Powder detergent composition

Abstract

The purpose of the present invention is to provide a powder detergent composition that contains a biodegradable additive and exhibits excellent cleaning performance when used as a powder detergent, and therefore has low environmental impact. The present invention relates to a powder detergent composition containing a vinyl alcohol polymer and a surfactant. The vinyl alcohol polymer has a structural unit (a) represented by formula (1) and may also have a structural unit (b) represented by formula (2) and an other structural unit (c) other than structural unit (a) and structural unit (b). The content ratio of each structural unit in relation to the total amount of 100 mol% of all of the structural units is structural unit (a) / structural unit (b) / other structural unit (c) = 50-100 / 0-50 / 0-20 mol%. The average degree of polymerization is 50-800. The content ratio of the surfactant in relation to 100 mass% of the powder detergent composition is 10-80 mass%. The content ratio of powder soap in relation to the total amount of 100 mass% of the surfactant is 1-100 mass%. The content ratio of a carboxyl group-containing polymer in relation to 100 mass% of the powder detergent composition is 0-1 mass%, and the content ratio of a phosphorus compound in relation to 100 mass% of the powder detergent composition is 0-1 mass%.

Description

Powder detergent composition

[0001] The present invention relates to a powder detergent composition.

[0002] Detergents mainly composed of surfactants have been developed in various types such as for clothing and for dishes. In addition to surfactants, various detergent additives are used in detergents. For example, polyvinyl alcohol is known as one of them (see, for example, Patent Documents 1 to 5).

[0003] Regarding detergents for clothing, in recent years, due to the spread of drum washing machines that can be washed with less water and the need to wash clothes in a short time for more efficient housework, the demand for liquid detergents that are easily soluble in water has been increasing.

[0004] Also, in response to the growing environmental problems, based on the actual state of the dirt on the objects to be cleaned, it has become increasingly necessary to design detergents that are more environmentally friendly and have a lower environmental impact than ever before. Regarding the reduction of the environmental impact caused by detergents, since the eutrophication problem of lakes and marshes in the 1980s, sodium tripolyphosphate, which had been used in large quantities until then, has been converted to zeolite (crystalline aluminosilicate) to eliminate phosphates. Furthermore, in recent years, biodegradation of detergent raw materials has been required, and the replacement of non-biodegradable synthetic polymers such as polyacrylic acid with biodegradable polymers has been under consideration.

[0005] JP-A-59-6299 JP-A-63-305198 JP-A-11-5992 WO 2002 / 046348 JP 2022-080076

[0006] In order to meet the above-mentioned demands and environmental problems, various additives conventionally used in powder detergents have been developed. However, in powder detergents, there is still room for further improving the cleaning performance of dirt. Also, due to the increasing interest of consumers in environmental protection, it is desired to use additives derived from sustainable resources such as compounds having biodegradability.

[0007] The present invention has been made in view of the above situation, and an object thereof is to provide a powder detergent composition with a small environmental load, which contains an additive having biodegradability and exhibits excellent cleaning performance when used as a powder detergent.

[0008] The inventor has conducted various studies on additives for detergents. As a result, by adding a vinyl alcohol-based polymer having biodegradability and an average degree of polymerization within a predetermined range to a composition containing a surfactant at a predetermined ratio, it has been found that excellent cleaning performance is exhibited when used as a powder detergent, and the inventor has conceived that the above problems can be solved perfectly and has reached the present invention.

[0009] The present invention includes the following powder detergent compositions and the like. [1] A powder detergent composition containing a vinyl alcohol-based polymer and a surfactant, wherein the vinyl alcohol-based polymer has the following formula (1);

[0010] and has a structural unit (a) represented by the following formula (2);

[0011] A powder detergent composition having a structural unit (b) represented by, and other structural units (c) other than the structural unit (a) and the structural unit (b), wherein the content ratio of each structural unit relative to the total amount of all structural units is structural unit (a) / structural unit (b) / other structural units (c) = 50-100 / 0-50 / 0-20 mol%, the average degree of polymerization is 50-800, the content ratio of the surfactant is 10-80% by mass relative to 100% by mass of the powder detergent composition, the content ratio of powder soap relative to the total amount of the surfactant is 1-100% by mass, the content ratio of carboxyl group-containing polymer is 0% by mass or more and 1% by mass or less relative to 100% by mass of the powder detergent composition, and the content ratio of phosphorus compounds is 0% by mass or more and 1% by mass or less relative to 100% by mass of the powder detergent composition. [2] The powder detergent composition according to [1], wherein the content of the surfactant is 10 to 40% by mass with respect to 100% by mass of the powder detergent composition. [3] The powder detergent composition according to any one of [1] to [2], wherein the surfactant includes an anionic surfactant. [4] The powder detergent composition according to any one of [1] to [3], wherein the surfactant includes an anionic surfactant and a nonionic surfactant. [5] The powder detergent composition according to any one of [1] to [4], wherein the surfactant includes an anionic surfactant and a nonionic surfactant, and the ratio of the anionic surfactant to 100% by mass of the total of the anionic surfactant and nonionic surfactant is 30% by mass or more. [6] The powder detergent composition according to any one of [1] to [5], which includes an enzyme. [7] The powder detergent composition according to [1] to [6], wherein the organic components contained in the powder detergent composition have a biodegradation rate of 40% or more after 28 days, as measured by a biodegradation test conducted in accordance with OECD 301F.

[0012] The powder detergent composition of the present invention has the above-described configuration, contains biodegradable additives, and exhibits excellent cleaning performance when used as a powder detergent, thus providing a powder detergent composition with a low environmental impact.

[0013] Preferred embodiments of the present invention will be described below in detail, but the present invention is not limited to the following descriptions and can be modified and applied as appropriate without changing the gist of the present invention. Furthermore, embodiments combining two or more of the individual preferred embodiments of the present invention described below also constitute preferred embodiments of the present invention.

[0014] [Powdered Detergent Composition] The powdered detergent composition of the present invention has a structural unit (a) represented by formula (1), and may further have a structural unit (b) represented by formula (2), and other structural units (c) other than structural unit (a) and structural unit (b), and the content ratio of each structural unit to the total amount of all structural units is structural unit (a) / structural unit (b) / other structural units (c) = 50 to 100 / 0 to 50 / 0 to 20 mol%, and comprises a vinyl alcohol polymer having an average degree of polymerization of 50 to 800, and a surfactant, wherein the content ratio of the surfactant is 10 to 80% by mass with respect to 100% by mass of the powdered detergent composition, the content ratio of powdered soap to the total amount of the surfactant is 1 to 100% by mass, and the content ratio of the carboxyl group-containing polymer is 0% by mass or more and 1% by mass or less with respect to 100% by mass of the powdered detergent composition. The phosphorus compound content is 0% by mass or more and 1% by mass or less based on 100% by mass of the powder detergent composition. Due to this composition, the powder detergent composition of the present invention exhibits excellent cleaning performance when used as a powder detergent, and also has excellent biodegradability. The powder detergent composition of the present invention is particularly excellent in cleaning mud stains.

[0015] The surfactant content in the powder detergent composition of the present invention may be 10 to 80% by mass, but preferably 10 to 60% by mass, based on 100% by mass of the powder detergent composition. In this case, the interaction between the surfactant and the vinyl alcohol polymer is considered to be greater, and the effect of the surfactant can be further enhanced. The surfactant content is more preferably 10 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 10 to 20% by mass.

[0016] The surfactant preferably includes an anionic surfactant, and its proportion is not particularly limited, but it is preferably 30% by mass or more based on 100% by mass of the total amount of surfactant in the powder detergent composition. More preferably it is 40 to 100% by mass, even more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass.

[0017] The surfactant preferably includes a nonionic surfactant, and its proportion is not particularly limited, but is preferably 0 to 70% by mass based on 100% by mass of the total amount of surfactant in the powder detergent composition. More preferably 0 to 60% by mass, even more preferably 10 to 60% by mass, and particularly preferably 10 to 50% by mass.

[0018] The surfactant preferably comprises an anionic surfactant and a nonionic surfactant. The total ratio of the anionic surfactant and the nonionic surfactant is not particularly limited, but is preferably 15 to 80% by mass based on 100% by mass of the total amount of surfactant in the powder detergent composition. More preferably 15 to 75% by mass, even more preferably 20 to 75% by mass, and particularly preferably 20 to 70% by mass.

[0019] The ratio of the anionic surfactant to the total of 100% by mass of the anionic surfactant and nonionic surfactant is not particularly limited, but is preferably 30% by mass or more. More preferably 40 to 100% by mass, even more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass.

[0020] The content of the vinyl alcohol polymer in the powder detergent composition of the present invention is not particularly limited, but is preferably 0.5 to 10% by mass based on 100% by mass of the powder detergent composition. More preferably it is 1 to 9% by mass, and even more preferably 2 to 8% by mass.

[0021] The content of the vinyl alcohol-based polymer in the powder detergent composition of the present invention is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 3 to 35% by mass, and even more preferably 10 to 35% by mass, based on 100% by mass of the surfactant.

[0022] The powder detergent composition of the present invention may contain other components besides the vinyl alcohol polymer and surfactant. The content of the other components is not particularly limited, but is preferably 10 to 90% by mass. More preferably 20 to 85% by mass, and even more preferably 30 to 80% by mass.

[0023] The powder detergent composition of the present invention uses powdered soap as the surfactant from the viewpoint of maintaining biodegradability. The amount of powdered soap used is not particularly limited as long as it is contained in the surfactant, but it is preferable that the content ratio of powdered soap to 100% by mass of the total amount of the surfactant is 1 to 100% by mass. More preferably it is 10 to 90% by mass, even more preferably 10 to 80% by mass, and particularly preferably 20 to 60% by mass.

[0024] From the viewpoint of maintaining biodegradability, the powder detergent composition of the present invention preferably contains a small amount of non-biodegradable components. Specifically, the content of the carboxyl group-containing polymer is preferably 0% by mass or more and 1% by mass or less, based on 100% by mass of the powder detergent composition of the present invention. More preferably, it is 0% by mass or more and 0.8% by mass or less, even more preferably 0% by mass or more and 0.5% by mass or less, and particularly preferably 0% by mass or more and 0.2% by mass or less. 0% by mass is also one embodiment.

[0025] Examples of the carboxyl group-containing polymers include polyacrylic acid, acrylic acid-maleic acid, acrylic acid, copolymers of maleic acid with sulfonic acid-containing monomers such as 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof. Examples of salts include sodium salts, potassium salts, and ammonium salts. It is preferable that the content of the aforementioned carboxyl group-containing polymer in the powder detergent composition of the present invention is low, as this improves the biodegradability of the organic components contained in the powder detergent composition of the present invention.

[0026] As described above, the powder detergent composition of the present invention preferably contains a small amount of non-biodegradable components, and more preferably contains a small amount of components that have a high environmental impact. Specifically, the content of phosphorus compounds is preferably 0% by mass or more and 1% by mass or less, based on 100% by mass of the powder detergent composition. More preferably 0% by mass or more and 0.5% by mass or less, even more preferably 0% by mass or more and 0.2% by mass or less, and particularly preferably 0% by mass.

[0027] Examples of the aforementioned phosphorus compounds include polyphosphate (salt), tripolyphosphate (salt), and the like.

[0028] Furthermore, from the viewpoint of environmental protection, the organic components contained in the powder detergent composition of the present invention preferably have a biodegradation rate of 40% or more after 28 days, as measured by a biodegradation test conducted in accordance with OECD 301F. More preferably, it is 50% or more, even more preferably 60% or more, and particularly preferably 70% or more. The organic components refer to organic compounds in general, and include the vinyl alcohol polymer and the surfactant used in the powder detergent composition of the present invention. In addition, other organic components composed of organic compounds that are used as auxiliary agents as described later are also included.

[0029] Furthermore, the powder detergent composition of the present invention preferably contains few non-biodegradable components, and preferably the non-biodegradable components are 10% by mass or less of the total amount of the powder detergent composition (100% by mass). More preferably, it is 8% by mass or less, even more preferably 4% by mass or less, and particularly preferably 2% by mass or less.

[0030] The above powder detergent composition may also be used as a flexible soluble solid sheet. Flexible soluble solid sheets are generally known to contain surfactants and / or other active ingredients in a water-soluble polymer carrier or matrix. Such sheets are particularly useful for delivering surfactants and / or other active ingredients when dissolved in water. Compared to conventional granular or liquid forms within the same product category, such sheets have better structural integrity, are more concentrated, and are easier to store, transport / carry, carry, and handle. Compared to solid tablet forms within the same product category, such sheets are more flexible, less brittle, and have a better sensory appeal to consumers. A flexible soluble solid sheet containing the powder detergent composition of the present invention is also one of the present inventions. The flexible soluble solid sheet may be porous. A form in which the flexible soluble solid sheet is a flexible porous soluble solid sheet is also one of the preferred embodiments. The above flexible soluble solid sheet may be in the form of a laminate of fibrous compositions containing a water-soluble polymer and a surfactant.

[0031] The above-described flexible soluble solid sheet can be formed from a wet premix containing a water-soluble polymer and a surfactant. More specifically, it can be produced by preparing a wet premix containing a water-soluble polymer and a surfactant, then aerating the premix by introducing gas, forming the aerated premix into a sheet, and finally drying the sheet at a high temperature. Such a water-soluble polymer can function in the resulting solid sheet as a film-forming agent, a structural agent, and a carrier for other active ingredients (e.g., surfactants, emulsifiers, builders, chelating agents, fragrances, colorants, etc.). The wet premix is ​​preferably in a form containing 3 to 20% by weight of the water-soluble polymer, more preferably in a form containing 5 to 15% by weight of the water-soluble polymer, and may also contain 7 to 10% by weight of the water-soluble polymer in a form.

[0032] After drying, the water-soluble polymer is preferably present in the flexible soluble solid sheet in an amount of 5 to 50% by weight, more preferably 8 to 40% by weight, even more preferably 10 to 30% by weight, and most preferably 12 to 25% by weight, relative to the total weight of the solid sheet. In a particularly preferred embodiment of the present invention, the total amount of water-soluble polymer present in the flexible soluble solid sheet of the present invention is 25% by weight or less, relative to the total weight of such sheet.

[0033] The weight-average molecular weight of the water-soluble polymer is not particularly limited, but is preferably 50,000 to 400,000. More preferably 60,000 to 300,000, even more preferably 70,000 to 200,000, and most preferably 80,000 to 150,000. The weight-average molecular weight is calculated by adding the average molecular weight of each polymer raw material multiplied by its respective relative weight percentage based on the total weight of the polymer present in the solid sheet. The weight-average molecular weight of the water-soluble polymer may affect the viscosity of the wet premix, which in turn may affect the number and size of bubbles during the aeration process and the pore expansion / opening results during the drying process. Furthermore, the weight-average molecular weight of the water-soluble polymer may affect the overall film-forming properties of the wet premix and its compatibility / incompatibility with certain surfactants.

[0034] As the water-soluble polymer, the polyvinyl alcohol copolymer of the present invention can be used. The water-soluble polymer is a polyvinyl alcohol copolymer characterized by a degree of hydrolysis in the range of preferably 40 to 100%, more preferably 50 to 95%, even more preferably 65 to 92%, and most preferably 70 to 90%. In a particularly preferred embodiment, the flexible soluble solid sheet contains 10 to 25% by weight, more preferably 15 to 23% by weight, of the total weight of such a sheet, a polyvinyl alcohol copolymer having a weight-average molecular weight in the range of 80,000 to 150,000 and a degree of hydrolysis in the range of 80 to 90%.

[0035] [Vinyl alcohol polymer] The vinyl alcohol polymer contained in the powder detergent composition of the present invention has a structural unit (a) represented by formula (1), and may further have a structural unit (b) represented by formula (2), as well as other structural units (c) other than structural unit (a) and structural unit (b), and the content ratio of each structural unit to the total amount of all structural units is structural unit (a) / structural unit (b) / other structural units (c) = 50 to 100 / 0 to 50 / 0 to 20 mol%, and the average degree of polymerization is 50 to 800.

[0036] The proportion of structural unit (a) in the vinyl alcohol polymer may be 50 to 100 mol% of the total amount of structural units (100 mol%), but is preferably 55 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 65 to 99 mol%, and particularly preferably 70 to 98 mol%. In one embodiment, a form in which the proportion of structural unit (a) is 5 to 100 mol% or 80 to 100 mol% of the total amount of structural units (100 mol%) is also one of the preferred embodiments. In one embodiment, it is also preferable that the proportion of structural unit (a) is 50 to 95 mol% of the total amount of structural units (100 mol%). This results in superior cleaning power against hydrophobic stains such as sebum and composite stains which are a combination of hydrophilic and hydrophobic stains. More preferably 60 to 90 mol%, and even more preferably 70 to 90 mol%. The proportion of structural unit (a) in vinyl alcohol polymers substantially corresponds to the degree of saponification of the polymer.

[0037] The proportion of structural unit (b) in the vinyl alcohol polymer may be 0 to 50 mol% of the total amount of structural units (100 mol%), but is preferably 0 to 45 mol%, more preferably 0 to 40 mol%, even more preferably 0 to 35 mol%, and particularly preferably 0 to 30 mol%. In one embodiment, forms in which the proportion of structural unit (b) is 0.1 to 25 mol%, 1 to 20 mol%, or 1 to 10 mol% of the total amount of structural units (100 mol%) are also preferred embodiments.

[0038] The proportion of structural unit (c) in the vinyl alcohol polymer may be 0 to 20 mol%, but preferably 0 to 15 mol%, more preferably 0 to 10 mol%, even more preferably 0 to 5 mol%, and particularly preferably 0 to 1 mol%. A form in which the proportion of structural unit (c) is 0 mol% is also one of the preferred embodiments of the present invention.

[0039] The vinyl alcohol-based polymer has an average degree of polymerization of 50 to 800. This allows the powder detergent composition of the present invention to exhibit excellent cleaning performance. The average degree of polymerization is preferably 50 to 700, more preferably 100 to 600, even more preferably 100 to 500, even more preferably 150 to 400, and particularly preferably 180 to 300. The average degree of polymerization can be measured by the method described in the examples.

[0040] The vinyl alcohol polymer may have structural unit (c), and structural unit (c) is not particularly limited as long as it is a structural unit other than structural unit (a) and structural unit (b). The monomer forming structural unit (c) can be any monomer copolymerizable with vinyl acetate, which is the raw material for structural units (a) and (b). Examples include: (meth)allyl alcohol, 3-methyl-3-buten-1-ol (isoprenol), and other unsaturated alcohols having 3 to 8 carbon atoms, and esters thereof with carboxylic acids having 2 to 8 carbon atoms; esters of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and citraconic acid, and alkoxy polyalkylene glycols such as methoxypolyethylene glycol; unsaturated alcohols such as allyl alcohol and isoprenol; alkylene oxide adducts such as ethylene oxide and propylene oxide to unsaturated alcohols such as allyl alcohol and isoprenol; acrylamide, sodium acrylamidepropanesulfonate, sodium 2-hydroxy-3-alyloxypropanesulfonate, hydroxyethyl acrylate, hydroxyethyl Examples include vinyl ethers such as methyl methacrylate, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, and hydroxybutyl vinyl ether, as well as alkylene oxide adducts such as ethylene oxide and propylene oxide, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, etc.; aromatic vinyl monomers such as styrene; olefin monomers such as ethylene and propylene; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; cyclic vinyl monomers such as N-vinylpyrrolidone; acrylonitrile; vinylformamide, vinylacetamide, etc.

[0041] [Method for producing vinyl alcohol polymers] The method for producing the vinyl alcohol polymer is not particularly limited, but if the vinyl alcohol polymer consists only of structural unit (a) or of structural units (a) and (b), it is preferable to polymerize vinyl acetate and then perform hydrolysis. If the vinyl alcohol polymer has structural unit (c), it is preferable to copolymerize vinyl acetate with the monomer that forms structural unit (c) and then perform hydrolysis.

[0042] The polymerization temperature during the production of the vinyl alcohol-based polymer is preferably 0 to 70°C. As polymerization initiators, low-temperature decomposition radical generating agents such as diisopropyl peroxydicarbonate, isobutylyl peroxide, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), bis(4-t-butylcyclohexol) peroxydicarbonate, dimyristil peroxydicarbonate, acetylcyclohexylsulfonyl peroxide, n-propyl peroxydicarbonate, α-cumyl peroxyneodecanoate, and 2,4,4-triethylpentyl peroxyphenoxyacetate can be effectively used, but are not limited to these. Furthermore, initiators such as 2,2'-azobisisobutyronitrile can be used in combination during UV irradiation. Furthermore, so-called redox initiator systems, which combine peroxide-based radical initiators with reducing agents such as dimethylaniline and Q-ascorbic acid, and oxidizing agents such as iron salts, are also effective. Initiating radical polymerization with electron beams or radiation is also effective.

[0043] Mercaptans may be used as chain transfer agents. A predetermined amount of the mercaptans may be added to the polymerization system before polymerization begins, and once polymerization has substantially started, the mercaptans may be continuously supplied to the polymerization system at a constant rate.

[0044] In the case of the vinyl alcohol polymer, it is preferable to initiate the saponification of the polyvinyl acetate ester in an alcohol containing an alkali catalyst of a predetermined concentration or higher. If the alcohol is methanol, it is desirable to initiate the saponification reaction of the polyvinyl acetate ester in methanol containing an alkali of at least 0.18 mol / l.

[0045] [Powder detergent composition and its manufacture] The powder detergent composition of the present invention requires several auxiliary agents. Common cleaning auxiliary agents include builders, enzymes, polymers not mentioned above, bleaching agents, bleaching activators, catalysts, and the like. Other cleaning aids used herein include various active ingredients or special substances such as foaming accelerators and antifoaming agents, for example, dispersible polymers other than those mentioned above (e.g., those from BASF Corp. or Rohm & Haas), color speckles, silvercare, rust inhibitors and / or corrosion inhibitors, dyes, fillers, disinfectants, alkali sources, hydrotropes, antioxidants, enzyme stabilizers, pro-fragrances, fragrances, solubilizers, carriers, processing aids, pigments, and, in the case of liquid formulations, solvents, chelating agents, color transfer inhibitors, dispersants, whitening agents, antifoaming agents, dyes, structure elasticizing agents, fabric softeners, abrasion inhibitors, hydrotropes, processing aids, and other fabric care agents, surface and skin care agents. Suitable examples of other cleaning aids and amounts of use can be found in U.S. Patent No. 5,576,282, No. 6,306,812 and No. 6,326,348.

[0046] In another embodiment, the final granular detergent product is produced by mixing the vinyl alcohol polymer with an optional dry mixed component and / or an optional liquid spray component. The final granular detergent product is typically formulated so that, during use in aqueous cleaning operations, the pH of the cleaning water is about 6.5 to about 12, preferably about 7.5 to 10.5. Techniques for controlling the pH at the recommended usage level include, but are not limited to, the use of buffers, alkalis, acids, etc., which are well known to those skilled in the art.

[0047] Generally, laundry detergent is a fully formulated powder detergent composition and not merely a part of the powder detergent composition, such as spray-dried particles or aggregated particles that form only a portion of the powder detergent composition. However, the use of further rinse additive compositions (e.g., fabric conditioners or enhancers) or main wash additive compositions (e.g., bleaching additives) in combination with the powder detergent composition of the present invention is also within the scope of the present invention. However, it may be preferable not to use the bleaching additive composition in combination with the powder detergent composition.

[0048] Generally, powder detergent compositions include spray-dryable base detergent particles and / or agglomerating base detergent particles and / or extruded base detergent particles, etc., surfactant particles (including surfactant aggregates, surfactant extruders, surfactant needles, surfactant noodles, surfactant flakes); polymer particles (e.g., cellulose polymer particles, polyester particles, polyamine particles, terephthalate polymer particles, polyethylene glycol polymer particles, etc.); builder particles (e.g., cobuilder particles of sodium carbonate and sodium silicate, phosphate particles, zeolite particles, silicate particles, carbonate particles, etc.); filler particles (e.g., sulfate particles, etc.); color transfer inhibitor particles; dye-fixing particles; bleaching agent particles (e.g., percarbonate particles, in particular coated percarbonate particles such as percarbonates coated with carbonates, sulfates, silicates, borosilicates, or any combination thereof, perborate particles, bleaching catalyst particles such as transition metal bleaching catalyst particles or oxaziridinium-based bleaching catalyst particles, preformed peracid particles, in particular coated preformed peracid particles, and bleaching activators and peroxidants). (e.g., co-bleaching particles with a hydrogen source and optionally a bleaching catalyst); bleaching activator particles (e.g., oxybenzenesulfonate bleaching activator particles and tetraacetylethylenediamine bleaching activator particles); chelating agent particles (e.g., chelating agent aggregates); hue dye particles; whitening agent particles; enzyme particles (e.g., protease globules, lipase globules, cellulase globules, amylase globules, mannanase globules, pectinate lyase globules, xyloglucanase globules, bleaching enzyme globules, cutinase globules, and co-globules of any of these enzymes) Clay particles (e.g., montmorillonite particles or clay and silicone particles); flocculant particles (e.g., polyethylene oxide particles); wax particles (e.g., wax aggregates); fragrance particles (e.g., fragrance microcapsules, especially melamine-formaldehyde fragrance microcapsules, starch-encapsulated fragrance accord particles, and Schiff base reaction product particles, etc.); aesthetic particles (e.g., colored noodles or needles or lamellar particles, and soap rings including colored soap rings);and includes multiple chemically distinct particles, typically two or more, three or more, four or more, five or more, six or more, or even ten or more particles, selected from any combination thereof.

[0049] (Detergent Components) The powder detergent composition of the present invention typically contains detergent components. These detergent components include detergent surfactants comprising anionic detergent surfactants, nonionic detergent surfactants, cationic detergent surfactants, bipolar ionic detergent surfactants, amphoteric detergent surfactants, and any combination thereof; polyester stain-releasing polymers such as carboxylate polymers, polyethylene glycol polymers, and terephthalate polymers; dye-fixing polymers such as amine polymers, cellulosic polymers, anti-dye transfer polymers, and optionally condensed oligomers produced by the condensation of imidazole and epichlorohydrin in a 1:4:1 ratio; hexamethylenediamine derivative polymers, and any combination thereof; builders comprising zeolites, phosphates, citrates, and any combination thereof; buffers comprising carbonates and / or silicates, and alkali sources; fillers comprising sulfates and biofiller materials; bleach activators, and sources of available oxygen. Bleaching agents comprising preformed peracids, bleaching catalysts, reducing bleaching agents, and any combination thereof; chelating agents; photobleaching agents; colorants; whitening agents; enzymes comprising proteases, amylases, cellulases, lipases, xyloglucanases, pectinate lyases, mannanases, bleaching enzymes, cutinases, and any combination thereof; fabric softeners comprising clays, silicones, quaternary ammonium fabric softeners, and any combination thereof; flocculants such as polyethylene oxide; fragrances comprising starch-encapsulated fragrance accords, fragrance microcapsules, fragrance-filled zeolites, Schiff base reaction products of ketone fragrance raw materials and polyamines, blooming fragrances, and any combination thereof; aesthetic agents comprising soaprings, lamellar aesthetic particles, gelatin beads, speckles of carbonates and / or sulfates, colored clays, and any combination thereof; and any combination thereof.

[0050] <Surfactants> The powder detergent composition of the present invention contains surfactants. Preferred surfactants include anionic detergent surfactants, nonionic detergent surfactants, cationic detergent surfactants, bipolar ionic detergent surfactants, amphoteric detergent surfactants, powder soaps, and any combination thereof.

[0051] <Powdered Soap> The powdered detergent composition of the present invention contains powdered soap as the surfactant. The powdered soap of the present invention is not particularly limited as long as it is a fatty acid having 10 to 22 carbon atoms or a salt thereof. Examples of fatty acid salts having 10 to 22 carbon atoms include monovalent or divalent alkali metal salts such as sodium salts, potassium salts, lithium salts and / or magnesium salts of fatty acids, ammonium salts and / or alkylammonium salts of fatty acids, preferably sodium salts. Preferred fatty acids (salts) are fatty acids (salts) having 10 to 20 carbon atoms, and more preferably fatty acids (salts) having 12 to 18 carbon atoms. Specific examples of the fatty acids (salts) include caprylic acid (salt), capric acid (salt), lauric acid (salt), myristic acid (salt), myristoleic acid (salt), palmitic acid (salt), palmitoleic acid (salt), sapienic acid (salt), stearic acid (salt), oleic acid (salt), elaidic acid (salt), vaccenic acid (salt), linoleic acid (salt), linoleidic acid (salt), α-linoleidic acid (salt), arachidic acid (salt), arachidonic acid (salt), eicosapentaenoic acid (salt), behenic acid (salt), erucic acid (salt), docosahexaenoic acid (salt), and mixtures thereof. The average particle size of the powder soap of the present invention is not particularly limited, but is usually about 50 microns to about 500 microns. For example, it may be 50 microns, 100 microns, 150 microns, 200 microns, 250 microns, or 300 microns. Alternatively, the particle size may be 400 microns, 500 microns, or any range in between. The powder soap of the present invention may contain a mixture of powder soap particles of different particle sizes. The powder soap used in the present invention can be manufactured by any known method. For example, the cleaning composition may contain pulverized soap produced by grinding PalmoSalt NP021 soap powder supplied by Taiko Palm Oleo Zhangjiagang Co., Ltd. using a pin mill under N2 gas or dry ice to cool the soap particles during cleaning. The powder soap of the present invention is not particularly limited, as long as the content ratio of powder soap to 100% by mass of the total amount of surfactant is 1 to 100% by mass.Preferably, the amount is 10 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 60% by mass. When the amount of the powder soap of the present invention is within the above range relative to 100% by mass of the total amount of the surfactant, it exhibits excellent cleaning power due to the combination of components such as anionic and nonionic cleaning surfactants that have high cleaning performance in hard water, and powder soap that has electrical adsorption capacity to mud particles and is highly biodegradable.

[0052] <Anionic Cleaning Surfactants> Examples of anionic cleaning surfactants include sulfate cleaning surfactants and sulfonate cleaning surfactants.

[0053] Preferably, the amount of the anionic cleaning surfactant is in the range of 5% to 50% by weight of the total composition. More preferably, the amount of the anionic surfactant is in the range of about 8% to about 35% by weight.

[0054] Examples of sulfonate cleaning surfactants include alkylbenzene sulfonates such as alkylbenzene sulfonates having 10 to 13 carbon atoms. Suitable alkylbenzene sulfonates (LAS) can be obtained by sulfonating commercially available linear alkylbenzenes (LABs), or are available for further acquisition. Suitable LABs include low 2-phenyl LABs such as those supplied by Sasol under the trade name Isochem® or by Petresa under the trade name Petrelab®. Other suitable LABs include high 2-phenyl LABs such as those supplied by Sasol under the trade name Hyblene®. Other anionic cleaning surfactants are alkylbenzene sulfonates obtained by the DETAL catalytic process, but other synthesis routes such as HF may be preferred.

[0055] Examples of sulfate cleaning surfactants include alkyl sulfates having 8 to 18 carbon atoms, or alkyl sulfates mainly having 12 carbon atoms. Alkyl sulfates may be derived from natural sources such as cocoa and / or taro. Alternatively, alkyl sulfates may be derived from synthetic sources such as alkyl sulfates having 12 to 15 carbon atoms.

[0056] Other sulfate cleaning surfactants are alkyl ethoxylated sulfates, or alkyl alkoxylated sulfates having 8 to 18 carbon atoms, or alkyl alkoxylated sulfates having 8 to 18 carbon atoms. Alkyl alkoxylated sulfates may have an average degree of alkoxylation of 0.5 to 20, or 0.5 to 10. Typically, alkyl alkoxylated sulfates may be alkyl ethoxylated sulfates having 8 to 18 carbon atoms having an average degree of ethoxylation of 0.5 to 10, or 0.5 to 7, or 0.5 to 5, or 0.5 to 3.

[0057] Alkyl sulfates, alkylalkoxylated sulfates, and alkylbenzene sulfonates may be linear or branched, and may be substituted or unsubstituted.

[0058] The anionic cleaning surfactant may be a medium-chain branched alkyl sulfate and / or a medium-chain branched alkylbenzene sulfonate, or other medium-chain branched anionic cleaning surfactants. The medium-chain branch is typically an alkyl group having 1 to 4 carbon atoms, such as a methyl group and / or an ethyl group.

[0059] Other anionic cleaning surfactants besides those mentioned above are alkylethoxycarboxylates.

[0060] Anionic cleaning surfactants typically exist in their salt form and are typically complexed with a suitable cation. A suitable counterion is Na. ＋ and K ＋ Examples include substituted ammonium compounds having 1 to 6 carbon atoms, such as monoethanolamine (MEA), triethanolamine (TEA), diethanolamine (DEA), and any combination thereof.

[0061] <Nonionic Cleaning Surfactants> Nonionic cleaning surfactants are selected from the group consisting of: C8-C18 alkyl ethoxylates such as Shell's NEODOL® nonionic surfactant; C6-C12 alkylphenol alkoxylates in which the alkoxylate unit is optionally an ethylene oxy unit, a propylene oxy unit, or a mixture thereof; condensates of ethylene oxide / propylene oxide block polymers such as BASF's Pluronic® with C12-C18 alcohols and C6-C12 alkylphenols; C14-C22 medium-chain branched-chain alcohols; C14-C22 medium-chain branched-chain alkyl alkoxylates having an average alkoxylation degree of 1-30; alkyl polysaccharides such as alkyl polyglycosides; polyhydroxy fatty acid amides; ether-terminated poly(oxyalkylated) alcohol surfactants; and mixtures thereof.

[0062] The nonionic cleaning surfactant is preferably an alkyl polyglucoside and / or an alkyl alkoxylated alcohol.

[0063] If present, nonionic cleaning surfactants are preferably used in an amount ranging from about 1% to about 20% by mass relative to 100% by mass of the powder detergent composition.

[0064] A more preferred form of nonionic cleaning surfactant is an alkylalkoxylated alcohol having 8 to 18 carbon atoms, or an alkylethoxylated alcohol having 8 to 18 carbon atoms. The alkylalkoxylated alcohol is not particularly limited as long as it is between 0.5 and 50, preferably between 1 and 30, more preferably between 1 and 20, and even more preferably between 1 and 10 in average alkoxylation degree. The alkylalkoxylated alcohol is not particularly limited as long as it is between 1 and 10, more preferably between 1 and 7, even more preferably between 1 and 5, or an alkylethoxylated alcohol having 8 to 18 carbon atoms with an average ethoxylation degree of 3 to 7. The alkylalkoxylated alcohol may be linear or branched, and may be substituted or unsubstituted.

[0065] Another preferred form of nonionic cleaning surfactant is a secondary alcohol-based cleaning surfactant having the following formula (11):

[0066] (In formula (11), R １１ R is a linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl group having 2 to 8 carbon atoms, １２ R is a linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl group having 2 to 8 carbon atoms, １１ Base and R １２ The total number of carbon atoms present in the base is in the range of 7 to 13, EO / PO is an alkoxy moiety selected from ethoxy, propoxy, or a mixture thereof, and optionally, the EO / PO alkoxy moiety can take the form of a random or block structure. n represents the average degree of alkoxylation, which is 4 to 10.

[0067] Other preferred nonionic cleaning surfactants include EO / PO block copolymer surfactants such as the Plurafac® series surfactants available from BASF, and sugar-derived surfactants such as alkyl N-methyl glucose amides.

[0068] A more preferred form of nonionic cleaning surfactant is a primary or secondary alcohol ethoxylate, which is not particularly limited, but is preferably an aliphatic alcohol having 8 to 20 carbon atoms ethoxylated with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, and more preferably a primary or secondary aliphatic alcohol having 10 to 15 carbon atoms ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Examples of non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamides (e.g., glucamide).

[0069] <Cationic Cleaning Surfactants> Examples of cationic cleaning surfactants include alkylpyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.

[0070] Preferably, it is a quaternary ammonium compound having the following formula (12):

[0071] (In formula (12), R ２１ is a linear or branched, substituted or unsubstituted alkyl or alkenyl moiety having 6 to 18 carbon atoms, R ２２ and R ２３ are independently selected from methyl or ethyl moieties, R ２４ is a hydroxyl, hydroxymethyl, or hydroxyethyl moiety, and X － is an anion that provides electrical neutrality, and examples of the anion include halides such as chloride, sulfate, and sulfonate). The cationic detergent surfactant is a monoalkylmono-hydroxyethyldimethylquaternary ammonium chloride having 6 to 18 carbon atoms. The cationic detergent surfactant in a preferred form is monoalkylmono-hydroxyethyldimethylquaternary ammonium chloride having 8 to 10 carbon atoms, monoalkylmono-hydroxyethyldimethylquaternary ammonium chloride having 10 to 12 carbon atoms, and monoalkylmono-hydroxyethyldimethylquaternary ammonium chloride having 10 carbon atoms.

[0072] Amphoteric and / or zwitterionic detergent surfactants: Suitable amphoteric and / or zwitterionic detergent surfactants include amine oxides such as dodecyldimethylamine N-oxide, alkanolamine sulfobetaines, cocoamidopropyl betaine, HN ＋ -R ２５ -CO ２ － -type surfactants (wherein R ２５ may be any crosslinking group such as alkyl, alkoxy, aryl, or amino acid). Many suitable detergent active compounds can be used, and are described in detail, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry, and Berch.

[0073] <Chelating Agents> Examples of chelating agents include diethylenetriaminepentaacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediamine-N'N'-nicuccinic acid, ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), hydroxyethanedi(methylenephosphonic acid), and any combination thereof. Preferably, ethylenediamine-N'N'-nicuccinic acid (EDDS) and / or hydroxyethanediphosphonic acid (HEDP). The powder detergent composition of the present invention may contain ethylenediamine-N'N'-nicuccinic acid or a salt thereof. Ethylenediamine-N'N'-nicuccinic acid may be in S,S enantiomer form. The powder detergent composition of the present invention may contain 4,5-dihydroxy-m-benzenedisulfonic acid disodium salt. A suitable chelating agent may also be a calcium crystal growth inhibitor. When using a chelating agent in the powder detergent composition of the present invention, it is preferable to use a biodegradable chelating agent. A specific example of a biodegradable chelating agent is dicarboxymethylalanine trisodium (product name: Neutrol MGDA; manufactured by BASF).

[0074] <Polymers> The powder detergent composition of the present invention may contain polymers. Specifically, examples include polyester stain-releasing polymers such as carboxylate polymers, polyethylene glycol polymers, and terephthalate polymers, amine polymers, cellulosic polymers, dye-transfer-inhibiting polymers, dye-fixing polymers such as condensed oligomers produced by the condensation of imidazole and epichlorohydrin in a ratio of 1:4:1 (optionally), hexamethylenediamine derivative polymers, and any combination thereof.

[0075] Examples of polycarboxylic acid polymers include maleic acid / acrylic acid random copolymers or polyacrylic acid homopolymers. The polycarboxylic acid polymer may be a polyacrylic acid homopolymer having a weight-average molecular weight of 4,000 to 9,000 or 6,000 to 9,000. Other polycarboxylic acid polymers are copolymers of maleic acid and acrylic acid, and may have a weight-average molecular weight in the range of 4,000 to 9,000. The powder detergent composition of the present invention may contain a carboxyl group-containing compound such as the polycarboxylic acid polymer, but its content is preferably 1% by mass or less per 100% by mass of the powder detergent composition of the present invention. More preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. 0% by mass is also one embodiment. It is preferable that the content of the carboxyl group-containing compound in the powder detergent composition of the present invention be within the above range, as this improves the biodegradability of the powder detergent composition of the present invention.

[0076] <Polyester stain-releasing polymer> The polyester stain-releasing polymer has a structure defined by one of the following structural formulas (13), (14), or (15): (13)-[(OCHR ３１ - CHR ３２ )a-O-OC-Ar-CO-] ｄ (14)-[(OCHR ３３ - CHR ３４ )b-O-OC-sAr-CO-] ｅ (15)-[(OCHR ３５ - CHR ３６ ) c-OR ３７ ] ｆ (In the formula, a, b, and c are between 1 and 200, d, e, and f are between 1 and 50, Ar is 1,4-substituted phenylene, and sAr is SO at position 5) ３ It is a 1,3-substituted phenylene substituted with Me, where Me is H, Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetraalkylammonium (the alkyl group is an alkyl or C1-C18 atom). ２ ~C １０R is a hydroxyalkyl group, or any mixture thereof. ３１ , R ３２ , R ３３ , R ３４ , R ３５ , and R ３６ R is independently selected from a hydrogen atom or an n- or iso-alkyl group having 1 to 18 carbon atoms. ３７ This refers to a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 9 carbon atoms, an aryl group having 8 to 30 carbon atoms, or an arylalkyl group having 6 to 30 carbon atoms.

[0077] A more preferred polyester stain-releasing polymer is a terephthalate polymer having the structure of (13) or (14) described above.

[0078] Specifically, examples include polymers from the Repel-O-Tex® series, such as Repel-O-Tex® SF2 (Rhodia), and / or polymers from the Texcare® series, such as Texcare® SRA300 (Clariant).

[0079] Other examples of fouling-releasing polymers include sulfonated and unsulfonated PET / POET polymers, and polyethylene glycol / polyvinyl alcohol graft copolymers with both ends protected and with unprotected ends (e.g., Sokolan® HP22).

[0080] A particularly preferred fouling-releasing polymer is the sulfonated unend-protected polyester described and claimed in International Publication No. 95 / 32997 (Rhodia Chimie).

[0081] <Amine Polymers> The powder detergent composition of the present invention may also contain amine polymers. Specifically, examples include polyethyleneimine polymers such as alkoxylated polyalkyleneimines containing polyethylene and / or polypropylene oxide blocks.

[0082] <Cellulose-based polymers> The powder detergent composition of the present invention may contain cellulose-based polymers such as alkylcellulose, alkylalkoxyalkylcellulose, carboxyalkylcellulose, alkylcarboxyalkyl, and polymers selected from any combination thereof. Preferably, these are selected from carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, and mixtures thereof. Carboxymethylcellulose has a carboxymethyl substitution degree of 0.5 to 0.9 and a weight-average molecular weight of 100,000 to 300,000. Another preferred cellulose-based polymer is hydrophobic modified carboxymethylcellulose such as Finnfix® SH-1 (CP Kelco).

[0083] Other cellulosic polymers are preferably those having a degree of substitution (DS) of 0.01 to 0.99 and a degree of block (DB) such that DS + DB is at least 1.00 or DB + 2DS - DS2 is at least 1.20. Substituted cellulosic polymers can have a degree of substitution (DS) of at least 0.55. Substituted cellulosic polymers are preferably those with a degree of block (DB) of at least 0.35. A more preferred degree of block (DB) is DS + DB of 1.05 to 2.00. Specifically, carboxymethylcellulose is preferred.

[0084] <Dye Transfer Prevention Polymer> The powder detergent composition of the present invention may contain a dye transfer prevention (DTI) polymer. Specifically, this includes polyvinylpyrrolidone (PVP), vinyl copolymer of pyrrolidone and imidazoline (PVPVVI), polyvinyl N-oxide (PVNO), and any mixture thereof.

[0085] <Hexamethylenediamine derivative polymer> The powder detergent composition of the present invention may contain a hexamethylenediamine derivative polymer having the following formula (16). R ６０ (CH ３ ) N ＋ (CH ２ ) ６ N ＋ (CH ３ ) R６０ ・2X － (16) (wherein, X － R represents the counterion, specifically the chloride ion. ６０ This is a poly(ethylene glycol) chain with an average ethoxylation degree of 20 to 30. ６０ The poly(ethylene glycol) chains within may be end-protected with sulfate and / or sulfonate groups, either identically or differently, and are typically X － Reduce the number of counterions, or (if the average degree of sulfated per molecule is greater than 2) Y ＋ The charge is equilibriumized by introducing a counterion represented by Y. ＋ A specific example of a counterion represented by this formula is the sodium cation.

[0086] In another embodiment, the powder detergent composition of the present invention may contain a citrate. Specifically, sodium citrate is an example of a citrate. Citric acid capable of forming a citrate in a cleaning solution may also be incorporated into the powder detergent composition of the present invention.

[0087] In another embodiment, the powder detergent composition of the present invention may contain a bleaching agent. Alternatively, the laundry detergent may not contain a bleaching agent substantially. Substantially not containing a bleaching agent means "not intentionally added." Examples of bleaching agents include bleaching activators, sources of available oxygen, preformed peracids, bleaching catalysts, reducing bleaching agents, and any combination thereof. When a bleaching agent is added, the bleaching agent, or any component thereof (e.g., preformed peracid), can be coated by encapsulation or the like, or clathrated by using urea or cyclodextrin.

[0088] In another embodiment, the powder detergent composition of the present invention comprises a bleach activator. Examples of bleach activators include tetraacetylethylenediamine (TAED); oxybenzene sulfonates such as nonanoyloxybenzene sulfonate (NOBS), capryliamide nonanoyloxybenzene sulfonate (NACA-OBS), 3,5,5-trimethylhexanoyloxybenzene sulfonate (Iso-NOBS), dodecyloxybenzene sulfonate (LOBS), and any mixture thereof; caprolactam; glucose pentaacetate (PAG); quaternary ammonium nitrile; imide bleach activators such as N-nonanoyl-N-methylacetamide; and any mixture thereof.

[0089] In another embodiment, the powder detergent composition of the present invention may include a source of available oxygen. The source of available oxygen (AvOx) is a source of hydrogen peroxide such as percarbonates and / or perborates, for example, sodium percarbonate. The source of percarbonate may be at least partially coated, or even completely coated, with a coating component such as carbonates, sulfates, silicates, borosilicates, or any mixture thereof. Percarbonates can be prepared by a fluidized bed process or a crystallization process. Examples of perborates include sodium perborate monohydrate (PB1), sodium perborate tetrahydrate (PB4), and anhydrous sodium perborate, also known as effervescent sodium perborate. Other sources of AvOx include persulfates such as oxone. Other sources of AvOx include hydrogen peroxide.

[0090] In another embodiment, the powder detergent composition of the present invention may contain a preforming peracid. An example of a preforming peracid is N,N-phthaloylaminocaproic acid peroxide (PAP).

[0091] In another embodiment, the powder detergent composition of the present invention may contain a bleaching catalyst. Examples of bleaching catalysts include oxaziridinium-based bleaching catalysts, transition metal bleaching catalysts, and bleaching enzymes.

[0092] In another embodiment, the powder detergent composition of the present invention may contain an oxaziridinium-based bleaching catalyst. An example of an oxaziridinium-based bleaching catalyst is the following formula (17).

[0093] (In the formula, R ７１ R is selected from the group consisting of hydrogen atoms, branched alkyl groups containing 3 to 24 carbon atoms, and linear alkyl groups containing 1 to 24 carbon atoms; ７１ R may be a branched alkyl group containing 6 to 18 carbon atoms, or a linear alkyl group containing 5 to 18 carbon atoms. ７１ This can be selected from the group consisting of 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, isononyl, isodecyl, isotridecyl, and isopentadecyl. ; R ７２ These are selected from the group consisting of a hydrogen atom, a branched alkyl group containing 3 to 12 carbon atoms, and a linear alkyl group containing 1 to 12 carbon atoms, either identical or different; optionally, R ７２ r is selected from the group consisting of a hydrogen atom, a methyl group, a branched alkyl group containing 3 to 12 carbon atoms, and a linear alkyl group containing 1 to 12 carbon atoms, and r is an integer from 0 to 1.) The oxaziridinium bleaching accelerator can be manufactured in accordance with U.S. Patent Application Publication No. 2006 / 0089284.

[0094] In another embodiment, the powder detergent composition of the present invention may contain a transition metal bleaching catalyst. The powder detergent composition of the present invention may typically contain cations of copper, iron, titanium, ruthenium, tungsten, molybdenum, and / or manganese, and may contain a transition metal bleaching catalyst. Examples of transition metal bleaching catalysts include manganese-based transition metal bleaching catalysts.

[0095] In another embodiment, the powder detergent composition of the present invention may contain a reducing bleaching agent. The powder detergent composition of the present invention may contain a reducing bleaching agent. However, the laundry detergent composition does not have to contain a reducing bleaching agent substantially. Substantially omitting means "intentionally not adding." Suitable reducing bleaching agents include sodium sulfite and / or thiourea dioxide (TDO).

[0096] In another embodiment, the powder detergent composition of the present invention may contain co-bleaching agent particles. The powder detergent composition of the present invention may contain co-bleaching agent particles. Typically, the co-bleaching agent particles may include a bleaching activator and a source of peroxide. It is preferable that a large amount of bleaching activator relative to the source of hydrogen peroxide is present in the co-bleaching agent particles. The weight ratio of the bleaching activator present in the co-bleaching agent particles to the source of hydrogen peroxide is not particularly limited as long as it is 0.3:1 or higher. Preferably it is 0.6:1 or higher, more preferably 0.7:1 or higher, even more preferably 0.8:1 or higher, even more preferably 0.9:1 or higher, particularly preferably 1.0:1.0 or higher, and particularly preferably 1.2:1 or higher.

[0097] The aforementioned co-bleaching particles may include (i) a bleaching activator such as TAED, and (ii) a source of hydrogen peroxide such as sodium percarbonate. The bleaching activator may be supplied with hydrogen peroxide in part or in whole.

[0098] The aforementioned co-bleaching particles may contain a binder. Examples of binders include carboxylate polymers such as polyacrylate polymers, and / or surfactants such as linear nonionic cleaning surfactants having 11 to 13 carbon atoms and / or anionic cleaning surfactants such as alkylbenzene sulfonates.

[0099] In another embodiment, the powder detergent composition of the present invention may contain a bleach stabilizer (heavy metal ion chelating agent). Examples of bleach stabilizers include ethylenediaminetetraacetic acid (EDTA) and polyphosphonates. Examples include Dequest® and EDTMP.

[0100] In another embodiment, the powder detergent composition of the present invention may contain a photobleaching agent. Specific examples of the photobleaching agent include sulfonated phthalocyanine zinc and / or aluminum.

[0101] In another embodiment, the powder detergent composition of the present invention may contain a whitening agent. The cleaning composition may preferably contain a whitening agent such as 4,4'-bis(2-sulfostyryl)biphenyl disodium (C.I. fluorescent whitening agent 351); C.I. fluorescent whitening agent 260; or an analog thereof in which the anilino or morpholino group is substituted with another group. A preferred C.I. fluorescent whitening agent 260 may have the following structural formula (18):

[0102] The C.I. fluorescent whitening agent 260 is mainly in α-crystalline form or mainly in β-crystalline form and has a weight-average primary particle size of 3 to 30 micrometers.

[0103] In another embodiment, the powder detergent composition of the present invention may contain a bleach-stable fluorescent whitening agent such as bis(sulfobenzofuranyl)biphenyl, which is commercially available from Ciba Specialty Chemicals as Tinopal® PLC.

[0104] In another embodiment, the powder detergent composition of the present invention may contain a fabric coloring agent (sometimes also referred to as a shading agent, bluing agent, or whitening agent). Generally, the coloring agent imparts a blue or violet hue to the fabric. The coloring agent can be used alone or in combination to create specific hues. Alternatively, it can color different types of fabrics. For example, it can be provided by mixing red and green-blue dyes to produce a blue or purple hue. The colorants may include, but are not limited to, acridines, anthraquinones (including polycyclic quinones), azines, premetallated azos (e.g., monoazo, diazo, trisazo, tetrakisazo, polyazo), benzodifurans and benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethane, formazan, hemicyanines, indigoids, methane, naphthalimide, naphthoquinone, nitros and nitroso, oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof, and may be selected from any known chemical classification of dyes.

[0105] Fabric colorants include dyes, dye-clay conjugates, and organic and inorganic pigments. Dyes include small molecule dyes and high molecular weight dyes. Small molecule dyes are classified into, for example, blue, violet, red, green, or black, and can be used alone or in combination to create desired shades. Small molecule dyes can be selected from the group consisting of dyes classified by the Color Index (C.I.) of direct dyes, basic dyes, reactive dyes, or hydrolyzed reactive dyes, hydrolyzed solvent dyes, or hydrolyzed disperse dyes. In another form, small molecule dyes include those classified by the Color Index (Society of Dyers and Colorists, Bradford, UK)) Numbers include Direct Violet Dyes 9, 35, 48, 51, 66, and 99, etc.; Direct Blue Dyes 1, 71, 80, and 279, etc.; Acid Red Dyes 17, 73, 52, 88, and 150, etc.; Acid Violet Dyes 15, 17, 24, 43, 49, and 50, etc.; Acid Blue Dyes 15, 17, 25, 29, 40, 45, 75, 80, 83, 90, and 113, etc.; Acid Black Examples of small molecule dyes include dispersion or solvent dyes such as Dye 1, Basic Violet Dyes 1, 3, 4, 10, and 35, Basic Blue Dyes 3, 16, 22, 47, 66, 75, and 159, those described in European Patent No. 1794275 or 1794276, or dyes disclosed in U.S. Patent No. 7,208,459, and mixtures thereof. In another form, small molecule dyes include small molecule dyes with C.I. numbers selected from the group consisting of Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113, or mixtures thereof.

[0106] Examples of polymer dyes include polymers containing covalently bonded (sometimes called conjugated) colorants, such as polymers copolymerized with a colorant to form the main chain of the polymer (dye-polymer conjugates), and polymer dyes selected from the group consisting of mixtures thereof. Examples of polymer dyes are described in International Publication No. 2011 / 98355, International Publication No. 2011 / 47987, U.S. Patent Application Publication No. 2012 / 090102, International Publication No. 2010 / 145887, International Publication No. 2006 / 055787, and International Publication No. 2010 / 142503.

[0107] As another form, specific examples of polymer dyes include direct fabric colorants marketed under the name Liquitint® (Milliken (Spartanburg, South Carolina, USA)), and polymer dyes selected from the group consisting of a dye-polymer conjugate formed from a polymer selected from the group consisting of a polymer containing at least one reactive dye and a polymer containing a portion selected from the group consisting of a hydroxyl portion, a primary amine portion, a secondary amine portion, a thiol portion, and mixtures thereof. Furthermore, as yet another form, specific examples of polymer dyes include Liquitint® Violet CT, and C.I. sold by Megazyme (Wicklow, Ireland) under the trade name AZO-CM-Cellulose and trade code S-ACMC. Examples include polymer dyes selected from the group consisting of carboxymethylcellulose (CMC), alkoxylated triphenyl-methane polymer colorants, alkoxylated thiophene polymer colorants, and mixtures thereof, which are covalently bonded to reactive blue, reactive violet, or reactive red dyes such as CMC conjugated with reactive blue 19.

[0108] Specific examples of hue dyes include the whitening agents found in International Publication Nos. 2008 / 87497, 2011 / 011799, and 2012 / 054835. Preferred hue agents for use in the present invention may be preferred dyes disclosed in these references, including those selected from Examples 1 to 42 in Table 5 of International Publication No. 2011 / 011799. Other preferred dyes are disclosed in U.S. Patent No. 8,138,222. Other preferred dyes are disclosed in International Publication No. 2009 / 069077.

[0109] Examples of dye clay conjugates include dye clay conjugates selected from the group consisting of at least one cationic / basic dye and smectite clay, and mixtures thereof. In another embodiment, examples of dye clay conjugates include dye clay conjugates selected from the group consisting of one cationic / basic dye selected from the group consisting of the following: C.I. Basic Yellow 1-108, C.I. Basic Orange 1-69, C.I. Basic Red 1-118, C.I. Basic Violet 1-51, C.I. Basic Blue 1-164, C.I. Basic Green 1-14, C.I. Basic Brown 1-23, C.I. Basic Black 1-11, and clays selected from the group consisting of montmorillonite clay, hectorite clay, saponite clay, and combinations thereof. Further preferred forms of dye clay conjugates include Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate, Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C. Examples of dye clay conjugates selected from the group consisting of I. Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic Blue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555 conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite Basic Red R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate, and mixtures thereof.

[0110] Examples of pigments include flavantron, indantron, chlorinated indantron having 1 to 4 chlorine atoms, pyrantron, dichloropyrantron, monobromodichloropyrantron, dibromodichloropyrantron, tetrabromopyrantron, perylene-3,4,9,10-tetracarboxylic acid diimide (the imide group may be unsubstituted or substituted with an alkyl or phenyl group having 1 to 3 carbon atoms or a heterocyclic radical, and this phenyl and heterocyclic radical may further have substituents that do not impart water solubility), anthrapyrimidine carboxylic acid amide, biolantron, isobiolantron, dioxazine pigment, copper phthalocyanine (which may have 2 or fewer chlorine atoms per molecule), polychloro-copper phthalocyanine, or polybromochloro-copper phthalocyanine (which has 14 or fewer bromine atoms per molecule), and pigments selected from the group consisting of these.

[0111] As another form, specific examples of pigments include pigments selected from the group consisting of ultramarine blue (C.I. Pigment Blue 29), ultramarine violet (C.I. Pigment Violet 15), and mixtures thereof.

[0112] The aforementioned fabric colorants can be used in combination (any mixture of fabric colorants can be used).

[0113] In another form, the powder detergent composition of the present invention may contain enzymes. Examples of enzymes include proteases, amylases, cellulases, lipases, xyloglucanases, pectin lyases, mannanases, bleaching enzymes, cutinases, and mixtures thereof. For enzymes, the accession numbers and IDs shown in parentheses refer to the entry numbers in the databases Genbank, EMBL, and / or Swiss-Prot. For any mutant, a standard single-letter notation of the amino acid is used to indicate deletions. Accession numbers preceded by DSM refer to microorganisms deposited in Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH (Mascheroder Weg 1b, 38124 Brunswick) (DSMZ).

[0114] <Protease> The powder detergent composition of the present invention may contain a protease. Examples of proteases include metalloproteases and / or serine proteases, including neutral or alkaline microbial serine proteases such as subtilisin (EC 3.4.21.62). Preferred proteases include those derived from animals, plants, or microorganisms, and one preferred form is that of microbial origin. Chemically or genetically modified mutants of the above-mentioned preferred proteases are also included. In one embodiment, the preferred protease may be an alkaline microbial protease and / or a serine protease such as a trypsin-type protease. Examples of neutral or alkaline proteases are as follows. (a) Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO), Bacillus subtilis, Bacillus amylolicefaciens (P00782, SUBT_BACAM), Bacillus pumilus (P07518), and Bacillus gibson (b) Subtilisins (EC 3.4.21.62) including those derived from the genus Bacillus, such as gibsonii (DSM 14391). (b) Trypsin-type or chymotrypsin-type proteases, such as Fusarium proteases and chymotrypsin proteases derived from Cellumonas (A2RQE2), such as trypsin (e.g., of porcine or bovine origin). (c) Metalloproteases, including those derived from Bacillus amyloricephaciens (P06832, NPRE_BACAM).

[0115] Specific examples of preferred proteases include those derived from Bacillus gibson or Bacillus lentus, such as subtilisin 309 (P29600) and / or DSM 5483 (P29599).

[0116] Preferred commercially available protease enzymes include those sold by Novozymes A / S (Denmark) under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase®, and Esperase®; Genencor Products sold by International under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase®, and Purafect OXP®; products sold by Solvay Enzymes under the trade names Opticlean® and Optimase®; products available from Henkel / Kemira, namely BLAP (P29599 having the following mutations S99D+S101R+S103A+V104I+G159S), and BLAP Examples include R (BLAP having S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP having S3T+V4I+V205I), and BLAP F49 (BLAP having S3T+V4I+A194P+V199M+V205I+L217D), as well as their variants (all manufactured by Henkel / Kemira); and Kao's KAP (Bacillus alkarophilus subtilisin having mutations A230V+S256G+S259N).

[0117] Alternatively, proteases may be catalytically active proteins that, when present as fabric stains in a hydrolysis reaction, break down or alter the types of proteins in the strain. The enzymes may originate from plants, animals, bacteria, or yeast, etc. Proteases or proteases of various qualities and origins, active in a wide range of pH levels from 4 to 12, are available. Proteases with high and low isoelectric points are preferred.

[0118] <Amylase> Amylase is an α-amylase that includes those of bacterial or fungal origin. It includes chemically or genetically modified mutants (mutants). Alkaline α-amylases include Bacillus licheniformis, Bacillus amyloricephasiens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus species, such as Bacillus species NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM 9375, DSM 12368, DSM no. The amylases are derived from strains of the genus Bacillus, such as 12649, KSM AP1378, KSM K36, or KSM K38. Preferred amylases include the following: (a) α-amylase derived from Bacillus licheniformis (P06278, AMY_BACLI), and its variants, particularly variants having substitutions at one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444. (b) AA560 amylase (CBU30457, HD066534), and its variants, in particular at positions 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 2 A mutant having one or more substitutions from 98, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, and optionally including deletions of D183* and G184*.(c) DSM 12649 having (a) mutations at one or more of the positions 9, 26, 149, 182, 186, 202, 257, 295, 299, 323, 339 and 345, and (b) optionally one or more, preferably all of the positions 118, 183, 184, 195, 320 and 458, with substitutions and / or deletions (preferably including R118K, D183*, G184*, N195F, R320K and / or R458K, if present). (d) mutants exhibiting at least 90% homology to the wild-type enzyme derived from Bacillus SP722 (CBU30453, HD066526), ​​particularly mutants having deletions at positions 183 and 184.

[0119] Preferred commercially available α-amylases include Duramyl®, Liquezyme®, Termamy®, Termamyl Ultra®, Natalase®, Supramyl®, Steinzyme®, Steinzyme Plus®, Fungamyl®, and BAN® (Novozymes A / S), Bioamylase® and its variants (Biocon India Ltd.), Kemzym® AT 9000 (Biozym Ges.m.b.H, Australia), Rapidase®, Puraster®, and Optisize HT. Examples include Plus®, Enzysize®, Powerase®, and Puraster Oxam®, Maxamyl® (Genencor International Inc.), and KAM® (Kao Corporation, Japan). More preferred amylases are NATALASE®, Stainzyme®, and Stainzyme Plus®.

[0120] <Cellulase> The powder detergent composition of the present invention may contain cellulase. Examples of cellulase include bacterial or fungal cellulases. Chemically modified or genetically engineered mutants are included. Preferred cellulases include those derived from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, and Acremonium, such as fungal cellulases produced from Humicola insolens, Myceliophysora thermophylla, and Fusarium oxysporum.

[0121] Examples of commercially available cellulases include Celluzyme® and Carezyme® (Novozymes A / S), Clazinase® and Puradax HA® (Genencor International Inc.), and KAC-500(B)® (Kao Corporation).

[0122] Other cellulases include endoglucanases derived from microorganisms exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4), such as endogenous bacterial polypeptides of Bacillus species AA349 and mixtures thereof. Preferred endoglucanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S (Bagsvaer, Denmark)).

[0123] Furthermore, preferred cellulases such as Whitezyme® include those with xyloglucanase activity.

[0124] <Lipase> The powder detergent composition of the present invention may contain lipase. Preferred lipases include those derived from bacteria or fungi. This includes chemically modified or genetically engineered mutants. Examples of useful lipases include, for example, lipases derived from the genus Humicola (also known as the genus Thermomyces), such as H. lanuginosa (T. lanuginosa) or H. insolens; for example, P. alcaligenes or P. pseudoalcaligenes, P. epasia, P. stutzeri, P. Lipases from the genus Pseudomonas, such as P. fluorescens, Pseudomonas SD 705 strain, and P. wisconsinensis; for example, lipases from the genus Bacillus, such as B. subtilis, B. stearothermophilus, or B. pumilus.

[0125] The lipase may be a "first-cycle lipase" and, if necessary, a variant of the wild-type lipase derived from Thermomyces lanuginosa containing the T231R and N233R mutations. The wild-type sequence is 269 amino acids (amino acids 23-291) (derived from Thermomyces lanuginosa (Humicola lanuginosa)) with Swissprot accession number Swiss-Prot O59952. Preferred lipases include those sold by Novozymes (Bagsvaerd, Denmark) under the trade names Lipex®, Lipolex®, and Lipoclean®.

[0126] The powder detergent composition of the present invention may contain a variant of Thermomyces lanuginosa (O59952) lipase having more than 90% homology to wild-type amino acids and optionally including substitutions of T231R and / or N233R in T231 and / or N233.

[0127] <Xyloglucanase> The xyloglucanase enzyme can have enzymatic activity toward both xyloglucan substrates and amorphous cellulose substrates. The enzyme may be a glycoside hydrolase selected from the glycosyl hydrolase (GH) family 5, 12, 44, 45, or 74. A glycosyl hydrolase selected from the GH family 44 is particularly preferred. Preferred glycoside hydrolases selected from the GH family 44 include the XYG1006 glycoside hydrolase derived from Paenibacillus polyxyma (ATCC 832) and its variants.

[0128] Particularly preferred are glycosyl hydrolases selected from the GH family 45 having a molecular weight of 17 kDa to 30 kDa, such as endoglucanases sold under the trade names Biotouch® NCD, DCC, and DCL (AB Enzymes, Darmstadt, Germany).

[0129] <Pectinate Lyase> Pectinate lyase can be either the wild type or mutant (CAF05441, AAU25568) of Bacillus-derived pectinate lyase sold under the trade names Pectawash®, Pectaway®, and X-Pect® (Novozymes A / S (Bagsvaerd, Denmark)).

[0130] <Mannanase> Mannanase is sold under the trade names Mannaway® (Novozymes A / S (Bagsvaer, Denmark)) and Purabrite® (Genencor International Inc. (Palo Alto, California)).

[0131] <Bleaching Enzymes> Bleaching enzymes are oxidoreductases. Specifically, these include oxidases such as glucose oxidase, choline oxidase, or carbohydrate oxidase; oxygenases; catalases; peroxidases such as haloperoxidase, chloroperoxidase, bromoperoxidase, lignin peroxidase, glucose peroxidase, or manganese peroxidase; dioxygenases; or laccases (phenol oxidase, polyphenol oxidase). Preferred commercial products include Guardzyme® and Denilite® from Novozymes. It is preferable to incorporate additional organic compounds, particularly aromatic compounds, together with the bleaching enzyme. These compounds interact with the bleaching enzyme to enhance the activity of the oxidoreductase (enhancement agents) or to promote electron flow between the oxidoenzyme and the dirt, usually across significantly different redox potentials (mediators).

[0132] Other preferred bleaching enzymes include perhydrolases that catalyze the formation of peracids from ester substrates and peroxygen sources. Preferred perhydrolases include mutants of the perhydrolase of Mycobacterium smegmatis, the so-called CE-7 perhydrolase mutant, and a mutant of the wild-type subtilisin Carlsberg that possesses perhydrolase activity.

[0133] <Cutinase> Optional cutinases may include those defined by E.C. class 3.1.1.73 that exhibit at least 90%, 95%, or most optionally at least 98% homology to the wild type derived from one of Fusarium solani, Pseudomonas mendocina, or Humicola insolens.

[0134] In another embodiment, the powder detergent composition of the present invention may contain a fabric softener. Preferred fabric softeners include clay, silicone, and / or quaternary ammonium compounds. Preferred clays include montmorillonite clay, hectorite clay, and / or laponite clay. A more preferred clay is montmorillonite clay. Preferred silicones include aminosilicone and / or polydimethylsiloxane (PDMS). Preferred softeners include clay and silicone-containing particles such as montmorillonite clay and PDMS-containing particles.

[0135] In another embodiment, the powder detergent composition of the present invention may contain a flocculant. Examples of flocculants include polyethylene oxide having an average molecular weight of 300,000 to 900,000.

[0136] In another embodiment, the powder detergent composition of the present invention may contain a foam inhibitor. Specific examples of foam inhibitors include silicones and / or fatty acids such as stearic acid.

[0137] In another embodiment, the powder detergent composition of the present invention may contain a fragrance. Specific examples of fragrances include fragrance microcapsules, polymer-assisted fragrance delivery systems including Schiff base fragrance / polymer complexes, starch-encapsulated fragrance accords, fragrance-filled zeolites, blooming fragrance accords, and any combination thereof. Preferred fragrance microcapsules are melamine-formaldehyde based and typically contain a fragrance encapsulated by a shell containing melamine-formaldehyde. Such fragrance microcapsules very preferably contain a cationic material and / or a cationic precursor material, such as polyvinylformamide (PVF) and / or cationic-modified hydroxyethylcellulose (catHEC), within the shell.

[0138] In another embodiment, the powder detergent composition of the present invention may contain other aesthetic agents. Specific examples of aesthetic agent particles include soap rings, lamellar aesthetic agent particles, gelatin beads, speckles of carbonates and / or sulfates, colored clay particles, and any combination thereof.

[0139] <Builders> Examples of builders include zeolite, citrate, and any combination thereof.

[0140] <Zeolite Builder> The powder detergent composition of the present invention may or may not contain a zeolite builder. The amount of zeolite builder contained in the powder detergent composition of the present invention is not particularly limited as long as it is 0 to 30% by mass. Preferably it is 0 to 25% by mass, and more preferably 0 to 15% by mass. Specific examples of zeolite builders include zeolite A, zeolite P, zeolite MAP, zeolite X, and zeolite Y.

[0141] Other inorganic builders that may be present in addition to or instead of these include sodium carbonate and / or sodium bicarbonate.

[0142] Examples of organic builders include polycarboxylate polymers, such as polyacrylate and acrylic acid / maleic acid copolymers; polyaspartate; monomer polycarboxylates, such as citrate, gluconate, oxydisuccinate, glycerol mono-, di-, and tri-succinate, carboxymethyl oxysuccinate, carboxymethyl oxymalonate, dipicolinate, hydroxyethyl iminodiacetate, alkyl- and alkenylmalonate and succinate; and sulfonated fatty acid salts. However, the content of non-biodegradable organic builders in the powder detergent composition of the present invention is preferably as low as possible.

[0143] (Buffering agents and alkali sources) Examples of buffering agents and alkali sources include double salts such as carbonates and / or silicates and / or burcite.

[0144] <Carbonates> The carbonates are sodium carbonate and / or sodium bicarbonate. The powder detergent composition of the present invention may contain bicarbonates. The powder detergent composition of the present invention may contain carbonates. The amount of carbonate contained in the powder detergent composition of the present invention is not particularly limited as long as it is between 0 and 30% by mass. Preferably it is between 0 and 25% by mass, and more preferably it is between 5 and 20% by mass.

[0145] The weight-average particle size of carbonates is 100 to 500 micrometers, or 10 to 25 micrometers.

[0146] (Silicate) The powder detergent composition of the present invention may contain 0% to 20% by mass of silicate. When the powder detergent composition of the present invention contains silicate, it is preferable that it contains 15% by mass or less. More preferably, it is 10% by mass or less, even more preferably 5% by mass or less, even more preferably 4% by mass or less, and particularly preferably contains only 2% by mass or less of silicate. It may contain more than 0% by mass, or more than 0.5% by mass, or even more than 1% by mass of silicate. The silicate may be crystalline or amorphous. Preferred crystalline silicates include crystalline layered silicates such as SKS-6. Other preferred silicates include 1,6R silicate and / or 2,0R silicate. The silicate is preferably sodium silicate. Another preferred silicate is sodium metasilicate.

[0147] <Fillers> The powder detergent composition of the present invention may contain 0% to 70% by mass of fillers. Examples of fillers include sulfates and / or biofiller materials.

[0148] A specific example of a sulfate is sodium sulfate. The weight-average particle size of sulfates is 100 to 500 micrometers, or 10 to 45 micrometers.

[0149] <Biofiller Materials> Examples of biofiller materials include alkaline-treated and / or bleached agricultural waste.

[0150] <Calcium carbonate crystal growth inhibitor> The powder detergent composition of the present invention may contain a calcium carbonate crystal growth inhibitor selected from the group consisting of 1-hydroxyethanediphosphonic acid (HEDP) and its salts, N,N-dicarboxymethyl-2-aminopentane-1,5-diic acid and its salts, 2-phosphonobutane-1,2,4-tricarboxylic acid and its salts, and any combination thereof.

[0151] <Anti-re-adhesion agent> The powder detergent composition of the present invention may contain cellulose ester and ether, and / or sodium carboxymethylcellulose.

[0152] Other components that may be included in the powder detergent composition of the present invention include solvents, hydrotropes such as sodium, or calcium cumene sulfonate, potassium naphthalene sulfonate, etc., fluorescent agents, foaming accelerators or foaming controllers (antifoamers) as needed, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulfate, sodium acetate, TEA-25 (polyethylene glycol ether of catyl alcohol), calcium chloride, other inorganic salts, flow aids such as silica and amorphous aluminosilicate, fabric conditioning compounds, further clay and stain removers / anti-re-adhesion agents, other fragrances or pro-fragrances, and one or more combinations of these cleaning aids.

[0153] [Method of Use of Powdered Detergent Composition] The powdered detergent composition of the present invention is used to wash and / or treat surfaces or fabrics. The "surface" may include surfaces such as dishes, glassware, and other cooking utensils, hard surfaces, hair, or skin. Such a method involves bringing an embodiment of the laundry detergent or cleaning composition, either in an undiluted form or diluted with a cleaning solution, into contact with at least a portion of the surface or fabric, and then, depending on the circumstances, rinsing the surface or fabric. The surface or fabric may undergo a washing step before the rinsing step described above. For the purposes of the present invention, "washing" includes, but is not limited to, rubbing, wiping, and mechanical agitation.

[0154] The pH of the powder detergent composition of the present invention, when diluted with water as an aqueous solution, can be selected to be most complementary to the target surface being cleaned, over a wide range of pH from approximately 5 to approximately 11. For personal care such as skin and hair washing, the pH of such composition is preferably approximately 5 to approximately 8, and for laundry detergent compositions, it is preferably approximately 8 to approximately 10. The powder detergent composition of the present invention is preferably used at a concentration of approximately 200 ppm to approximately 10,000 ppm in the solution. The water temperature is preferably in the range of approximately 5°C to approximately 100°C.

[0155] The powder detergent composition of the present invention is suitable for use in laundry applications. Therefore, the present invention includes a method for washing fabrics. The method may include the step of bringing the powder detergent composition of the present invention, which contains the vinyl alcohol polymer, into contact with the fabric to be washed. The fabric is any common fabric that can be washed under standard consumer use conditions. The pH of the aqueous solution of the powder detergent composition of the present invention is preferably about 8 to about 10.5. When the aqueous solution of the powder detergent composition of the present invention is prepared, it may be used at a concentration of about 500 ppm to about 15,000 ppm in the solution, and optionally, weaker washing conditions may be used. The water temperature is in the range of about 5°C to about 90°C under normal use. The water-to-fabric ratio is about 1:1 to about 30:1 under normal use.

[0156] The method of washing fabrics can be carried out using a top-loading or front-loading automatic washing machine, or it can be used for hand washing. In these applications, the resulting wash solution and the concentration of the laundry detergent composition in the wash solution are those of the main wash cycle. When determining the amount of wash solution, the addition of water in any rinse cycle is not included.

[0157] The washing solution may consist of 40 liters or less of water, or 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or even 6 liters or less. The washing solution may consist of more than 0 to 15 liters, or 2 liters or more and 12 liters or less, or even 8 liters or less. Under dilute washing conditions, especially under hand washing conditions, the washing solution may consist of 150 liters or less of water, 100 liters or less of water, 60 liters or less of water, or 50 liters or less of water, and should be appropriately selected considering the number of rinses.

[0158] You should add 0.01 kg to 2 kg of fabric per liter of cleaning solution. For example, you may add 0.01 kg or more, or 0.05 kg or more, or 0.07 kg or more, or 0.10 kg or more, or 0.15 kg or more, or 0.20 kg or more, or 0.25 kg or more of fabric per liter of cleaning solution.

[0159] Optionally, a cleaning solution may be formed by contacting water with 50 g or less, or 45 g or less, or 40 g or less, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g or less, or even 15 g or less, or even 10 g or less of the powder detergent composition of the present invention.

[0160] [Composite Composition] The present invention also relates to a composite composition in which a powder detergent composition is enclosed in a film for detergent packaging, wherein the powder detergent composition comprises a vinyl alcohol polymer and a surfactant, and the vinyl alcohol polymer has a structural unit (a) represented by formula (1), and may further have a structural unit (b) represented by formula (2), and other structural units (c) other than structural unit (a) and structural unit (b), and the content ratio of each structural unit relative to the total amount of all structural units is structural unit (a) / structural unit (b) / other structural units (c) = 50-100 / 0-50 / 0-20 mol%.

[0161] The preferred form of the powder detergent composition in the aforementioned composite composition is as described with respect to the powder detergent composition.

[0162] The film for packaging the detergent in the composite composition is not particularly limited as long as it can encapsulate the powder detergent composition of the present invention, but it is preferably water-soluble. More preferably, it is a water-soluble polymer. Examples of water-soluble polymers include polyvinyl alcohol, polyalkylene glycol, starch or modified starch, cellulose or modified cellulose, polyacrylate, polymethacrylate, polyacrylamide, and polyvinylpyrrolidone. One or more of these can be used. Among these, polyvinyl alcohol is preferred because it is biodegradable.

[0163] The average degree of polymerization of the polymer constituting the film is not particularly limited, but is preferably 500 to 10000, more preferably 1000 to 8000, and even more preferably 1000 to 5000.

[0164] The thickness of the film is not particularly limited, but is preferably 20 μm to 150 μm. More preferably 35 μm to 125 μm, and even more preferably 50 μm to 100 μm.

[0165] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "mass%".

[0166] <Measurement of Average Degree of Polymerization> The average degree of polymerization of a polymer can be determined by the method described in JIS K6726. Alternatively, the average degree of polymerization of a polymer can be determined from GPC measurement of the polymer. Equipment: Waters Alliance HPLC Detector: RI Column: Shodex OHpak SB-806M HQ x 3 Columns Temperature: 40°C Flow rate: 1.0 mL / min Calibration curve: GL Sciences PEG standard Sample Eluent: 100 mM sodium phosphate aqueous solution / acetonitrile = 92 / 8

[0167] <Measurement of Saponification Degree> The degree of saponification of a polymer can be determined by the method described in JIS K6726. Furthermore, the degree of saponification of a polymer is 1 ＨIt can also be determined from NMR measurement. The degree of saponification of the polymer obtained in the following manufacturing example is 1 Ｈ The results were calculated from NMR measurements. Instrument: Varian VNMRS600 Nuclide: 1H Resonance frequency: 600 MHz Signal acquisition time: 3.4 seconds Delay time: 5 seconds Solvent: Dimethyl sulfoxide-d6 Number of integrations: 16 The results were calculated from the ratio of the peak area at 3.70–4.00 ppm (derived from vinyl alcohol-adjacent methine protons in the polymer main chain) to the peak area at 1.90–2.20 ppm (derived from acetate esters in the side chains) of the obtained spectrum.

[0168] <Biodegradability Test> The obtained vinyl alcohol polymer was subjected to a biodegradability test in accordance with OECD 301F.

[0169] Preparation of culture medium: Culture medium stocks A to D were prepared by the following method. Solution A: Potassium dihydrogen phosphate (KH ２ PO ４ ) 0.850g, dipotassium hydrogen phosphate (K ２ HPO ４ ) 2.175 g, disodium hydrogen phosphate dodecahydrate (Na ２ HPO ４ 12H ２ O) 6.7217 g, ammonium chloride (NH ４ 0.050 g of Cl was weighed into a 50 ml sample bottle, dissolved in an appropriate amount of water, transferred to a 100 ml volumetric flask, and then water was added to the mark. Solution B: Calcium chloride dihydrate (CaCl) ２ ・2H ２ O) Dissolve 3.640 g in an appropriate amount of water and transfer to a 100 ml volumetric flask, then add water to the mark. Solution C: Magnesium sulfate heptahydrate (MgSO4) ４ 7H ２ O) Dissolve 2.250 g in an appropriate amount of water and transfer to a 100 ml volumetric flask, then add water to the mark. Solution D: Iron(III) chloride hexahydrate (FeCl ３ 6H ２O) 0.025 g was dissolved in an appropriate amount of water and transferred to a 100 ml volumetric flask, then water was added to the mark. The culture medium stocks A to D were heated to 25°C, and 10 ml of A was added to a 1 L volumetric flask using a volumetric pipette and diluted with approximately 800 ml of water. Then, 1 ml each of B, C, and D were added using a volumetric pipette and diluted to the mark with water heated to 25°C. Multiple quantities of the culture medium were prepared according to the amount required for the test. The prepared culture medium was transferred to a 5 L beaker and mixed, and bubbling was performed for at least 1 hour while stirring.

[0170] Preparation of sludge solution: The sludge used for the biodegradability test was obtained from the Minami-Suita Sewage Treatment Plant. First, the concentration of the obtained sludge was measured using the following method. The obtained sludge was bubbling while being stirred, 5 ml was taken using a volumetric pipette, and filtered by suction using filter paper. Five filter papers from which sludge was collected were prepared, dried in a dryer at 105°C for 1 hour, and the sludge concentration was calculated from the average weight loss of the five papers. This sludge was diluted with the culture medium prepared above to prepare a 1000 ppm sludge solution. Preparation of polymer aqueous solution: The obtained polymer was diluted with pure water to obtain a 2% by mass polymer aqueous solution. As a standard substance, sodium benzoate was diluted with pure water to obtain a 2% by mass sodium benzoate aqueous solution.

[0171] BOD Test: A pressure sensor type BOD meter was used to measure BOD. 144.75 g of the culture medium prepared above was weighed into a glass bottle, and 0.75 g of 2% polymer aqueous solution was added. For the blank measurement, 0.75 g of pure water was added, and for the standard substance measurement, 0.75 g of 2% sodium benzoate aqueous solution was added. The pH of the solution was then measured, and the pH was adjusted with 0.1 M hydrochloric acid aqueous solution so that the pH value of the solution was 7.4 ± 0.2. Then, 4.5 ml of 1000 ppm sludge solution was added to make the test solution. After adding a stirring bar to the glass bottle, CO ２ 1.8g of CO2 absorbent (Yabashi Lime) was placed in the absorbent holder, and the BOD sensor was attached. The flask with the BOD sensor attached was stirred in a 24°C constant temperature bath, and the BOD value was calculated from the pressure sensor.

[0172] Calculation of decomposition rate: The theoretical oxygen demand (ppm) of the polymer was calculated, and the decomposition rate was calculated from the difference in BOD values ​​from the blank measurement. The decomposition rate after 28 days from the start of the test was defined as the biodegradation rate. [Formula] Decomposition rate (%) = (Biochemical oxygen consumption from polymer) / (Theoretical oxygen demand of polymer) × 100

[0173] <Evaluation of cleaning power for mud stains> [Cleaning process] (1) DigiEye System (manufactured by VeriVide) was used on mud-stained cloth KC-140 (Warwick Equest) and standard white cloth. ＊ a ＊ , b ＊The values ​​were measured. (2) 59.0 g of calcium chloride dihydrate and 27.2 g of magnesium chloride hexahydrate were mixed with 913.8 g of deionized water to prepare hard mother liquor (i). (3) A 1% polymer aqueous solution was prepared with deionized water so that the polymer solid content was 1%. (4) 2.84 g of alkylbenzene sulfonate sodium aqueous solution (Neoperex G65, manufactured by Kao), 0.21 g of polyoxyethylene lauryl ether (Emulgen 108, manufactured by Kao), 0.81 g of sodium oleate, 0.50 g of sodium silicate, 4.01 g of sodium carbonate, and 12.68 g of sodium sulfate were mixed with 479.14 g of deionized water to prepare powder detergent solution (ii). Of the powder detergent composition, the zeolite and polymer were added to each pot as described later in (7). For Comparative Example 1, since no polymer was used, the preparation was carried out using the same mass of deionized water as the polymer. (5) Add 4094.7 g of deionized water and 84.3 g of powder detergent solution (ii) to 21.0 g of hard mother liquor (i) and stir to prepare detergent solution (iii). (6) Using a Tergot-o-meter (manufactured by Daiei Kagaku Co., Ltd., product name: TM-4), 996.5 g of detergent solution (iii) was added to each of the four pots and the temperature was adjusted to 35°C. (7) After adding 0.04 g of zeolite to each pot, 3.5 g of deionized water or 1% polymer aqueous solution was added and stirred for 1 min. (8) After adding three mud-contaminated cloths and a bath ratio adjustment cloth (an amount so that the total amount of cloth is 50 g) to each pot, a washing process was carried out at 120 rpm for 20 min. (9) The contaminated cloths and bath ratio adjustment cloths were removed from each pot, the water was squeezed out by hand, and then dewatered for 1 min in a dewatering machine. [Rinsing Process] (1) Add 4179.0 g of deionized water to 21.0 g of hard hydride (i) and stir to prepare a rinsing solution. (2) Put 1000 g of the rinsing solution into a pot and adjust the temperature to 35°C. Then add the washed soiled cloths and bath ratio adjustment cloths and stir at 120 rpm for 3 min to rinse. (3) Remove the soiled cloths and bath ratio adjustment cloths from each pot, squeeze out the water by hand, and then dehydrate them in a dehydrator for 1 min. (4) Repeat steps (1) to (3). [Drying Process] The soiled cloths that had undergone the washing and rinsing processes were air-dried overnight.[Calculation of cleaning rate] For the mud-stained cloth and standard white cloth after cleaning, the cleaning rate was calculated using the DigiEye System, L. ＊ a ＊ , b ＊ The values ​​were measured. The Stain Removal Index (SRI) was calculated from the following formula.

[0174]

[0175] <Example 1> 53.36 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries) was charged into a glass reaction vessel equipped with a thermometer, nitrogen inlet tube, reflux condenser, and stirrer. After purging the reaction vessel with nitrogen, the temperature was raised to 60°C while stirring. Under stirring, 75.00 g of vinyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries) and two types of initiator solutions (a mixed solution of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, V-65) 2.16 g and 19.47 g of ethanol) were added dropwise to the 60°C reaction vessel, each from separate dropping nozzles. Regarding the start time of dropwise addition, vinyl acetate and the initiator solution were added dropwise simultaneously, with vinyl acetate added dropwise over 180 minutes and the initiator solution over 240 minutes. After all dropwise addition was complete, the reaction solution was heated and aged at 60°C for a further 8 hours to obtain a polyvinyl acetate solution. Next, 120.00 g of the obtained polyvinyl acetate solution was placed in a glass reaction vessel equipped with a thermometer and a stirrer, and 180 g of methanol was added. The mixture was heated to 50°C while stirring to obtain a homogeneous solution. Subsequently, 13.94 g of a 4% sodium hydroxide-methanol suspension was added, and the mixture was stirred while maintaining the temperature at 50°C. After 120 minutes, the precipitation of the polymer was confirmed, and the reaction product was filtered using a Kiriyama funnel to collect the precipitate. Subsequently, the precipitate was dried under reduced pressure at 60°C for 3 hours to obtain polymer (1). The degree of polymerization was 192 and the degree of saponification was 97. The biodegradability was 73%.

[0176] <Example 2> Polyvinyl alcohol with an average degree of polymerization of 262 and a degree of saponification of 80 (SIGMA-ALDRICH polyvinyl alcohol Mw 9000-10000 80% hydrolyzed) was used as polymer (2).

[0177] In addition to the surfactant, the above-described cleaning power evaluation was performed using polymer (1), polymer (2) obtained in Production Example 1, and ion-exchanged water. The composition ratio (%) of each component constituting the powder detergent composition of the present invention is shown in Table 1, and the cleaning power evaluation results are shown in Table 2. When the powder detergent composition of the present invention containing the vinyl alcohol-based polymers of Example 1 and Example 2 was used, the mud cleaning power was improved compared to when polymer (1) and polymer (2) were not added.

[0178]

[0179]

Claims

1. A powder detergent composition comprising a vinyl alcohol polymer and a surfactant, wherein the vinyl alcohol polymer has the following formula (1); It has a structural unit (a) represented by the following formula (2); A powder detergent composition having a structural unit (b) represented by, and other structural units (c) other than the structural unit (a) and the structural unit (b), wherein the content ratio of each structural unit relative to the total amount of all structural units is structural unit (a) / structural unit (b) / other structural units (c) = 50-100 / 0-50 / 0-20 mol%, the average degree of polymerization is 50-800, the content ratio of the surfactant is 10-80% by mass relative to 100% by mass of the powder detergent composition, the content ratio of powder soap relative to the total amount of the surfactant is 1-100% by mass, the content ratio of carboxyl group-containing polymer is 0% by mass or more and 1% by mass or less relative to 100% by mass of the powder detergent composition, and the content ratio of phosphorus compounds is 0% by mass or more and 1% by mass or less relative to 100% by mass of the powder detergent composition.

2. The powder detergent composition according to claim 1, wherein the content ratio of the surfactant is 10 to 40% by mass with respect to 100% by mass of the powder detergent composition.

3. The powder detergent composition according to claim 1 or 2, wherein the surfactant includes an anionic surfactant.

4. The powder detergent composition according to any one of claims 1 to 3, wherein the surfactant comprises an anionic surfactant and a nonionic surfactant.

5. The powder detergent composition according to any one of claims 1 to 4, wherein the surfactant comprises an anionic surfactant and a nonionic surfactant, and the ratio of the anionic surfactant to 100% by mass of the total of the anionic surfactant and the nonionic surfactant is 30% by mass or more.

6. A powder detergent composition according to any one of claims 1 to 5, comprising an enzyme.

7. A powder detergent composition in which the organic components contained in the powder detergent composition according to any one of claims 1 to 6 have a biodegradation rate of 40% or more after 28 days, as measured by a biodegradation test conducted in accordance with OECD 301F.

Images