Detergent article

Abstract

To improve detergency and the flowability of a detergent composition, while minimizing the occurrence of undissolved remnants of the detergent composition.SOLUTION: A detergent article comprises: a detergent composition containing components (a), (b), (c), and (d) described below, the component (d) having a coating layer composed of the component (b), and the coating layer composed of the component (b) having a thickness of 0.1 μm or more and 50 μm or less; and a water-soluble film for packaging the detergent composition. Components (a): a nonionic surfactant; (b): an anionic surfactant; (c): an oil absorption carrier; and (d): an alkaline agent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cleaning agent article comprising a cleaning agent composition packaged in a water-soluble film. [Background technology]

[0002] In recent years, with an increasing preference for convenience among consumers, there has been a demand for cleaner compositions that are easier to use. From the viewpoint of improving the usability of the cleaner composition, for example, a cleaner article in which the cleaner composition is packaged in a water-soluble film has been disclosed.

[0003] Patent Document 1 discloses a packaged detergent in which a cleaning composition is packaged in a predetermined polyvinyl alcohol film. Patent Document 2 discloses a packaged detergent in which a cleaning composition containing (a) a nonionic surfactant, (b) a porous oil-absorbing carrier, and (c) a crystalline aluminosilicate under specified conditions is packaged in a water-soluble film having a thickness of 10 to 150 μm. Patent Document 3 discloses a detergent composition package comprising a powder detergent composition packaged in a water-soluble film, in which the detergent composition contains an alkaline component (A) in 70 to 99.9 mass % of the total detergent composition, a nonionic surfactant (B) in 0.1 to 10 mass % of the total detergent composition, and 80 mass % or more of the alkaline component (A) is an alkali metal silicate. Patent Document 4 discloses a granular detergent composition containing (a) potassium α-olefin sulfonate, (b) potassium alkylbenzene sulfonate, (c) a nonionic surfactant having an average alkylene oxide addition mole number of 10 to 30, and (d) an aluminosilicate under specified conditions, the granular detergent composition having an average particle size of 200 to 550 μm and a ratio of particles having a particle size of less than 177 μm of 10% by weight or less. It also discloses that this granular detergent composition is combined with a packaging material to obtain a packaged detergent. Patent Document 5 discloses detergent particles containing (A) base granules 1 containing a water-insoluble inorganic salt, a nonionic surfactant, an anionic surfactant, and an alkaline builder. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-116598 [Patent Document 2] Japanese Patent Application Publication No. 5-214398 [Patent Document 3] JP 2019-52252 A [Patent Document 4] JP 2001-262194 A [Patent Document 5] WO 99 / 29830 Summary of the Invention [Problem to be solved by the invention]

[0005] Although a solid detergent composition is preferable from the viewpoint of efficient cleaning, there is a risk of impairing the finish due to the generation of insoluble residues. Also, from the viewpoint of workability when packaging the detergent composition with a water-soluble film, there is a demand for improving the flowability of the detergent composition. The present invention provides a detergent article comprising a detergent composition packaged in a water-soluble film, which has excellent cleaning properties and flowability of the detergent composition and is suppressed from leaving undissolved residue of the detergent composition. [Means for solving the problem]

[0006] The present invention relates to a detergent article comprising: a detergent composition containing the following components (a), (b), (c), and (d), wherein component (d) has a coating layer of component (b), and the coating layer of component (b) has a thickness of 0.1 μm or more and 50 μm or less; and a water-soluble film for packaging the detergent composition: (a) Component: Nonionic surfactant (b) Component: Anionic surfactant (c) Component: Oil-absorbing carrier (d) Ingredient: Alkaline agent Effect of the Invention

[0007] According to the present invention, there is provided a detergent article in which a detergent composition is packaged in a water-soluble film, which has excellent cleaning properties and flowability of the detergent composition and in which residual undissolved detergent composition is suppressed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The mechanism by which the detergent article of the present invention has excellent cleaning properties and excellent fluidity of the detergent composition and is suppressed from leaving undissolved residue of the detergent composition is not clear, but is presumed to be as follows. It is presumed that the cleaning properties of the detergent article of the present invention are improved by the combined use of the nonionic surfactant as component (a), the anionic surfactant as component (b), and the alkaline agent as component (d). For example, when the (d) component is dissolved in cold water, the dissolution of the (d) component is promoted by the heat generated by the (d) component, but the cooling by the cold water tends to leave lumps remaining undissolved. In the cleaning article of the present invention, the (d) component has a coating layer of the (b) component, so that the heat generated when the (d) component is dissolved in water is suppressed, and the dissolution of the primary particles of the (d) component is delayed. It is presumed that this suppresses the generation of lumps due to the coalescence of particles of the cleaning composition containing the (d) component, and the undissolved portion of the composition. It is also presumed that the (d) component has a coating layer of the (b) component, so that even if lumps are generated due to the coalescence of particles of the composition, the lumps are easily dispersed. Furthermore, it is believed that the combination of components (a) to (d) ensures the flowability of the powder detergent composition. However, the action mechanism of the cleaning article of the present invention is not limited to the above.

[0009] [Cleaning products] The cleaning article of the present invention comprises a cleaning composition containing the following components (a), (b), (c), and (d), and a water-soluble film for packaging the cleaning composition: (a) Component: Nonionic surfactant (b) Component: Anionic surfactant (c) Component: Oil-absorbing carrier (d) Ingredient: Alkaline agent

[0010] <Component (a)> Component (a) is a nonionic surfactant. From the viewpoint of detergency, component (a) can be one or more selected from polyoxyalkylene alkyl or alkenyl ethers, alkyl (poly)glycosides (glycoside-type nonionic surfactants), sorbitan-based nonionic surfactants, compounds in which alkylene oxide is added between the ester bonds of long-chain fatty acid alkyl esters, fatty acid monoglycerides, and sucrose fatty acid esters.

[0011] The nonionic surfactant of the component (a) is preferably a nonionic surfactant (a1) that contains alkyleneoxy groups and has an average added mole number of alkyleneoxy groups of 1 or more and 30 or less (hereinafter referred to as component (a1)). The alkyleneoxy group of the component (a1) is preferably one or more groups selected from alkyleneoxy groups having from 2 to 4 carbon atoms. The alkyleneoxy group having from 2 to 4 carbon atoms is preferably one or more groups selected from an ethyleneoxy group and a propyleneoxy group. The average number of moles of alkyleneoxy groups added in the component (a1) is 1 or more, preferably 6 or more, more preferably 10 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, from the viewpoint of cleaning properties.

[0012] The component (a1) is preferably a nonionic surfactant represented by the following general formula (a1). R 1a (CO) m O-(A 1a O) n -R 2a (a1) [In the formula, R 1ais an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R 2a is a hydrogen atom or a methyl group. CO is a carbonyl group, and m is the number 0 or 1. A 1a The O group is an alkyleneoxy group containing an ethyleneoxy group and having 2 to 4 carbon atoms. n is the average number of moles added and is a number of 1 to 30.

[0013] In general formula (a1), R 1a From the viewpoint of cleaning properties, the number of carbon atoms is 8 or more, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less. R 1a R is an aliphatic hydrocarbon group, preferably a group selected from an alkyl group and an alkenyl group. 1a is more preferably an alkyl group having a carbon number in the above range.

[0014] In general formula (a1), A 1a The O group is an alkyleneoxy group having 2 to 4 carbon atoms and containing an ethyleneoxy group, preferably an alkyleneoxy group having 2 to 3 carbon atoms and containing an ethyleneoxy group, and more preferably an ethyleneoxy group. 1a The O group may be an alkyleneoxy group, including an ethyleneoxy group and another alkyleneoxy group, such as a propyleneoxy group. The other alkyleneoxy group is preferably a propyleneoxy group. 1a When the O group contains an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be bonded in a block type or a random type.

[0015] In the general formula (a1), n ​​is A 1a It is the average number of moles of O groups added, and is a number of 1 or more and 30 or less. In general formula (a1), n ​​is 1 or more, preferably 6 or more, more preferably 10 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, from the viewpoint of cleaning properties. In the general formula (a1), m is preferably 0 from the viewpoint of cleaning properties. In general formula (a1), R 2aFrom the viewpoint of cleaning properties, is preferably a hydrogen atom.

[0016] Specific examples of nonionic surfactants having no alkyleneoxy group other than the component (a1) include one or more selected from sucrose fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, alkyl glycosides, and glyceryl monoethers.

[0017] <(b) Component> The component (b) is an anionic surfactant. From the viewpoint of detergency, the component (b) is preferably at least one selected from alkylarylsulfonic acid type surfactants, sulfate ester type surfactants, alkanesulfonic acid type surfactants, olefinsulfonic acid type surfactants, sulfosuccinic acid alkyl ester type surfactants, sulfofatty acid ester type surfactants, and fatty acids and their salts, more preferably at least one selected from alkylarylsulfonic acid type surfactants, sulfate ester type surfactants, sulfosuccinic acid alkyl ester type surfactants, and fatty acids and their salts, and even more preferably at least one selected from alkylarylsulfonic acid type surfactants, and fatty acids and their salts. When component (b) is a salt, examples of the salt include inorganic salts such as sodium salt, potassium salt, ammonium salt, magnesium salt, etc., and organic salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, morpholine salt, etc. The salt of component (b) is preferably an inorganic salt selected from alkali metal salts such as sodium salt, potassium salt, etc. and alkaline earth metal salts such as magnesium salt, etc., more preferably an alkali metal salt, and even more preferably a sodium salt.

[0018] The component (b) may be one or more compounds selected from the group consisting of a compound represented by the following general formula (b1) (hereinafter referred to as the component (b1)), a compound represented by the general formula (b2) (hereinafter referred to as the component (b2)), a compound represented by the general formula (b3) (hereinafter referred to as the component (b3)), and a compound represented by the general formula (b4) (hereinafter referred to as the component (b4)). From the viewpoints of detergency and solubility, the component (b) is preferably one or more compounds selected from the compounds represented by the following general formula (b1), and from the viewpoint of solubility, it is preferably one or more compounds selected from the compounds represented by the following general formula (b2). From the viewpoints of cleaning power and solubility, the component (b) preferably contains one or more compounds selected from the compounds represented by the following general formula (b1) and one or more compounds selected from the components represented by the following general formula (b2). R 1b -B-SO3M (b1) [In formula (b1), R 1b represents an alkyl group having 8 to 18 carbon atoms, B represents a benzene ring, and R bonded to the carbon atom of B 1b The carbon atom of is a secondary carbon atom, and M represents a cation. 1b In contrast, the sulfonic acid group is bonded to the ortho, meta or para position. R 2b -COOM (b2) [In formula (b2), R 2b represents an alkyl or alkenyl group having 8 to 18 carbon atoms, and M represents a cation. R 3b -O-(AO) n -SO3M (b3) [In formula (b3), R 3b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, the AO group is one or more alkyleneoxy groups selected from an ethyleneoxy group and a propyleneoxy group, n is a number of 0 to 20, and M is a cation. R 4b -CH(SO3M)COOR 5b (b4) [In formula (b4), R 4b represents an alkyl group having 8 to 18 carbon atoms, and R 5b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and M represents a cation.

[0019] In general formula (b1), R 1bis preferably an alkyl group having 10 or more carbon atoms, more preferably 11 or more, even more preferably 12 or more carbon atoms, and preferably 18 or less, more preferably 16 or less, even more preferably 14 or less carbon atoms. In the general formula (b1), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1 / 2 atom) such as magnesium or calcium, or an organic ammonium. The organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal such as sodium or potassium, or an alkanolammonium such as monoethanolammonium or diethanolammonium, more preferably sodium.

[0020] As the component (b1), p-alkylbenzenesulfonate salts in which the alkyl group has 11 or more and 14 or less carbon atoms are preferred, and sodium p-alkylbenzenesulfonate salts in which the alkyl group has 11 or more and 14 or less carbon atoms are more preferred. That is, the component (b1) is represented by the general formula (b1), 1b is an alkyl group having 11 to 14 carbon atoms, and M is sodium.

[0021] In general formula (b2), R 2b R is an alkyl or alkenyl group having 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less. 2b may be saturated or unsaturated and have a straight or branched chain, and is more preferably saturated and has a straight chain. In the general formula (b2), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1 / 2 atom) such as magnesium or calcium, or an organic ammonium. The organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is more preferably an alkali metal such as sodium or potassium, or an alkanolammonium such as monoethanolammonium or diethanolammonium, and further preferably sodium.

[0022] The component (b2) is preferably one or more selected from lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, and salts thereof, and more preferably one or more selected from lauric acid, myristic acid, and salts thereof. The component (b2) is represented by the general formula (b2), R 2b is an alkyl group having 11 to 17 carbon atoms, and M is a cation, and one or more compounds selected from the group consisting of compounds in which M is hydrogen or sodium are more preferred.

[0023] In general formula (b3), R 3b is preferably 10 or more, more preferably 11 or more, even more preferably 12 or more, and is preferably 18 or less, more preferably 16 or less, even more preferably 14 or less. 3b is a straight-chain or branched-chain aliphatic hydrocarbon, preferably a straight-chain aliphatic hydrocarbon, more preferably a straight-chain alkyl group.

[0024] In the general formula (b3), the AO group is one or more alkyleneoxy groups selected from an ethyleneoxy group and a propyleneoxy group. When the AO group contains an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be in a block bond or a random bond. From the viewpoint of improving cleaning properties, the AO group is preferably a group containing an ethyleneoxy group.

[0025] In general formula (b3), n is the average number of moles of AO groups added and is a number from 0 to 20. From the viewpoint of improving cleansing ability, n is preferably 1 or more, more preferably 2 or more, and from the viewpoint of improving cleansing ability, n is 20 or less, preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, and still more preferably 4 or less.

[0026] In general formula (b3), when the AO group contains a propyleneoxy group, the average number of moles of the propyleneoxy group added is preferably 4 or less, more preferably 3 or less, and preferably 0 or more. In general formula (b3), the average number of moles of the propyleneoxy group added may be 0. In general formula (b3), when the AO group contains an ethyleneoxy group, the average number of moles of the ethyleneoxy group added is preferably 0.5 or more, more preferably 1 or more, even more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, even more preferably 4 or less.

[0027] In the general formula (b3), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1 / 2 atom) such as magnesium or calcium, or an organic ammonium. The organic ammonium may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal such as sodium or potassium, or an alkanolammonium such as monoethanolammonium or diethanolammonium, more preferably sodium.

[0028] In general formula (b4), R 4b is preferably an alkyl group having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 18 or less, more preferably 16 or less carbon atoms. In general formula (b4), R 5b is preferably an alkyl group having 1 or more carbon atoms and preferably 5 or less, more preferably 4 or less carbon atoms.

[0029] In the general formula (b4), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1 / 2 atom) such as magnesium or calcium, or an organic ammonium. The organic ammonium may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal such as sodium or potassium, or an alkanolammonium such as monoethanolammonium or diethanolammonium, more preferably sodium.

[0030] As the component (b4), in the general formula (b4), R 4b Alkyl groups with 11 to 14 carbon atoms, R 5b is a methyl group.

[0031] <(c) component> The component (c) is an oil-absorbing carrier. The type of the component (c) is not particularly limited, but from the viewpoint of improving the solubility of the detergent article in water by holding a surfactant, it is preferable that the oil-absorbing capacity is 120 mL / 100 g or more, and more preferably 180 mL / 100 g or more. The upper limit is not particularly limited. When the detergent composition contains multiple types of oil-absorbing carriers, it is preferable that the oil-absorbing carrier contains an oil-absorbing carrier having an oil-absorbing capacity of 120 mL / 100 g or more, and more preferably an oil-absorbing carrier having an oil-absorbing capacity of 180 mL / 100 g or more, from the viewpoint of improving the solubility of the detergent article in water. In addition, when a detergent composition contains a plurality of oil-absorbing carriers, from the viewpoint of improving the solubility of the detergent article in water, the content of the oil-absorbing carriers having an oil absorption capacity of 120 mL / 100 g or more, and further 180 mL / 100 g or more in the oil-absorbing carrier is preferably 50 mass % or more, more preferably 70 mass % or more, further preferably 90 mass % or more, and preferably 100 mass % or less, and may be 100 mass %. The oil absorption capacity of the oil-absorbing carrier can be measured based on JIS K 5101-13-2. In the present invention, from the above viewpoints, the oil-absorbing carrier is preferably one or more selected from amorphous silica, calcium silicate, crystalline aluminosilicate, amorphous aluminosilicate, and clay minerals, more preferably one or more selected from amorphous silica, calcium silicate, amorphous aluminosilicate, and clay minerals, and even more preferably one or more selected from amorphous silica and calcium silicate. Component (c) is preferably a water-insoluble carrier. With respect to component (c), "water-insoluble" means that 0.1 g or more does not dissolve in 100 g of water at 20°C.

[0032] The average primary particle size of component (c) is preferably 0.1 μm or more, more preferably 1 μm or more, and preferably 1000 μm or less, more preferably 500 μm or less, and even more preferably 100 μm or less. The average primary particle size of component (c) is measured by a laser diffraction / scattering type particle distribution measuring device. This average primary particle size is the D50 (median size) of the cumulative particle size distribution based on volume.

[0033] Specific examples of component (c) include amorphous aluminosilicates (oil absorption capacity: 285 mL / 100 g) described in JP-A-9-132794, JP-A-7-10526, JP-A-6-227811, JP-A-8-119622, etc. More specifically, the calcium silicate of component (c) may be Fluorite R (manufactured by Tokuyama Corp., oil absorption capacity: 400 to 500 mL / 100 g), the amorphous silica of component (c) may be Tokusil NR (manufactured by Tokuyama Corp., oil absorption capacity: 210 to 270 mL / 100 g) or Silopure (manufactured by Fuji Silysia Chemical Ltd., oil absorption capacity: 240 to 280 mL / 100 g), and the amorphous aluminosilicate of component (c) may be TIXOREX25 (manufactured by Hanfutsu Chemical Co., Ltd., 220 to 270 mL / 100 g).

[0034] In addition, the crystalline aluminosilicate of the component (c) may be zeolite. Specific examples of zeolite include crystalline aluminosilicates such as A-type, X-type, and P-type zeolite. A-type zeolite (e.g., trade name "Toyobuilder" manufactured by Tosoh Corporation, oil absorption capacity according to JIS K 5101 method: 40 mL / 100 g or more) is preferable as the crystalline aluminosilicate. Other suitable examples include P-type (e.g., trade names "Doucil A24", "ZSEO64", etc.; both manufactured by Crosfield; oil absorption capacity 60 to 150 mL / 100 g), X-type (e.g., trade name "WessalithXD" manufactured by Degussa; oil absorption capacity 80 to 100 mL / 100 g), and hybrid zeolites described in International Publication No. 98 / 42622.

[0035] Moreover, the clay mineral of the component (c) may be bentonite. The bentonite preferably has an ion exchange capacity of 50 to 100 meq / 100 g. The bentonite may be at least one selected from the group consisting of alkali metal or alkaline earth metal montmorillonite, smectitic clays selected from the group consisting of saponite or hectorite, illite, attapulgite, and kaolinite. Powdered or granulated bentonite may be used. For example, granulated clay minerals as disclosed in JP 2008-189719 A may be referred to.

[0036] <(d) component> Component (d) is an alkaline agent, and examples of component (d) include one or more alkaline agents selected from alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal silicates, and tripolyphosphates. Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate, with sodium carbonate being preferred. Examples of the alkali metal hydrogen carbonate include sodium hydrogen carbonate and potassium hydrogen carbonate. The alkali metal silicate includes sodium silicate and potassium silicate. Tripolyphosphates include alkali metal salts of tripolyphosphate.

[0037] From the viewpoint of storage stability, the component (d) is preferably one or more alkaline agents selected from alkali metal carbonates and alkali metal hydrogen carbonates, more preferably one or more alkaline agents selected from alkali metal carbonates, even more preferably one or more alkaline agents selected from sodium carbonate and potassium carbonate, and still more preferably sodium carbonate.

[0038] The average primary particle size of component (d) is preferably 0.1 μm or more, more preferably 1 μm or more, even more preferably 10 μm or more, and preferably 1000 μm or less, more preferably 500 μm or less. The average primary particle size of component (d) is measured using a low-tap type sieve shaker. Specifically, the average primary particle size of component (d) is determined by sieving a sample using standard sieves specified in JIS Z 8801, measuring the mass of the sample remaining on each sieve, and calculating the mass fraction according to the size of the sieve openings. The component (d) may be a water-soluble oil-absorbing carrier. From the viewpoint of retaining the surfactant, the component (d) preferably has an oil-absorbing capacity of 120 mL / 100 g or more. There is no particular upper limit. The oil-absorbing capacity of the component (d) can be measured based on JIS K 5101-13-2. Regarding component (d), "water-soluble" means that 0.1 g or more dissolves in 100 g of water at 20°C.

[0039] Component (d) has a coating layer of component (b). The coating layer of component (b) may be formed by spraying component (d) with an acid precursor of component (b). The thickness of the coating layer of component (b) is, from the viewpoint of solubility, 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 3.5 μm or more, still more preferably 4.5 μm or more, and from the viewpoint of solubility, 50 μm or less, preferably 30 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less. The thickness of the coating layer of component (b) is calculated by cutting an arbitrarily sampled sample of component (d) with a blade such as a scalpel and observing the cut sample with a scanning electron microscope (SEM). Specifically, the thickness of the coating layer of the (b) component particles on the (d) component particles is calculated based on images (magnification: 500x) of the cut surfaces of 10 randomly sampled particles of the (d) component, and the average thickness is used to determine the value.

[0040] <Composition, etc.> The detergent composition of the present invention contains the component (a) in an amount of preferably 1 mass % or more, more preferably 5 mass % or more, and even more preferably 10 mass % or more from the viewpoint of detergency, and in an amount of preferably 50 mass % or less, more preferably 30 mass % or less, and even more preferably 20 mass % or less from the viewpoint of storage stability.

[0041] The cleaning composition of the present invention contains, from the viewpoint of solubility, preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more of component (b), and from the viewpoint of solubility, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less. The mass of component (b) is to be calculated in terms of the sodium salt.

[0042] The detergent composition of the present invention contains, from the viewpoint of powder flowability, preferably 1 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more of component (c), and from the viewpoint of powder flowability, preferably 50 mass % or less, more preferably 30 mass % or less, and even more preferably 10 mass % or less.

[0043] The cleaning agent composition of the present invention contains the component (d) in an amount of preferably 1 mass % or more, more preferably 10 mass % or more, and even more preferably 20 mass % or more from the viewpoint of detergency, and in an amount of preferably 50 mass % or less, more preferably 40 mass % or less, and even more preferably 30 mass % or less from the viewpoint of solubility.

[0044] In the cleaning composition of the present invention, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, from the viewpoint of solubility, and is preferably 10 or less, more preferably 7 or less, even more preferably 4 or less, from the viewpoint of solubility.

[0045] In the cleaning composition of the present invention, the mass ratio (a) / (c) of the content of the component (a) to the content of the component (c) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1 or more, from the viewpoint of powder flowability, and is preferably 10 or less, more preferably 7 or less, and even more preferably 4 or less, from the viewpoint of solubility.

[0046] In the cleaning composition of the present invention, the mass ratio (b) / (d) of the content of the component (b) to the content of the component (d) is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 0.15 or more, from the viewpoint of solubility, and is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, and still more preferably 0.5 or less, from the viewpoint of detergency.

[0047] When the cleaning composition of the present invention contains the component (b1) and the component (b2), the mass ratio (b1) / (b2) of the content of the component (b1) to the content of the component (b2) in the cleaning composition of the present invention is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 0.5 or more, from the viewpoint of solubility, and is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, from the viewpoint of solubility.

[0048] <(e) component> From the viewpoint of antibacterial activity, the cleaning composition of the present invention may optionally contain, as component (e), a surfactant other than components (a) and (b). The component (e) may be one or more types selected from cationic surfactants and amphoteric surfactants.

[0049] Examples of cationic surfactants include alkyltrimethylammonium salts in which the alkyl group has 8 to 22 carbon atoms, dialkyldimethylammonium salts in which the alkyl group has 8 to 22 carbon atoms, alkyldimethylbenzylammonium salts in which the alkyl group has 8 to 22 carbon atoms, and benzethonium salts. Examples of these salts include halogen salts and alkyl sulfates in which the carbon number is 1 to 3.

[0050] Examples of amphoteric surfactants include N-alkanoylaminopropyl-N,N-dimethylamine oxide, N-alkyl-N,N-dimethylamine oxide, N-alkanoylaminopropyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine. In these, the alkanoyl group is, for example, lauroyl or myristyl. In addition, in these, the alkyl group is, for example, lauryl or myristyl.

[0051] When the cleaning composition of the present invention contains the component (e), the cleaning composition of the present invention contains the component (e) in an amount of preferably 0.1 mass % or more, more preferably 1 mass % or more, and even more preferably 3 mass % or more from the viewpoint of antibacterial activity, and preferably 30 mass % or less, more preferably 10 mass % or less, and even more preferably 5 mass % or less from the viewpoint of storage stability. In addition, when the cleaning composition of the present invention contains a cationic surfactant as component (e), the mass of the cationic surfactant as component (e) is defined as a value converted into a chloride salt.

[0052] <Component (f)> The cleaning composition of the present invention may optionally contain, as component (f), one or more enzymes selected from proteases, lipases and amylases. Proteases include, for example, serine proteases (EC 3.4.21) and metalloproteases (EC 3.4.17 or EC 3.4.24). Examples of suitable proteases include neutral or alkaline serine proteases such as subtilisin (EC 3.4.21.62). Examples of lipases include triacylglycerol lipase (EC 3.1.1.3), phospholipase A2 (EC 3.1.1.4), lysophospholipase (EC 3.1.1.5), monoglyceride lipase (EC 3.1.1.23), galactolipase (EC 3.1.1.26), phospholipase A1 (EC 3.1.1.32), and lipoprotein lipase (EC 3.1.1.34). Examples of amylases include α-amylase (EC 3.2.1.1), β-amylase (EC 3.2.1.2) and / or glucoamylase (EC 3.2.1.3), etc. Suitable examples of amylases include neutral or alkaline α-amylases, preferably of microbial origin, such as bacteria or fungi.

[0053] When the cleaning composition of the present invention contains the component (f), from the viewpoint of detergency, the cleaning composition of the present invention contains the component (f) in an amount of preferably 0.01 mass % or more, more preferably 0.1 mass % or more, even more preferably 0.3 mass % or more, and preferably 30 mass % or less, more preferably 20 mass % or less, and even more preferably 10 mass % or less.

[0054] <(g) component> The cleaning composition of the present invention may optionally contain, as component (g), one or more compounds selected from inorganic sulfates and inorganic halogen compounds. Examples of component (g) include compounds selected from sodium sulfate, magnesium sulfate, sodium chloride, and magnesium chloride. Component (g) may be either a hydrate or an anhydride.

[0055] When the cleaning composition of the present invention contains the component (g), from the viewpoint of detergency, the cleaning composition of the present invention contains the component (g) in an amount of preferably 2 mass% or more, more preferably 5 mass% or more, even more preferably 10 mass% or more, still more preferably 20 mass% or more, still more preferably 30 mass% or more, and preferably 60 mass% or less, more preferably 50 mass% or less, and even more preferably 40 mass% or less.

[0056] <(h) component> The cleaning composition of the present invention may optionally contain, as component (h), a polymer having a carboxylic acid group or a salt thereof and a weight average molecular weight of 3,000 or more. Examples of the component (h) include a polymer selected from polyacrylic acid or a salt thereof, and a copolymer of acrylic acid and maleic acid or a salt thereof (hereinafter referred to as component (h1)). Examples of polyacrylic acid or a salt thereof include polyacrylic acid, sodium polyacrylate, potassium polyacrylate, etc., and preferably sodium polyacrylate and potassium polyacrylate. Examples of the copolymer of acrylic acid and maleic acid or its salt include a copolymer of acrylic acid and maleic acid, a sodium salt of a copolymer of acrylic acid and maleic acid, a potassium salt of a copolymer of acrylic acid and maleic acid, etc., and preferably a sodium salt of a copolymer of acrylic acid and maleic acid, or a potassium salt of a copolymer of acrylic acid and maleic acid. The molar ratio of the copolymer of acrylic acid and maleic acid, in terms of the number of moles of acrylic acid / the number of moles of maleic acid, is preferably 1 / 99 or more, more preferably 10 / 90 or more, and is preferably 99 / 1 or less, more preferably 90 / 10 or less.

[0057] The component (h1) may be a copolymer containing a monomer other than acrylic acid and maleic acid that is copolymerizable with acrylic acid and / or maleic acid, so long as it does not interfere with the manifestation of the effects of the present invention. Examples of monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and / or maleic acid include vinyl monomers, acrylic monomers, styrene monomers, etc., and more specifically, examples of monomers include methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, styrene, etc. The molar ratio of monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and / or maleic acid in the component (h1) is preferably 0 mol% or more, and preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 0 mol%. Therefore, the polyacrylic acid or a salt thereof, and the copolymer of acrylic acid and maleic acid or a salt thereof of the present invention may be a polymer or copolymer containing, among all the constituent monomers, monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and / or maleic acid in an amount in the range of 0 mol % or more and 5 mol % or less.

[0058] The weight average molecular weight of component (h) is 3,000 or more, preferably 3,500 or more, more preferably 4,000 or more, even more preferably 5,000 or more, even more preferably 6,000 or more, even more preferably 7,000 or more, even more preferably 8,000 or more, even more preferably 9,000 or more, even more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less. The weight average molecular weight can be measured according to the following method for measuring weight average molecular weight.

[0059] <Method for measuring weight average molecular weight> The weight average molecular weight of component (h) can be measured by GPC (gel permeation chromatography) and the weight average molecular weight (Mw) can be calculated using a conversion standard substance. The GPC measurement conditions are as follows. Column: Tosoh Corporation, product name: TSK-GEL guard PWXL Manufactured by Tosoh Corporation, product name: TSK-GEL G4000 PWXL Manufactured by Tosoh Corporation, product name: TSK-GEL G2500 PWXL Mobile phase: 0.1 mol / L potassium dihydrogen phosphate and 0.1 mol / L sodium dihydrogen phosphate aqueous solution / acetonitrile = 90 / 10 (volume ratio) Detector: Refractive index detector Column temperature: 40℃ ·Flow rate: 1.0mL / min Conversion standard material: Polyacrylic acid (American Standard Corporation) Sample: Add ion-exchanged water to an aqueous polymer solution containing 0.8 g of solids to make the total volume 200 mL, and then take 10 μL of this solution and inject it into the column.

[0060] When the cleaning composition of the present invention contains the component (h), from the viewpoints of cleaning performance and stability, the cleaning composition of the present invention contains the component (h) in an amount of preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 2 mass % or more, and preferably 20 mass % or less, more preferably 15 mass % or less, and even more preferably 10 mass % or less.

[0061] <Component (i)> The cleaning composition of the present invention may optionally contain, as component (i), a polyalkylene glycol having a weight average molecular weight of 100 or more and 100,000 or less. The component (i) may be one or more selected from polyethylene glycol and polypropylene glycol. The weight average molecular weight of component (i) is 100 or more, preferably 1,000 or more, and 100,000 or less, preferably 10,000 or less, and more preferably 2,000 or less. The weight average molecular weight herein is a value determined by gel permeation chromatography using polystyrene as a standard substance.

[0062] When the cleaning composition of the present invention contains component (i), from the viewpoint of stability, the cleaning composition of the present invention contains component (i) in an amount of preferably 0.001 mass% or more, more preferably 0.01 mass% or more, even more preferably 0.1 mass% or more, still more preferably 1 mass% or more, still more preferably 5 mass% or more, still more preferably 10 mass% or more, and preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less.

[0063] The cleaning agent composition of the present invention may optionally contain other components known in the field of laundry detergents, such as bleaching agents (perborates, bleach activators, etc.), anti-redeposition agents, reducing agents (sulfites, etc.), fluorescent brightening agents, foam suppressors (silicones, etc.), organic solvents, fragrances, colorants, antibacterial agents, etc. (excluding those corresponding to components (a) to (i)).

[0064] The cleaning composition of the present invention may be a solid cleaning composition. The cleaning composition of the present invention may be in the form of a powder, a granule, or a granule. From the viewpoint of solubility, the cleaning composition of the present invention is preferably one or more cleaning compositions selected from the group consisting of a powder, a granule, and a granule. The cleaning composition of the present invention may also be a powder cleaning composition.

[0065] The detergent composition of the present invention can be produced by a known method, for example, a spray drying method, a dry neutralization method, a dry granulation method, a dry blending method, a fluidized bed drying method, a thin film drying method, an extrusion granulation method, a tumbling granulation method, agitation granulation method, a compaction granulation method, a surfactant supporting method, or a combination of methods selected from these.

[0066] The bulk density of the detergent composition of the present invention varies depending on the production method, but is preferably 0.2 g / cm 3 More preferably, 0.3 g / cm 3 More preferably, 0.35 g / cm 3 More than 1 g / cm 3 Less than or equal to 0.95 g / cm 3More preferably, 0.9 g / cm 3 The following is the result.

[0067] When the cleaning composition of the present invention is a powder cleaning composition, the average particle size of the cleaning composition of the present invention is preferably 100 μm or more, more preferably 150 μm or more, even more preferably 200 μm or more, and preferably 800 μm or less, more preferably 750 μm or less, even more preferably 700 μm or less. The average particle size is determined using a low tap type sieve shaker. Specifically, the average particle size is determined by sieving a sample using standard sieves specified in JIS Z 8801, measuring the mass of the sample remaining on each sieve, and calculating the mass fraction according to the size of the sieve openings.

[0068] <Method of producing the cleaning composition> The cleaning composition of the present invention can be produced by mixing the components (a), (b), (c), (d) and other optional components. The amounts of components (a) to (d) and other optional components in the cleaning composition of the present invention can be applied by replacing the preferred contents in the cleaning composition of the present invention with the blending amounts.

[0069] The cleaning composition of the present invention can be produced, for example, by the following steps 1 to 3. However, the method for producing the cleaning composition of the present invention is not limited to this method. Step 1: A step of impregnating component (c) with component (a). Step 2: forming a coating layer of component (b) on component (d) Step 3: A step of mixing component (c) impregnated with component (a), component (d) having a coating layer of component (b), and other components.

[0070] In step 1, component (c) can be mixed with component (a) to impregnate component (c) with component (a). Alternatively, in step 1, supported granules containing component (c) may be produced and the supported granules may be impregnated with component (a).

[0071] In step 2, a coating layer of component (b) is formed on component (d). For example, a coating layer of component (b) can be formed on component (d) by spraying an acid precursor of component (b) onto component (d). Examples of the acid precursor of component (b) that can be used in the present invention include alkylbenzenesulfonic acid, alkyl or alkenyl ether sulfuric acid, alkyl or alkenyl sulfuric acid, α-olefinsulfonic acid, α-sulfonated fatty acid, alkyl or alkenyl ether carboxylic acid, fatty acid, etc. The amount of the acid precursor of component (b) used, per 100 parts by mass of component (d), is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less.

[0072] In the method for producing the cleaning composition of the present invention, by blending the components (b1) and (b2), the amount of the powdered cleaning composition adhering to the inside of a mixer is reduced, the powdered cleaning composition can be produced stably, and the powdered cleaning composition can be easily packaged in a water-soluble film. In the method for producing the cleaning composition of the present invention, the mass ratio (b1) / (b2) of the blended amount of the component (b1) to the blended amount of the component (b2) is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 0.5 or more, from the viewpoint of solubility, and is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, from the viewpoint of solubility.

[0073] <Cleaning products> The cleaning article of the present invention comprises the cleaning composition of the present invention and a water-soluble film that packages the cleaning composition. The detergent composition of the present invention may be a detergent article comprising the detergent composition of the present invention packaged in a water-soluble film.

[0074] In the present invention, the term "water-soluble" in relation to a water-soluble film means that, after placing 500 g of 30°C ion-exchanged water in a 1-liter glass beaker, placing a Teflon (registered trademark) stirrer with a diameter of 8 cm, adding 1 g of the film to be evaluated, and stirring at 100 rpm for 30 minutes, no insoluble matter is apparent. In addition, from the viewpoints of preventing accidental ingestion and solubility, the thickness of the water-soluble film is preferably 1 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, and preferably 200 μm or less, more preferably 150 μm or less, even more preferably 100 μm or less.

[0075] The water-soluble film is preferably composed of a polymer. The water-soluble film can be obtained by methods known in the art, such as casting, blowing, extrusion, injection molding of polymers, etc. Non-limiting examples of polymers for producing water-soluble films include polyvinyl alcohol (PVA), vinyl alcohol copolymers, polyvinylpyrrolidone, polyalkylene oxides, (modified) cellulose, (modified) cellulose-ethers or -esters or -amides, polycarboxylic acids and their salts such as polyacrylates, maleic acid / acrylic acid copolymers, polyamino acids or peptides, polyamides such as polyacrylamides, polysaccharides such as starch and gelatin, natural gums such as xanthan and carragum. Vinyl alcohol copolymers are copolymers of vinyl alcohol with other monomers, such as ethylene, acrylic acid. Preferably, the water-soluble film comprises a polymer selected from the group consisting of polyacrylates and water-soluble acrylates, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, maltodextrin, polymethacrylates, polyvinyl alcohol, vinyl alcohol copolymers, hydroxypropylmethylcellulose (HPMC), and combinations thereof. More preferably, the water-soluble film comprises a polymer selected from polyvinyl alcohol, vinyl alcohol copolymers, and hydroxypropylmethylcellulose. Even more preferably, the water-soluble film comprises polyvinyl alcohol, such as Solvron available from Aicello Co., Ltd. Suitable polymers for producing water-soluble films are described, for example, in U.S. Pat. No. 6,995,126.

[0076] In the detergent article of the present invention, the total area of ​​the water-soluble film that comes into contact with the detergent composition of the present invention is preferably 2 cm2 or less from the viewpoint of further improving the product stability. 2 More than 5cm, preferably 5cm 2 More than 7cm, more preferably 2 More preferably, 15 cm 2 From the same viewpoint, preferably 100 cm2 Less than or equal to 70cm, preferably 2 Less than 60cm, more preferably 2 Less than 45cm, more preferably 45cm 2 The following is the result.

[0077] The cleaning article of the present invention can be made by any suitable process known in the art, such as known detergent pouch making processes. Exemplary pouch making processes are described in U.S. Patent Nos. 6,995,126, 7,127,874, 8,156,713, 7,386,971, 7,439,215, and U.S. Patent Application Publication No. 2009 / 199877.

[0078] The amount of contents per cleaning article of the present invention is preferably 5 g or more, more preferably 8 g or more, even more preferably 10 g or more, and preferably 50 g or less, more preferably 30 g or less, even more preferably 25 g or less.

[0079] The preferred shape and size of each of the cleaning articles of the present invention is, for example, a quadrilateral, with the length of one side being preferably 1 cm or more and 5 cm or less, and the thickness being preferably 1 cm or more and 5 cm or less, more preferably 1 cm or more and 4 cm or less. The weight of each of the cleaning articles of the present invention is preferably 5 g or more, more preferably 10 g or more, even more preferably 15 g or more, and preferably 50 g or less, more preferably 40 g or less, even more preferably 30 g or less.

[0080] Another preferred shape and size of each of the detergent articles of the present invention is, for example, a rectangular parallelepiped shape, with a vertical length of preferably 5 cm to 20 cm, more preferably 7 cm to 15 cm, a horizontal length of preferably 0.5 cm to 4 cm, more preferably 1 cm to 2 cm, and a thickness of preferably 0.5 cm to 5 cm, more preferably 1 cm to 2 cm. The mass of each of the detergent articles of the present invention is preferably 5 g or more, more preferably 10 g or more, and preferably 50 g or less, more preferably 40 g or less, even more preferably 30 g or less, and even more preferably 20 g or less.

[0081] The detergent article of the present invention can be suitably used for textile products, for hard surfaces such as tableware, and for automatic dishwashers, and is preferably used for textile products.

[0082] When a textile product is cleaned with the cleaning agent article of the present invention, the fiber to be cleaned may be either hydrophobic or hydrophilic. Examples of hydrophobic fibers include protein fibers (milk protein casein fiber, promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride / polyvinyl alcohol copolymer fibers (polycral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), polyfluoroethylene fibers (polytetrafluoroethylene, etc.), glass fibers, carbon fibers, alumina fibers, silicone carbide fibers, rock fibers (rock fibers), slag fibers (slag fibers), and metal fibers (gold thread, silver thread, steel fiber). Examples of hydrophilic fibers include seed hair fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), palm fibers, rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fibers (domestic silk, wild silk), feathers, and cellulosic fibers (rayon, polynosic, cupra, acetate, etc.). From the viewpoint of finishing quality, the fiber is preferably a fiber containing cotton fiber. From the viewpoint of finishing quality of the fiber, the content of cotton fiber in the fiber is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 40% by mass or more, still more preferably 60% by mass or more, still more preferably 80% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.

[0083] In the present invention, the textile product refers to fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics using the hydrophobic fibers or hydrophilic fibers, and products obtained using the same, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, and tights.

[0084] <How to wash textile products> The present invention provides a method for cleaning textile products, which comprises cleaning the textile products with a cleaning liquid (hereinafter referred to as the cleaning liquid of the present invention) comprising a mixture of the cleaning agent article of the present invention and water. In the method for cleaning textile products of the present invention, the embodiments described in the detergent article of the present invention and the detergent composition of the present invention can be applied. In the method for washing textile products of the present invention, the cleaning agent article of the present invention and water may first be charged into a washing tank and mixed to prepare the cleaning solution of the present invention, and then the textile product to be washed is charged and the textile product is washed. However, from the viewpoint of enjoying the effects of the present invention, a method is preferred in which the cleaning agent article of the present invention, water, and the textile product are charged into a washing tank, and the cleaning solution of the present invention is prepared while the cleaning agent article of the present invention is dissolved in the water, and the textile product is washed at the same time.

[0085] In the cleaning solution of the present invention, the amount of water when mixing the cleaning article of the present invention with water is prepared so that the total amount of the cleaning composition of the present invention contained in the cleaning article of the present invention is preferably 0.01 g or more, more preferably 0.1 g or more, even more preferably 0.3 g or more, and preferably 10 g or less, more preferably 1 g or less, and even more preferably 0.5 g or less, per 1 L of water, from the viewpoints of environmental consideration and cleaning performance.

[0086] Moreover, water used in the method for washing textile products, such as water used for preparing a washing liquid, water used for rinsing, etc., is preferably water having hardness. From the viewpoint of detergency, the hardness of the water is preferably 1°dH or more, more preferably 2°dH or more, and preferably 20°dH or less, more preferably 15°dH or less, even more preferably 10°dH or less, and even more preferably 5°dH or less, on the German hardness scale. Here, German hardness (°dH) in this specification refers to the concentration of calcium and magnesium in water expressed as 1 mg / L (ppm) = approximately 0.056°dH (1°dH = 17.8 ppm) in CaCO3 equivalent concentration. The calcium and magnesium concentrations for this German hardness are determined by a chelate titration method using disodium ethylenediaminetetraacetic acid. A specific method for measuring the German hardness of water in this specification is shown below.

[0087] <Method of measuring water hardness in Germany> 〔reagent〕 0.01 mol / L EDTA·2Na solution: 0.01 mol / L aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01M EDTA-Na2, manufactured by Sigma-Aldrich) ·Universal BT indicator (product name: Universal BT Co., Ltd., manufactured by Dojindo Laboratories) Ammonia buffer solution for hardness measurement (67.5 g of ammonium chloride dissolved in 570 mL of 28 w / v% ammonia water, and the total volume made up to 1000 mL with ion-exchanged water) [Measurement of hardness] (1) Using a volumetric pipette, collect 20 mL of sample water into a conical beaker. (2) Add 2 mL of ammonia buffer solution for hardness measurement. (3) Add 0.5 mL of Universal BT indicator. After addition, confirm that the solution is reddish purple. (4) While shaking the conical beaker well, add 0.01 mol / L EDTA·2Na solution dropwise from the burette until the sample water turns blue, which is the endpoint of the titration. (5) Total hardness is calculated using the following formula. Hardness (°dH)=T×0.01×F×56.0774×100 / A T:0.01mol / L Titration amount of EDTA・2Na solution (mL) A: Sample volume (20 mL, volume of sample water) F: Factor of 0.01mol / L EDTA·2Na solution

[0088] The cleaning solution of the present invention contains the component (a) in an amount of preferably 1 ppm or more, more preferably 10 ppm or more, and even more preferably 20 ppm or more from the viewpoint of detergency, and in an amount of preferably 500 ppm or less, more preferably 300 ppm or less, and even more preferably 100 ppm or less from the viewpoint of solubility.

[0089] The cleaning solution of the present invention contains the component (b) in an amount of preferably 0.5 ppm or more, more preferably 5 ppm or more, and even more preferably 10 ppm or more from the viewpoint of detergency, and in an amount of preferably 300 ppm or less, more preferably 150 ppm or less, and even more preferably 50 ppm or less from the viewpoint of solubility.

[0090] The cleaning solution of the present invention contains the component (c) in an amount of preferably 0.5 ppm or more, more preferably 5 ppm or more, and even more preferably 10 ppm or more, from the viewpoint of solubility, and preferably 300 ppm or less, more preferably 150 ppm or less, and even more preferably 50 ppm or less, from the viewpoint of solubility.

[0091] The cleaning solution of the present invention contains the component (d) in an amount of preferably 1 ppm or more, more preferably 10 ppm or more, and even more preferably 50 ppm or more from the viewpoint of detergency, and in an amount of preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 200 ppm or less from the viewpoint of solubility.

[0092] When the cleaning solution of the present invention contains component (e), it contains component (e) in an amount of preferably 0.1 ppm or more, more preferably 1 ppm or more, and even more preferably 5 ppm or more from the viewpoint of antibacterial activity, and preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 20 ppm or less from the viewpoint of storage stability.

[0093] When the cleaning solution of the present invention contains the component (f), from the viewpoint of detergency, the component (f) is preferably contained in an amount of 0.01 ppm or more, more preferably 0.1 ppm or more, and even more preferably 1 ppm or more, and from the viewpoint of detergency, the component (f) is preferably contained in an amount of 100 ppm or less, more preferably 50 ppm or less, and even more preferably 20 ppm or less.

[0094] When the cleaning solution of the present invention contains the component (g), from the viewpoint of detergency, the component (g) is preferably contained in an amount of 1 ppm or more, more preferably 10 ppm or more, and even more preferably 100 ppm or more, and from the viewpoint of detergency, the component (g) is preferably contained in an amount of 3000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less.

[0095] When the cleaning solution of the present invention contains component (h), it contains component (h) in an amount of preferably 0.1 ppm or more, more preferably 1 ppm or more, and even more preferably 2 ppm or more, from the viewpoint of cleaning power, and preferably 1000 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.

[0096] In recent years, washing machines have become larger, and the value of the liquor ratio, which is the ratio of the mass of the textile product (kg) to the amount of water in the cleaning solution (liters), i.e., the amount of water in the cleaning solution (liters) / mass of the textile product (kg) (hereinafter, this ratio may be referred to as the liquor ratio), tends to decrease. When a household washing machine is used, if the liquor ratio is small, the textile products may be rubbed against each other by agitation during washing, which may impair the finish of the textile product. From the viewpoint of cleaning performance, the liquor ratio is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, and from the viewpoint of washing efficiency, it is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less.

[0097] The method for washing textile products of the present invention is suitable for a method of immersing textile products in a liquid used for scouring while feeding the textile products with rollers or the like, and a rotary washing method. The rotary washing method means a washing method in which a textile product not fixed to a rotating device rotates around a rotating shaft together with the washing liquid. The rotary washing method can be carried out by a rotary washing machine. Therefore, in the present invention, in order to finish the textile products more beautifully, it is preferable to wash the textile products using a rotary washing machine. Specific examples of the rotary washing machine include a drum washing machine, a pulsator washing machine, and an agitator washing machine. For these rotary washing machines, those commercially available for home use can be used. EXAMPLES

[0098] <Composition ingredients> In the examples and comparative examples, the following components were used. [Component (a)] Emulgen 110L: Polyoxyethylene alkyl ether (alkyl group carbon number 12, average number of oxyethylene added moles 10), manufactured by Kao Corporation [(b) component] (b1) Component LAS-Na: Sodium laurylbenzenesulfonate, Neopelex G-65, manufactured by Kao Corporation (b2) Component Fatty acids: Lunac L-98, lauric acid, manufactured by Kao Corporation [(c) component] · Toxil: Amorphous silica, Toxil NR, Oriental Silicas Corporation Fluorite: Calcium silicate, Fluorite R, manufactured by Tomita Pharmaceutical Co., Ltd. Zeolite: Synthetic zeolite, A-4, powder, 75μm (200mesh), Fujifilm Wako Pure Chemical Industries, Ltd. [(d) component] Sodium carbonate, Fujifilm Wako Pure Chemical Industries, Ltd. [(e) component] Cationic surfactant: alkyl dimethyl benzyl ammonium chloride, Sanisol B-50, manufactured by Kao Corporation [Component (f)] Enzymes: Proteases, Savinase 18T, Novozymes [(g) Component] Sodium sulfate: Fujifilm Wako Pure Chemical Industries, Ltd. Magnesium sulfate: Fujifilm Wako Pure Chemical Industries, Ltd. [(h) component] Polyacrylic acid: sodium polyacrylate, weight average molecular weight 10,000, product name Poise 536, manufactured by Kao Corporation [Component (i)] Polyethylene glycol: weight average molecular weight 6,000, Fujifilm Wako Pure Chemical Industries, Ltd.

[0099] <Preparation of cleaning composition> 1. Examples 1 to 15 The above-mentioned components were used to prepare the cleaning compositions shown in Table 1 by the following method. Component (a) was mixed with component (c) in the amounts shown in Table 1, and component (a) was adsorbed to component (c). A liquid acid precursor of component (b) adjusted to 60°C was mixed with component (d) to carry out a dry neutralization reaction. Then, the particles in which component (a) was adsorbed to component (c) and the particles in which component (b) was mixed with component (d) to carry out a neutralization reaction were mixed. After that, the components shown in Table 1 were added and stirred to obtain the blending composition shown in Table 1, and various powdered cleaning agent compositions were prepared. 2. Comparative Examples 1 to 5 The cleaning composition of Comparative Example 1 was prepared by mixing component (c) with particles that had been neutralized by mixing component (b) with component (d) using the method described above, and then adding and stirring each of the components listed in Table 1 in the same manner as in 1 above. The cleaning composition of Comparative Example 2 was prepared by mixing the particles in which component (a) was adsorbed onto component (c) by the above-mentioned method with component (d), and then adding and stirring each of the components listed in Table 1 in the same manner as in 1 above. The cleaning composition of Comparative Example 3 was prepared by adding and mixing component (a) to particles that had been neutralized by mixing component (b) with component (d) using the above-mentioned method, and then adding and stirring each of the components listed in Table 1 in the same manner as in 1 above. The cleaning compositions of Comparative Examples 4 and 5 were prepared by adding and mixing the particles in which component (a) was adsorbed onto component (c) by the above-mentioned method with a sodium neutralized form of component (b) (a 65% aqueous solution of LAS-Na, a 25% aqueous solution of sodium fatty acid), and then adding and stirring the components listed in Table 1 in the same manner as in 1 above.

[0100] <Preparation of cleaning agent article> Two sheets of water-soluble film made of polyvinyl alcohol (length 13 cm, width 2 cm, thickness 76 μm, M8685, manufactured by Monosol Co., Ltd.) were stacked and three sides were fused using a heat sealer (manufactured by Fuji Impulse Co., Ltd.) to prepare a bag with only one side open, and 13 g of each of the detergent compositions listed in Table 1 was placed in this bag. The open side of the bag was then fused and closed by heat sealing to obtain a detergent article in which each detergent composition was packaged in a water-soluble film. The total area of ​​the water-soluble film in contact with the detergent composition was 30 cm 2 The cleaning article of the present invention is not limited to the above-mentioned production method.

[0101] <Evaluation of sebum stain cleaning ability> 1. Preparation of artificially soiled cloth Next, artificial soiling composed of the following composition was gravure coated onto a 6 cm x 6 cm cotton / polyester broadcloth (cotton / polyester ratio = 35 / 65, purchased from Tanigashira Shoten) so that the amount was 100 mg per sheet, to prepare an artificially soiled cloth. *Artificial dirt The artificial soil was a composition containing the following A, B, C, D, and E. The mass% of each is the proportion in the artificial soil of the final composition, and the amount of B was adjusted so that the total was 100 mass%. A: Adjusted oil (used in an amount such that the mass percentages in the artificial dirt are 0.44 mass% lauric acid, 3.15 mass% myristic acid, 2.35 mass% pentadecanoic acid, 6.31 mass% palmitic acid, 0.44 mass% heptadecanoic acid, 1.6 mass% stearic acid, 7.91 mass% oleic acid, 13.33 mass% triolein, 2.22 mass% n-hexadecyl palmitate, and 6.66 mass% squalene) B: Hard water obtained by weighing out 105 mg of calcium chloride (dihydrate) and dissolving it in distilled water to make 1,000 mL. C: 1.98% by mass of egg white lecithin liquid crystals (11.37 g of arginine hydrochloride, 4.20 g of histidine, and 2.44 g of serine were dissolved in 80 mL of distilled water, and the pH was adjusted to 5.0 with concentrated hydrochloric acid. The solution was then thoroughly mixed with egg white lecithin in a mixer to obtain an egg white lecithin liquid crystals). D: Kanuma red soil 8.11% by mass E: Carbon black 0.025% by mass

[0102] 2. Cleaning evaluation The three pieces of artificially soiled cloth prepared in 1 above were washed in a tergotometer (Ueshima MS-8212) at 100 rpm for 10 minutes. The specific washing conditions were as follows: one detergent article packaged in a water-soluble film as shown in Table 1 was dissolved in 1 L of ion-exchanged water to prepare an aqueous detergent solution. This aqueous detergent solution was then diluted 30 times to prepare 30 L of a cleaning solution. At this time, the cleaning solution was prepared to have a German hardness of 2° dH and a water temperature of 30°C. The three pieces of artificially soiled cloth and the cleaning solution were placed in the tergotometer, and the artificially soiled cloth was washed at 100 rpm for 10 minutes. The water with a German hardness of 2° dH was prepared by mixing calcium chloride and magnesium chloride in ion-exchanged water at a ratio of Ca / Mg = 6 / 4 (mass ratio) to give a German hardness of 2° dH. After washing, the fabric was rinsed twice with city water (30° C.) for 1 minute. After rinsing, the fabric was press-dried using a dryer (OT-20S, manufactured by Tosen Corporation). The reflectance at a wavelength of 550 nm of the original fabric of the artificially soiled cloth and the artificially soiled cloth before and after cleaning was measured using a spectrophotometer (SE2000, manufactured by Nippon Denshoku Co., Ltd.), and the cleaning rate (%) was calculated based on the following formula (1). The cleaning ability of the cleaner article was evaluated based on this cleaning rate (%). The cleaning rate (%) is the average value of three pieces of artificially soiled cloth. The results are shown in Table 1. It can be said that the higher the cleaning rate, the higher the cleaning ability of the cleaner article. The reflectance of the original fabric of the artificially soiled cloth is the reflectance of the above-mentioned cotton / polyester broadcloth spun cloth to which no artificial dirt is applied. Cleaning rate (%) = 100 × [(reflectance of artificially soiled cloth after cleaning - reflectance of artificially soiled cloth before cleaning) / (reflectance of original cloth - reflectance of artificially soiled cloth before cleaning)] (1)

[0103] <Measurement of the thickness of the coating layer of an anionic surfactant in an alkaline agent> From the cleaning composition prepared by the method described above in <Preparation of cleaning composition>, 10 (b) anionic surfactant-coated (d) alkaline agent particles were randomly sampled. The sampled alkaline agent particles were cut in half with a scalpel along the plane containing the maximum particle diameter so as not to break them, and the cross section was observed under a scanning electron microscope (S-3000, Hitachi, Ltd., magnification 500x). From the images obtained with the scanning electron microscope, the thickness of the coating layer of the anionic surfactant in the alkaline agent, i.e., the coating layer of component (b) in component (d), was calculated. Table 1 shows the average thickness of the coating layer of component (b) calculated for 10 pieces of component (d).

[0104] <Evaluation of Powder Flowability of Detergent Composition> The detergent composition prepared by the method described in the above <Preparation of detergent composition> was added to a container with a volume of 50 cm 3 Put it into a cylindrical container and pour it into a 50cm 3 of the cleaning composition was measured out. This cleaning composition was poured into a cone-shaped container (8.5 cm long, 8.5 cm wide, 14 cm high) with a 1 cm diameter hole at the bottom, and the time (in seconds) until all of the cleaning composition poured into the container had fallen out was measured, using the time it took to pour the composition as the base time. The shorter this time, the more excellent the fluidity of the detergent composition. In addition, when the detergent composition remained in the container and this time could not be measured, this is indicated by "X" in the table.

[0105] <Solubility evaluation> The solubility of the detergent articles in Table 1 was evaluated based on the diameter of the undissolved residue of the detergent composition that remained after washing. The diameter of the undissolved residue of the detergent composition was measured by the following method. 1 kg of a cotton shirt (100% cotton, manufactured by Gunze) was washed for 10 minutes in a fully automatic washing machine (NA-FR80H6, manufactured by Panasonic) with 20 L of water. The specific washing conditions were as follows: 1 kg of a cotton shirt and one detergent article in which 13 g of each detergent composition listed in Table 1 was packaged in a water-soluble film were placed in the fully automatic washing machine, 20 L of water was poured in, and the detergent article was dissolved in water to prepare a cleaning solution, and at the same time, the cotton shirt was washed for 10 minutes. The bath ratio (water (kg) / cotton shirt (kg)) was 20. The water temperature of each cleaning solution was 20°C. After washing, the fabric was rinsed twice with city water (20° C.) for 3 minutes. After rinsing, the fabric was press-dried using a dryer (OT-20S, manufactured by Tosen Corporation). After washing, the cotton shirt was visually inspected and the residue of the detergent composition that had not dissolved was collected. The diameter (mm) of the collected residue was measured with a caliper and the average value is shown in Table 1. The smaller the size of the residue, or even if no residue was found, the better the solubility of the detergent composition and the detergent article.

[0106] [Table 1]

Claims

1. A detergent article comprising: a detergent composition containing the following components (a), (b), (c), and (d), wherein component (d) has a coating layer of component (b), and the coating layer of component (b) has a thickness of 0.1 μm or more and 50 μm or less; and a water-soluble film for packaging the detergent composition: Component (a): Nonionic surfactant Component (b): Anionic surfactant (c) Component: Oil-absorbing carrier Component (d): Alkaline agent

2. 2. The detergent article according to claim 1, wherein in the detergent composition, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is 0.1 or more and 10 or less.

3. 3. The detergent article according to claim 1 or 2, wherein in the detergent composition, the mass ratio (a) / (c) of the content of the component (a) to the content of the component (c) is 0.1 or more and 10 or less.

4. 3. The detergent article according to claim 1 or 2, wherein in the detergent composition, the mass ratio (b) / (d) of the content of the component (b) to the content of the component (d) is 0.01 or more and 5 or less.

5. The detergent article according to claim 1 or 2, wherein the coating layer of the component (b) is formed by spraying an acid precursor of the component (b) onto the component (d).

6. 3. The detergent article according to claim 1 or 2, wherein the component (b) comprises (b1) an alkylbenzenesulfonic acid and / or a salt thereof (hereinafter referred to as the component (b1)), and (b2) a fatty acid and / or a salt thereof (hereinafter referred to as the component (b2)).

7. The detergent article according to claim 6, wherein the mass ratio (b1) / (b2) of the content of the component (b1) to the content of the component (b2) is 0.01 or more and 10 or less.

8. The detergent article according to claim 1 or 2, wherein component (c) is a water-insoluble oil-absorbing carrier.

9. 3. The detergent article according to claim 1, wherein the component (c) is at least one selected from amorphous silica, calcium silicate, crystalline aluminosilicate, amorphous aluminosilicate, and clay minerals.

10. The detergent article according to claim 1 or 2, wherein the component (a) is supported on the component (c).

11. 3. The detergent article according to claim 1, wherein the component (d) is a powder having an average primary particle size of 10 μm or more and 1000 μm or less.

12. The detergent article according to claim 1 or 2, wherein component (d) is a water-soluble oil-absorbing carrier.

13. The cleaning article according to claim 1 or 2, which is for textile products.