of the parameters of Applicants' invention as such invention is described and claimed herein. Understand what must be done.

  Unless otherwise stated, all concentrations of a component or composition relate to the activity level of the component or composition and exclude impurities that may be present in commercial sources, such as residual solvents or by-products.

  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.

  It should be understood that any maximum numerical limitation set forth throughout this specification includes all lower numerical limits as if they were expressly set forth herein. Every minimum numerical limitation described throughout this specification includes every higher numerical limitation as if such a larger numerical limitation was expressly set forth herein. Any numerical range recited throughout this specification is intended to include any numerical range narrower than that falling within such broader numerical ranges, all such narrower numerical ranges being expressly recited herein. Include as if.

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

Active substance-containing delivery particles that are not surfactants The applicant's active substance-containing delivery particles are active substance components that are not surfactants, and the active substance component is sufficiently uniformly dispersed in the coating to be 20%. A component that provides a relative standard deviation of less than 10% or less, or even 5% or less; a solid coating having a median particle size of less than 50 microns, about 0.5 microns to about 40 microns, or even about 1 micron to about 30 microns An auxiliary component; and a binder component, wherein the binder component is less than about 4 Pa · s (4,000 cps), about 0.001 Pa · s (1 cps) to about 2 Pa · s (2,000 cps), or even about A first coating comprising a component having a viscosity of 0.005 Pa · s (5 cps) to about 1 Pa · s (1,000 cps); and a core material Wherein at least a portion of the core material is coated with the first coating and the core material is a median particle of at least 150 microns, 212 microns to about 1,000 microns, or even about 300 microns to about 850 microns. A core material having a diameter and a distribution range of 1 to about 2, 1 to about 1.5, or even 1 to about 1.25; and optionally at least one additional coating.

  In a first aspect of Applicants' invention, the core material is at least 300 grams per liter, from 300 grams per liter to about 1,600 grams per liter, or even from about 400 grams per liter to 1 It has a bulk density of about 1,000 grams per liter.

  In another aspect of Applicants' invention, the core material has a bulk density of at least 800 grams per liter, or even 800 grams per liter to 1600 grams per liter.

  In one embodiment of Applicants' invention, the particles comprise 10 wt% or less of the binder component, about 0.5 to 10 wt% of the binder component, or further based on the total weight of the particles About 1 to about 5% by weight of the binder component.

  In one embodiment of Applicants' invention, the particles comprise 20% by weight or less of any one non-surfactant active material, 10% by weight or less of any one interface, based on the total weight of the particles. An active substance that is not an active agent, or an active substance that is not any one surfactant is further contained in an amount of 5% by weight or less.

  In one embodiment of Applicants' invention, the particles have a ratio of the median particle size of the core material to the median particle size of the solid coating aid of at least 10: 1, 10: 1 to about 500: 1, or Furthermore, it is about 20: 1 to about 100: 1.

  In one embodiment of Applicants' invention, the particles comprise at least one additional coating. Each additional coating can coat any previously applied coating, or any previously uncoated portion of the core material. Thus, the first coating can be coated by any additional coating. The additional coating may comprise a hydrophilic or hydrophobic material, such as a colloidal wax emulsion, or an additional binder-type material may be used.

  In one embodiment of Applicants' invention, the particles comprise a material selected from dyes, pigments, and mixtures thereof.

  Active substances that are not suitable surfactants include substances that the formulator desires to use at low concentrations and deliver in a uniform manner. Active substances that are not useful surfactants include substances selected from the group consisting of oxidation catalysts, free radical initiators, bleach activators, enzymes, perfumes, and mixtures thereof. Examples of oxidation catalysts include organic bleach catalysts such as 2- [3-[(2-ethylhexyl) oxy] -2- (sulfooxy) propyl] -3,4-dihydroisoquinolinium, inner salts and 3, 4-dihydro-2-methylisoquinolinium, methanesulfonate; photobleaching agents such as phthalocyanines such as zinc phthalocyanine tetrasulfonate; metal bleaching catalysts such as dichloro-5,12-dimethyl-1,5,8,12- Tetraazabicyclo [6.6.2] hexadecane manganese (II) and [MnIV2 (μ-O) 3L′2] 2+ (L ′ = 1,4,7-trimethyl-1,4,7-triazacyclononane) And mixtures thereof. Examples of free radical initiators include chemical, photo or thermal radical initiators such as phenyl (2,4,6-trimethylbenzoyl) phosphinic acid, ethyl ester, and 2-hydroxy-2-methyl. Examples include -1- [4- (1-methylethenyl) phenyl] -1-propanone homopolymers and mixtures thereof. Examples of bleach activators include nonanoic acid, 4-sulfophenyl ester, sodium salt, N, N, N ', N'-tetraacetylethylenediamine and mixtures thereof. Examples of enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenol oxidases, Lipoxygenases, ligninases, pullulanases, tannases, pentosanases, maranases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. Examples of perfumes include aldehydes such as 3- (4-t-butylphenyl) -2-methylpropanal, 3- (4-t-butylphenyl) -propanal, 3- (4-isopropylphenyl)- 2-methylpropanal, 3- (3,4-methylenedioxyphenyl) -2-methylpropanal, and 2,6-dimethyl-5-heptenal; ketones such as α-damascone, β-damascone, δ- Damascone, β-Damacenone, 6,7-dihydro-1,1,2,3,3-pentamethyl-4 (5H) -indanone, methyl-7,3-dihydro-2H-1,5-benzodioxepin 3-one, 2- [2- (4-methyl-3-cyclohexenyl-1-yl) propyl] cyclopent-2-one, 2-sec-butylcyclohexanone, and β- Dihydroionone; alcohols such as linalool, ethyl linalool, tetrahydro linalool, and dihydromyrcenol, and encapsulated fragrances, and solid materials such as zeolites impregnated with fragrances. Suitable non-surfactant actives can be prepared according to the examples included in this application, or Firmenich (Geneva, Switzerland), Givaudan (Argenteuil, France), IFF (NJ, USA) Hazlet, Quest (Mount Olive, New Jersey, USA), Rhodia Inc. (Cranbury, New Jersey, USA), Frontier Scientific, Inc. (Logan, Utah, USA), Fratelli Lamberti SpA (Italy), BASF AG (Ludwigshafen, Germany), Genencor International, Inc. (California, USA) State Palois Can be obtained from the preparative (Palo Alto)), and Bruno Vo enzyme (Novozymes A / S) (Denmark).

Suitable solid coating aids include materials selected from the group consisting of acetates, sulfates, carbonates, borates, phosphates, and mixtures thereof. Examples of acetates include magnesium acetate, Mg (CH ₃ COO) ₂ ; and sodium acetate, NaCH ₃ COO. Examples of sulfates include magnesium sulfate, MgSO ₄ ; and sodium sulfate, Na ₂ SO ₄ . Examples of carbonates include sodium carbonate, Na ₂ CO ₃ ; potassium carbonate, K ₂ CO ₃ . Examples of borates include sodium borate and Na ₂ B ₄ O ₇ . Examples of phosphates include sodium phosphate dibasic, Na ₂ HPO ₄ ; and sodium tripolyphosphate, Na ₅ P ₃ O ₁₀ . Such coating aids may be incorporated into the coating process as substantially anhydrous salts. Without being bound by theory, it is believed that their conversion to a stable hydrate phase provides the moisture removal action of the binder and allows processing that does not require a drying step. Suitable solid coating aids include PQ Corporation (Valley Forge, PA, USA); FMC Corporation (Philadelphia, PA, USA); Mallinckrodt Baker, Inc. (Philipsburg, NJ, USA).

  Suitable binders include materials selected from the group consisting of polymers, surfactants, solvents and mixtures thereof. Examples of polymers include sodium polyacrylate, acrylic-maleic copolymers, polyethylene glycol, polyvinyl acetate, polyvinyl pyrrolidone, cellulose ethers and hydroxypropyl cellulose. Examples of surfactants include anionic, cationic, zwitterionic, and nonionic surfactants. Examples of the solvent include water, alcohols, linear alcohols, branched alcohols, and aliphatic alcohols. Suitable binders are BASF (Ludwigshafen, Germany); Dow Chemical Company (Midland, Michigan); Hercules Incorporated (Wilming, Delaware, USA) Shell Chemical LP (Houston, Texas, USA); Procter & Gamble Chemicals (Cincinnati, Ohio, USA); and Rohm and Haas ( Rohm and Hass Company) (Philadelphia, Pennsylvania, USA).

  Suitable core materials include detergent components such as sodium sulfate, sodium carbonate and sodium phosphate, and composite detergent component compositions made by methods such as spray drying, agglomeration, compression, or extrusion methods. . Examples of such composite compositions include granules containing detergent builders, surfactants and optionally polymer components, and nonanoic acid, 4-sulfophenyl ester, sodium salts and N, N, N ′, N′-tetraacetyl. A detergent component composition containing ethylenediamine may be mentioned. Suitable cores, such as detergent granules, are usually manufactured as intermediates in detergent product factories, but suitable cores and core ingredients are FMC Corporation (Philadelphia, PA, USA); Host Chemicals ( Jost Chemicals (St. Louis, MO); and General Chemical Corporation (Parsippany, NJ).

  Non-limiting examples of dyes and pigments include organic and inorganic pigments, aqueous and other solvent soluble dyes. Such dyes and pigments include Ciba Specialty Chemicals Corporation (Newport, Delaware, USA); Clariant Corporation (Charlotte, North Carolina, USA); Available from Milliken Chemical Company (Spartanburg, South Carolina, USA).

Method for Producing Active Substance-Containing Delivery Particles That Are Not Surfactants Active substance-containing delivery particles that are not surfactants disclosed herein may be produced according to the teachings and examples disclosed herein. In one embodiment of Applicants' invention, the non-surfactant-containing delivery particles combine a non-surfactant active agent component and a solid coating aid component to form a pre-mixture; Produced by coating a portion with a binder component and the pre-mixture to form non-surfactant-containing delivery particles. In another aspect of Applicants' invention, an active substance-containing delivery particle that is not a surfactant combines a non-surfactant active ingredient component and a binder component to form a premix; and then at least a portion of the core substance Is coated with the premix and then with a solid coating aid to form non-surfactant-containing delivery particles. In one embodiment of Applicants' method, the binder component is evenly distributed on the surface of the core material before the solid coating auxiliary component is incorporated. Regardless of which process is used, when the active agent component that is not a surfactant is a solid, such an active agent is usually such that the active agent component and the solid coating auxiliary component have similar particle sizes. Selected. Regardless of the process used, the starting materials have the necessary properties so that suitable surfactant-active material-containing delivery particles can be formed via the method. Detailed characteristics of each of the non-surfactant active substance component, solid coating auxiliary component, binder component, and core material, and representative ingredients are disclosed in the non-surfactant-containing active substance-containing delivery particles section of this application. The

Applicants have recognized that Stokes numbers can be used to define process parameters for stratification and agglomeration processes. Accordingly, Applicants' method may be performed according to the following process parameters: less than 10, a stratified Stokes number of about 0.001 to about 10 or even about 0.001 to about 5, and 0.5. A core agglomeration Stokes number of greater than about 1 to about 1000 or even about 2 to about 1000. The aforementioned Stokes number can be calculated as follows:
St _mixer = (0.0001) · N · R · ρ · δ / η
The variables in the above equation are specified using the unit of measurement as follows:
N is the rotation speed of the main stirring impeller shaft of the mixer (number of revolutions per minute, abbreviated as RPM)
R is the radial sweep distance of the main agitating impeller from the center of the impeller shaft to the tip of the impeller tool (abbreviated as meters, m);
ρ is the bulk density of the core particles (gram / liter, abbreviated as g / L);
η is the binder viscosity (abbreviated centipoise, cps); and δ is the effective particle size used to describe stratification or agglomeration (abbreviated micron, μm) ,here:
δ _layering is defined as 2 · (d _Core · d _coating) / (d _core + d _coating)) and δ _{core - agglomeration} is defined as d _core; where d _core is the core material And d _coating is the median particle size of the solid coating adjuvant material.

Based on the above, two variants of the Stokes formula can be defined, one describing the layering of coating aids on the core particle (St _layering ), the other being the core particle and the other core And agglomeration (St _{Core-Agglomeration} ).

Layered Stokes number, St _layering = (0.0001) · N · R · ρ · δ _layering / η
Number of core agglomeration Stokes =
St _{Core-Agglomeration} = (0.0001) · N · R · ρ · δ _{Core-Agglomeration} / η
Suitable equipment for carrying out the methods disclosed herein includes paddle mixers, plowshare mixers, ribbon blenders, vertical axis granulators and drum mixers (both batch-wise, when available) Is in the form of a continuous process). These devices include Lodge GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence, Kentucky, USA), Forberg AS (Lalvik, Norway) Larvik)), Glatt Ingenieurtechnik GmbH (Weimar, Germany).

Cleaning compositions comprising active substance-containing delivery particles that are not surfactants The cleaning compositions of the present invention include embodiments of active substance-containing delivery particles that are not surfactants as disclosed herein. While the exact concentration of non-surfactant-containing delivery particles used depends on the type of cleaning composition and the end use, in one aspect of Applicants' invention, the cleaning composition comprises a cleaning composition. 15% or less, 10% or less, or even 5% by weight of any non-surfactant-containing delivery particles based on the total weight of the product. In one embodiment of Applicants' invention, the cleaning composition comprises 2 wt% or less, 0.5 wt% or less, or even 0.2 wt% or less of any one non-surfactant active material, The active agent is delivered to the cleaning composition by active agent-containing delivery particles that are not the surfactant. In another aspect of Applicants' invention, the median particle size of non-surfactant-containing delivery particles is typically 15-95 percentile of the cumulative particle size distribution based on the mass of the cleaning composition, 15 It is in the range of -85 percentile, or even 30-70 percentile.

  The cleaning compositions disclosed herein are typically formulated so that the pH of the cleaning water is about 6.5 to about 12, or about 7.5 to 10.5 during use in an aqueous cleaning operation. Is done. Liquid dishwashing product formulations typically have a pH of about 6.8 to about 9.0. The cleaning product is usually formulated to have a pH of about 7 to about 12. Techniques for controlling pH at the recommended use concentration include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Adjunct Materials Although not essential for the purposes of the present invention, the non-limiting list of adjuvants exemplified below is suitable for use in an immediate cleaning composition and they can be Desirably, to assist or improve performance, to treat the substrate to be cleaned, or to change the aesthetics of the cleaning composition, such as when using fragrances, colorants, dyes, etc. It can be incorporated into certain embodiments of the invention. It will be appreciated that such adjuvants are added to the ingredients supplied via Applicants' delivery particles. The specific 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 And / or pigments, but are not limited to these. In addition to the disclosure below, suitable examples and concentrations of such other adjuvants are described in US Pat. Nos. 5,576,282, 6,306,812 B1, and 6,326,348 B1. Found and incorporated herein by reference.

  Surfactant-Preferably, the cleaning composition according to the invention comprises a surfactant or a surfactant system, wherein the surfactant is a nonionic and / or anionic and / or cationic interface. It can be chosen from active agents and / or amphoteric and / or bipolar and / or semipolar nonionic surfactants.

  Surfactants are typically from about 0.1%, preferably about 1%, more preferably about 5% by weight of the cleaning composition to about 99.9%, preferably about 5% by weight of the cleaning composition. It is present at a concentration of 80% by weight, more preferably about 35% by weight, most preferably up to about 30% by weight.

  Builders-The cleaning compositions of the present invention preferably comprise one or more detergent builders or builder systems. When present, the composition is typically at least about 1% by weight builder, preferably from about 5% by weight, more preferably from about 10% to about 80% by weight, preferably up to about 50% by weight, More preferably, up to about 30% by weight of detergent builder.

  Builders include, but are not limited to, alkali metal, ammonium and alkanol ammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builder polycarboxylate compounds, ether hydroxy polycarboxylates. Rates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid; various ethylenediaminetetraacetic acids And alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as nitrilotriacetic acid; and mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, cal Polycarboxylates such as carboxymethyl oxy acid, as well as those soluble salts.

  Chelating Agents-The cleaning compositions herein may optionally contain one or more copper, iron and / or manganese chelating agents.

  If used, these chelating agents generally comprise from about 0.1% to about 15%, more preferably 3.0% by weight of the cleaning compositions herein.

  Anti-transfer agents—The cleaning compositions of the present invention may also include one or more anti-transfer agents. Suitable polymeric dye transfer inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. However, it is not limited to these.

  When present in the cleaning compositions herein, the dye transfer inhibitor is present from about 0.0001%, more preferably from about 0.01%, most preferably from about 0.05% by weight of the cleaning composition. Present in a concentration of up to about 10%, more preferably about 2%, most preferably up to about 1% by weight of the cleaning composition.

  Dispersants-The cleaning compositions of the present invention can also contain dispersants. Suitable water-soluble organic substances are homopolymer or copolymer acids or their salts, in which the polycarboxylic acids are at least two carboxyl radicals separated from one another by no more than two carbon atoms. including.

  Enzyme-cleaning compositions may include one or more detergent 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, keratanases, reductases, oxidases, phenol oxidases , Lipoxygenases, ligninases, pullulanases, tannases, pentosanases, maranases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, and amylases, or mixtures thereof For example, but not limited to. A typical combination is a mixture of a conventional applicable enzyme such as protease, lipase, cutinase, and / or cellulase and amylase.

  Enzyme stabilizers-Various techniques can be used to stabilize enzymes used in detergents. The enzyme used herein can be stabilized in the final composition by the presence of a water-soluble source of calcium and / or magnesium ions that supplies calcium ions and / or magnesium ions to the enzyme.

  Catalytic metal complexes-Applicants' cleaning compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a transition metal cation with limited bleach catalyst activity, such as a cation of copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese, a cation of zinc or aluminum. Auxiliary metal cations with little or no bleaching catalyst activity, as well as sequestering agents with limited stability constants for catalytic metals and cations of auxiliary metals, especially ethylenediaminetetraacetic acid, ethylenediaminetetra A catalyst system comprising (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in US Pat. No. 4,430,243 (Bragg, issued February 2, 1982).

  If desired, the compositions herein can be catalyzed by 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 (Miracle et al.).

  Cobalt bleach catalysts useful herein are known, for example, US Pat. No. 5,597,936 (Perkins et al., Issued Jan. 28, 1997); US Pat. No. 5,595,967. (Miracle et al., Issued January 21, 1997). Such cobalt catalysts are readily prepared by known procedures, for example, as taught in US Pat. No. 5,597,936 and US Pat. No. 5,595,967.

  The compositions herein preferably also include a transition metal complex of a macropolycyclic rigid ligand, abbreviated as “MRL”. As a practical matter, but not for the purpose of limitation, the compositions and cleaning methods herein are tailored to provide active MRL species on the order of at least on the order of 100 million in aqueous cleaning media. Preferably, about 0.005 ppm to about 25 ppm, more preferably about 0.05 ppm to about 10 ppm, and most preferably about 0.1 ppm to about 5 ppm of MRL species is provided in the cleaning solution.

  Preferred transition metals in the present transition metal bleach catalyst include manganese, iron, and chromium. Preferred MRLs herein are a special class of ultra-fixed ligands that are bridged, such as 5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane. It is.

  Suitable transition metal MRLs are readily prepared by known procedures such as taught, for example, in PCT International Publication No. WO 00/332601 and US Pat. No. 6,225,464.

Methods for making and using cleaning compositions The cleaning compositions of the present invention can be formulated into any suitable form selected by the formulator, and can be prepared by any method, and their non- Examples are US Pat. No. 5,879,584 (Bianchetti et al., Issued March 9, 1999); US Pat. No. 5,691,297 (Nassano et al., November 1997). U.S. Pat. No. 5,574,005 (Welch et al., Issued November 12, 1996); U.S. Pat. No. 5,569,645 (Dinniwell et al., Oct. 29, 1996) U.S. Pat. No. 5,565,422 (Del Greco et al., Issued Oct. 15, 1996); U.S. Pat. No. 5,516,448 (Capeci et al., 1996) U.S. Pat. No. 5,489,392 (Capesi et al., Issued Feb. 6, 1996); U.S. Pat. No. 5,486,303 (Kapesi et al., Issued Jan. 23, 1996) All of which are incorporated herein by reference.

Methods of Use The cleaning compositions containing the non-surfactant-containing delivery particles disclosed herein can be used to clean certain locations, particularly fabric surfaces. Typically, at least a portion of the location is contacted with an embodiment of Applicants' cleaning composition in neat form or diluted in a cleaning solution, and then the location is washed and / or rinsed. For purposes of this invention, washing includes, but is not limited to, rubbing and mechanical agitation. The fabric may include almost any fabric that can be washed under normal consumer use conditions. A cleaning solution comprising the disclosed cleaning composition may have a pH of about 8 to about 10.5. Such compositions are typically used at a concentration of about 500 ppm to about 15,000 ppm in solution. When the washing solvent is water, the temperature of the water is usually about 5 ° C to about 90 ° C, and when the location includes fabric, the weight ratio of water to fabric is usually about 1: 1 to about 30: 1. It is.

Test Methods The test methods disclosed in the Test Methods section of this application are for measuring each value of the parameters of Applicants' invention as such invention is described and claimed herein. Understand what must be used.

1. ) Relative standard deviation distribution test of non-surfactant active substance particles a. ) Obtain a 10 gram sample representative of active agent-containing delivery particles that are not surfactants. When samples are obtained from bulk containers, typical sampling is used, for example sampling according to ISO 9138, "Abrasive grains-Sampling and splitting" (issued February 1993).

    b. ) According to ISO 9138, a suitable Jones Type Riffler sample splitter or preferably a rotating reflector, for example a Microscal ™ rotating refller model SR1A (Microscal Limited (UK W10 5AL)) The above sample is divided into 10 samples of 1 gram using Southern Row London 79).

c. ) Measure the concentration of each non-surfactant active in each gram of sample using a test method that gives an accuracy of at least ± 5% Examples of test methods suitable for the oxidation catalyst 2- [3-[(2-ethylhexyl) oxy] -2- (sulfooxy) propyl] -3,4-dihydro-isoquinolinium, inner salt are detailed below:
(I) Principle: 2- [3-[(2-ethylhexyl) oxy] -2- (sulfooxy) propyl] -3,4-dihydro-isoquinolinium, a non-surfactant-containing delivery particle containing an inner salt A 1 gram sample of is dissolved in a 50:50 solution of acetonitrile: water and quantified using UV detection at 290 nm against an external standard calibration curve prepared from a known activity standard.

  (Ii) Apparatus: PDA detector, HP ChemStation data collection integration system, Phenomenex Columbus (C18 100 mm × 2.0 mm) reverse phase column, and sample filtration unit HP / Agilent 1100 solvent delivery system with (0.45 micron PTFE Acrodisc CR disc filter).

(Iii) Reagents and solutions

(Iv) Procedure Preparation of Standard Stock Solution Add about 25 mg of standard to a 25 mL volumetric vessel and dilute to that volume to give about 1000 μg / mL 2- [3-[(2-ethylhexyl) oxy] -2- Prepare a 50/50 stock solution of (sulfooxy) propyl] -3,4-dihydro-isoquinolinium, inner salt standard acetonitrile / water. Sonicate for 10 minutes, followed by stirring for 20 minutes.
Preparation of calibration solution Take approximately 1.0, 0.5, and 0.25 mL of standard stock solution and dilute each to its volume in a 10 mL volumetric container to obtain approximately 10, 5, and 2.5 μg / mL. A 50/50 mixed solution of standard acetonitrile / water is prepared. Mix thoroughly.
Sample analysis 2- [3-[(2-ethylhexyl) oxy] -2- (sulfooxy) propyl] -3,4-in a 50/50 mixture of acetonitrile / water in a separate 50 mL volumetric flask. Ten 50 mL solutions containing about 1 gram each of non-surfactant-containing delivery particles containing dihydro-isoquinolinium and inner salt are prepared. Sonicate for 10 minutes, then stir for 20 minutes. Take 1 mL aliquots from each of the 50 mL solutions and dilute 10: 1 with 50/50 acetonitrile / water in a 10 mL volumetric vessel. The concentration of 2- [3-[(2-ethylhexyl) oxy] -2- (sulfooxy) propyl] -3,4-dihydro-isoquinolinium, inner salt should be in the range of 25-100 ppm of the calibration curve.
Measurement operation:
Injection volume: 5 μL Solvent: A = H ₂ O, C = acetonitrile, D = 5% formic acid.
Analysis wavelength @ 290 nm. Absorbance units (AU) are maintained below 1 AU.
Solvent gradient profile

  (V) Calculation: The peak area from the calibration injection is used to determine the response factor, thereby 2- [3-[(2-ethylhexyl) oxy] -2- (sulfooxy) propyl]-in each 1 gram sample. The weight percentage of 3,4-dihydro-isoquinolinium, inner salt is determined.

  d. ) For each non-surfactant active identified, use the measured weight percent of the non-surfactant active found in each gram sample (step c) and use the relative standard for each such non-surfactant active Calculate the deviation. For the purposes of the present invention, such relative standard deviation is considered to be the relative standard deviation of non-surfactant particles for the particular active substance being tested.

2. ) Median particle size test of solid coating aids This test method must be used to determine the median particle size of solid coating aids. The particle size test of the solid coating auxiliary component is measured according to ISO 8130-13 “Coating powder—13 parts: particle size analysis by laser diffraction”. Suitable laser diffraction particle size analyzers with dry powder feeders are Horiba Instruments Incorporated (Irvine, CA); Malvern Instruments Ltd (Worcestershire, UK) Worcestershire)); and Beckman-Coulter Incorporated (Fullerton, Calif., USA).
The results are ISO 9276-1: 1998, particle size analysis result display—Part 1: graph display, FIG. 4. Displayed according to “cumulative distribution Q ₃ plotted on graph paper using logarithmic abscissas”. The median particle size is defined as the abscissa value at the point where the cumulative distribution (Q ₃ ) is equal to 50 percent.

3. ) Binder Component Viscosity Test This test method must be used to measure the binder component viscosity.
For binder component viscosities greater than about 0.1 Pa · s (100 cps), the viscosity is ISO 2555 (2nd edition, published on February 1, 1989, reissued with correction on February 1, 1990). "Measurement of Apparent Viscosity in Liquid State or Plastic-Resin-Brookfield Test Method as Emulsion or Dispersion". As described in this method, type “A” viscometers are applicable to the viscosity ranges described herein. Viscosity measurements are made at the same binder component temperature that is incorporated into the method for producing active agent-containing delivery particles where the binder component is not such a surfactant.
For viscosities less than about 0.1 Pa · s (100 cps), the viscosity is measured according to ASTM D2857-95 “Standard Techniques for Diluted Solution Viscosity of Polymers” (issued April 1995). Viscosity measurements are made at the same binder component temperature that is incorporated into the method for producing active agent-containing delivery particles where the binder component is not such a surfactant.

4). ) Core material median particle size and distribution range test This test method must be used to measure the median particle size of the core material.
The particle size test for the core material is ASTM D502-89 “Standard Test Method for Particle Size of Soaps and Other Detergents” (approved May 26, 1989). And a further description of the sieve size used in the analysis is performed to determine the median particle size of the core material. According to item 7, “Procedure using machine-sieving method”, US standard (ASTM E 11) sieve # 12 (1700 μm), # 18 (1000 μm), # 20 (850 μm), # 30 ( A clean dry sheave nest containing 600 μm), # 40 (425 μm), # 50 (300 μm), # 70 (212 μm), # 100 (150 μm) is required. The specified mechanical sieving method is used with the above-mentioned sieve nest. A core material is used as a sample. A suitable sieve-shaker is described in W.W. S. It can be obtained from WS Tyler Company (Mentor, Ohio, USA).

  Cumulative percent material data is plotted against the micron aperture size of each sieve, where the micron size aperture is represented on the abscissa using a logarithmic scale, and the cumulative mass percent data is ordinated using a linear scale. It is represented by Data points in the semilog plot are connected by straight line segments. The median particle size of the core material is defined as the abscissa value at the point where the cumulative mass percent is equal to 50 percent.

  Examples of the above data display are ISO92776-1: 1998, “particle size analysis result display—Part 1: graph display”, FIG. 4 is given. Note that this sieve-shaking method identifies straight line segments for interpolation between data points. If the 50th percentile value is less than the finest sieve size (150 μm) or greater than the coarsest sieve size (1700 μm), 1.5 or less until the median falls between the two measured sieve sizes Additional sheaves must be added to the nest according to the geometric series.

The distribution range of the core material is a measured value of the core size distribution width around the median value. It is calculated as follows:
Range = [(D84 / D50) + (D50 / D16)] / 2
Where D84 and D16 are the particle sizes at the 16th and 84th percentiles, respectively, in the cumulative mass percent plot.
If the D16 value is less than the finest sieve size (150 μm), the range is calculated as follows:
Range = (D84 / D50)
In the formula, D50 is the median particle size.
If the D84 value exceeds the coarsest sieve size (1700 μm), the range is calculated as follows:
Range = (D50 / D16).
If the D16 value is less than the finest sheave size (150 μm) and the D84 value exceeds the coarsest sheave size (1700 μm), the range is a maximum value of 5.7.

5. ) Core Material Bulk Density Test The bulk density of the core material is determined according to ASTM Standard E727-02 “Standard Test Methods for Determining Bulk Density of Granular Carriers and Granular. Pesticides) ”(certified on October 10, 2002), measured according to test method B, loose-fill density of granule material.

6). ) Cumulative particle size distribution test based on the mass of non-surfactant-containing delivery particles / cleaning composition This test method is based on the mass-based mass of the cleaning composition in which the median particle size of non-surfactant-containing delivery particles Must be used to determine if the cumulative particle size distribution is within the claimed percentile range. This exam:
a) the median particle size of the non-surfactant-containing delivery particles, and b) the “core material median particle” described above, except that it is used to measure the selected percentile size value of the cleaning composition. Follow the same procedure specified in the Diameter Test.
In part (a), the "core material median particle size test" is performed using delivery material containing active material that is not a surfactant as a sample instead of the core material. The median particle size is calculated in the same manner.
In part (b), the “core material median particle size test” is a complete cleaning composition comprising a representative weight fraction of all mixed components in the complete composition other than the non-surfactant-containing delivery particles. It is done using things. Cumulative percent material data is plotted against the micron aperture size of each sheave, where the micron size aperture of each sheave is plotted on the abscissa using a logarithmic scale, and the cumulative mass percent data is plotted using a linear scale. Plotted on the ordinate. Data points in the semilog plot are connected by straight line segments. The 15, 30, 70, 85 and 95 percentile particle sizes are determined according to the abscissa value of the point where the cumulative mass percent is equal to 15%, 30%, 70%, 85% and 95%, respectively. If any of the above percentile values is less than the finest sieve size (150 μm) or greater than the coarsest sieve size (1700 μm), the percentile in question falls between the two measured sieve sizes Until then, additional sheaves must be added to the nest according to a geometric series of 1.5 or less.

Example 1: Preparation of mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (2-ethyl-hexyloxymethyl) -ethyl] ester sulfate, inner salt of sulfuric acid addition funnel, Attach a dry argon inlet, a magnetic stir bar, a thermometer, and a cooling bath to a flame-dried 250 mL three-necked round bottom flask with 3,4-dihydroisoquinoline (5.0 g, 0.038 mol) and acetonitrile (50 mL). Added. To the addition funnel is added methylene chloride (10 mL) and crude anhydrous sulfuric acid (SO ₃ ) (3.05 g, 0.038 mol). Place the reaction vessel in an ice bath and cool the contents to 5 ° C. To the reaction solution, a SO ₃ / CH ₂ Cl ₂ solution is added dropwise over 30 minutes while keeping the temperature below 10 ° C. A white precipitate forms upon addition of anhydrous sulfuric acid. When the addition is complete, the reaction is allowed to warm to room temperature and the white suspension is stirred for 1 hour under argon. To the reaction is added 2-ethylhexyl glycidal ether (7.1 g, 0.038 mol) and the reaction is placed in a 90 ° C. oil bath. Methylene chloride is removed via a Dean-Stark trap, after which an internal reaction temperature of 75 ° C. to 80 ° C. is obtained while the reaction turns clear / amber. The reaction is stirred at 75-80 ° C. for 72 hours. The reaction is then cooled to room temperature, evaporated to dryness and the brown residue is recrystallized from isopropanol to give the desired product, 10.3 g (68%), 19% by weight of the final reaction mixture. The raw materials can be obtained from Aldrich (Milwaukee, Wis., USA) and BASF AG (Ludwigshafen, Germany).

実施例１に従って調製される硫酸モノ−［２−（３，４−ジヒドロ−イソキノリン−２−イル）−１−（２−エチル−ヘキシルオキシメチル）−エチル］エステル，分子内塩又はその他の界面活性剤でない活性物質。 Example 2-Formulation of non-surfactant-containing delivery particles and cleaning compositions comprising the same Non-surfactant-containing delivery particles having the following formulation are prepared according to the teachings disclosed herein .

Mono- [2- (3,4-dihydro-isoquinolin-2-yl) -1- (2-ethyl-hexyloxymethyl) -ethyl] ester, inner salt or other interface prepared according to Example 1 An active substance that is not an active agent.

（実施例３）−界面活性剤でない活性物質含有デリバリー粒子の製造方法
この方法は、７．５ｃｍの放射状スイープを有する垂直軸駆動のインペラを備えたフードプロセッサ（ミキサー）にて行われる。 A cleaning composition having the following formulation is prepared in accordance with the teachings disclosed herein.

Example 3 Method for Producing Delivery Particles Containing Active Substances That Are Not Surfactants This method is performed in a food processor (mixer) equipped with a vertical axis driven impeller having a 7.5 cm radial sweep.

  A powdered non-surfactant active material is blended with a magnesium sulfate powder grade having a median particle size of about 10 μm in a ratio of 40 parts non-surfactant active material to 60 parts magnesium sulfate powder to form a fine powder mixture. obtain. To improve blend uniformity, the mixture is passed through a micronization mill. The core material is a sodium sulfate granule having a median particle size of 664 μm, a distribution range of about 1.2, and a bulk density of 1500 g / L. Charge the mixer with 925 grams of core material. The mixer is started at a rotational speed of about 54 rad / s (500 RPM). 15 grams of a polymer binder solution (approximately 22% aqueous sodium polyacrylate) is dropped from a syringe onto the mixer, where the droplet contacts the surface of the moving particles in the mixer and the droplet Are arranged so that they do not overlap. The mixer is turned off and 50 grams of the premixed blend of solid coating adjuvant and cleaning active is added to the top of the wet core, and the mixer is then restarted at about 54 rad / s (500 RPM). A binder viscosity of 0.04 Pa · s (40 cps) gives a layered Stokes number of about 4 and a core agglomeration Stokes number of about 90 at these conditions. After about 1 minute of mixing, another 10 grams of binder solution is similarly dropped into the mixer and mixing is continued for another 30 seconds. The batch is removed from the metal tray used to dissipate the heat of hydration from the reaction of the coating aid and the aqueous fraction of the binder. It can be seen that the product obtained has a relative standard deviation of less than 5% of non-surfactant active substance particles and a median particle size of 704 μm. This corresponds to an average particle coating thickness of about 20 μm.

Example 4-Method for producing active substance-containing delivery particles that are not surfactants This method is carried out in a food processor (mixer) equipped with a vertical axis driven impeller having a 7.5 cm radial sweep.

  The powdered non-surfactant active substance and binder component are blended in a ratio of 30 parts non-surfactant active substance to 70 parts binder component to form a paste. The binder component includes aliphatic alcohols having a carbon chain length of 12-18. The core material is a spray-dried detergent granule having a median particle size of 520 μm, a distribution range of about 1.35, and a bulk density of about 480 g / L. Fill the mixer with 360 grams of core material. The mixer is started at a rotational speed of about 104.7 rad / s (1000 RPM). Twenty grams of non-surfactant active and binder component premix is dropped into the mixer from a syringe. Stop the mixer and add 15 grams of magnesium sulfate with a median particle size of about 10 μm to the upper part of the wet core. The mixer is restarted at approximately 104.7 rad / s (1000 RPM). A binder component viscosity of about 0.2 Pa · s (200 cps) results in a layered Stokes number of about 0.35 and a core agglomeration Stokes number of about 9 at these conditions. After mixing for about 1 minute, 5 grams of an aqueous solution of sodium polyacrylate having a solid content of about 22% is similarly added dropwise to the mixer. After mixing for about 30 seconds, the batch is removed from the metal tray used to dissipate the heat of hydration from the reaction of the coating aid and the aqueous fraction of the binder. The resulting product is found to have a relative standard deviation of less than 10% non-surfactant active agent particles and a median particle size of about 550 μm.

Example 5-Method for Producing Non-Surfactant Active Substance-Containing Delivery Particles This method comprises a plowshare batch mixer Lodige M20 with a set of plowshare stirred impellers driven by a horizontal shaft. Done with. The radial sweep of the stirring impeller is 14.5 cm. Do not use the high-speed chopper unless otherwise instructed.

  Powdered non-surfactant active material is blended in a ratio of magnesium sulfate powder grade having a median particle size of about 10 μm to 30 parts non-surfactant active material and 60 parts magnesium sulfate powder to obtain a fine powder premix Get. Pass the mixture through a micronization mill to improve blend uniformity.

  The core material is a detergent builder and compressed detergent agglomerate particles consisting of a complex of surfactants with a median particle size of 500 μm, a distribution range of 1.3, and a bulk density of about 800 g / L. Fill the mixer with 5 kilograms of core material. The mixer is started at a rotational speed of about 16 rad / s (150 RPM). 100 grams of a binder component comprising an aqueous polyethylene glycol solution having a solid content of 30% (MW is about 4,000) is sprayed onto the mixer using a pressure atomizer at a rate of about 5 grams / second. Stop the mixer and add 270 grams of premix to the top of the wet core material, then restart the mixer at about 16 rad / s (150 RPM). At this point, the chopper is temporarily activated to help disperse the coating aid powder with the wet core. After about 10 seconds of chopper operation, stop it. A binder component viscosity of about 0.02 Pa · s (20 cps) results in a layered Stokes number of about 1.7 and a core agglomeration Stokes number of 44 under these conditions. After mixing for about 1 minute, an additional 50 grams of binder component is sprayed onto the mixer using a pressure atomizer and mixing is continued for an additional 30 seconds. The mixer jacket may be cooled with cold water to remove heat from hydration of the solid coating aid and moisture in the binder solution. It can be seen that the product obtained has a relative standard deviation of less than 20% of non-surfactant active substance particles and a median particle size of 525 μm.

  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 (18)

A delivery particle containing an active substance that is not a surfactant,
a. ) A first coating comprising:
(I) a non-surfactant active substance component selected from the group consisting of oxidation catalysts, free radical initiators, bleach activators, enzymes, fragrances, and mixtures thereof, the non-surfactant activity An ingredient that is sufficiently uniformly dispersed in the coating to give a relative standard deviation of 20% or less non-surfactant particles calculated using the measured concentration (weight percent);
(Ii) a solid coating aid having a median particle size of less than 50 microns selected from the group consisting of acetates, sulfates, carbonates, borates, phosphates, and mixtures thereof; and (iii) polymers A binder component selected from the group consisting of a surfactant, a solvent, a solvent and mixtures thereof, wherein the binder component has a viscosity of less than 4 Pa · s (4,000 cps); and b. ) A core material having a median particle size of at least 150 microns and a distribution range of 1-2 , wherein at least a portion of the core material comprises a combination of an active material component that is not the surfactant and the binder component. Core material coated with the mixture and then with the solid coating aid , wherein the distribution range is the formula [(D84 / D50) + (D50 / D16)] / 2, where D84 and D16 Is the measured value of the core size distribution width around the median calculated by the cumulative mass percent plot, which is the particle size at the 16th and 84th percentiles, respectively, but the D16 value is the finest When the sheave size is less than 150 μm, it is calculated by the formula (D84 / D50) (where D50 is the median particle size), and the D84 value is the coarsest 4. When exceeding the sieve size (1700 μm), calculated by the formula of (D50 / D16), when the D16 value is less than the finest sieve size (150 μm) and the D84 value exceeds the coarsest sieve size (1700 μm). A delivery particle containing an active substance that is not a surfactant containing a maximum value of 7.   c. 2. The non-surfactant-containing delivery particle according to claim 1 further comprising at least one additional coating.   The non-surfactant activity of claim 1 or 2, wherein the non-surfactant active agent component is sufficiently uniformly dispersed in the coating to provide a relative standard deviation of 10% or less non-surfactant active agent particles. Substance-containing delivery particles.   The non-surfactant activity of claim 1 or 2, wherein the non-surfactant active agent component is sufficiently uniformly dispersed in the coating to provide a relative standard deviation of 5% or less non-surfactant active agent particles. Substance-containing delivery particles.   The active substance-containing delivery particle that is not a surfactant according to any one of claims 1 to 4, wherein the median particle size of the core substance is 150 to 1000 microns.   The surfactant of claim 5, wherein the particles comprise 20% by weight or less of any one non-surfactant active material and 10% by weight or less of the binder component, based on the total weight of the particles. Not active substance-containing delivery particles.   Non-surfactant-containing delivery particles according to any one of claims 1 to 6, comprising at least one additional coating.   The active substance-containing delivery particle that is not a surfactant according to any one of claims 1 to 7, comprising a substance selected from dyes, pigments, and mixtures thereof.   9. Active substance containing non-surfactant according to any one of the preceding claims, wherein the particles have a ratio of the median particle size of the core material to the median particle size of the solid coating auxiliary component of at least 10: 1. Delivery particles.   10. Active substance-containing delivery particles that are not surfactants according to any one of the preceding claims, wherein the particles have a core substance bulk density of at least 300 grams per liter.   A cleaning composition comprising active substance-containing delivery particles that are not surfactants according to any one of claims 1-10.   12. The cleaning composition of claim 11, wherein the cleaning composition comprises 15% by weight or less of any one non-surfactant-containing delivery particle based on the total weight of the cleaning composition.   The cleaning composition comprises 2% by weight or less of any one non-surfactant active substance, based on the total weight of the cleaning composition, the active substance being by the non-surfactant containing active substance-containing delivery particles The cleaning composition of claim 12, wherein the cleaning composition is delivered to the cleaning composition.   14. The median particle size of the active substance-containing delivery particles that are not the surfactant is in the range of 15-95 percentile of the mass-based cumulative particle size distribution of the cleaning composition. The cleaning composition according to Item.   15. The cleaning composition of claim 14, wherein the median particle size of the active agent-containing delivery particles that are not surfactants is in the range of 15-85 percentile of the mass-based cumulative particle size distribution of the cleaning composition. . A method for producing an active substance-containing delivery particle that is not a surfactant according to any one of claims 1 to 10, wherein the method comprises:
a. A) combining an active ingredient component that is not a surfactant and a binder component having a viscosity of less than 4 Pa · s (4,000 cps) to form a pre-mixture; and b. ) Coat and coat at least a portion of the core material having a median particle size of at least 150 microns and a distribution range of 1-2 with the premix and then a solid coating aid having a median particle size of less than 50 microns. Wherein the distribution range is [(D84 / D50) + (D50 / D16)] / 2 where D84 and D16 are 16 in the cumulative mass percent plot, respectively. Is the measured value of the core size distribution width around the median value calculated by (the particle size at the 84th and 84th percentiles), but if the D16 value is less than the finest sieve size (150 μm), D84 / D50) (where D50 is the median particle size) and the D84 value exceeds the coarsest sieve size (1700 μm) The D16 value is less than the finest sieve size (150 μm) and the D84 value exceeds the coarsest sieve size (1700 μm), the maximum value is 5.7;
Including methods. A cleaning method comprising:
a. ) Contact at least a portion of a location with a composition comprising a cleaning composition according to any one of claims 11 to 15 and / or a cleaning composition according to any one of claims 11 to 15. A step; and b. ) The method then comprises the step of cleaning and / or rinsing the location or part of the location.   The non-surfactant active agent component is sufficiently uniformly distributed in the coating to provide a relative standard deviation of no more than 10% non-surfactant active agent particles, wherein the particles are at least 10: 1 of the core material. 11. A method according to any one of claims 6 to 10 having a ratio between the median particle size and the median particle size of the solid coating aid, wherein the core material of the particles has a bulk density of at least 300 grams per liter. Active substance-containing delivery particles that are not surfactants.