Liquid cleaning agents

Abstract

To provide a liquid detergent that excels in a stable appearance of liquid component (component other than particles), stable dispersion of the particles including after storage, a stable appearance of the particles, and persistency.SOLUTION: A liquid detergent contains component (A): at least one structuring agent selected from bacterial cellulose, non-bacterial cellulose and a specific compound, component (B): particles with a volume-average particle size of 100 μm or more. The component (B) shows a smaller particle size when dissolved in water. Relative to the total mass of the liquid detergent, water content is less than 30 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid cleaning agent. [Background technology]

[0002] In recent years, consumers have been demanding that liquid detergents not only have cleaning performance but also other functionalities such as softness and lingering fragrance. Furthermore, in the detergent product market, there is a demand for liquid detergent products to have a distinctive aesthetic appearance in order to distinguish them from other products. To meet such demands, a technique is known in which visible particles containing functional components are blended into a liquid detergent. However, when these particles are suspended in a liquid detergent, the particles may not be uniformly dispersed. To achieve uniform dispersion of the particles, it is necessary to impart suitable rheological properties to the liquid detergent. Furthermore, the particles must be uniformly dispersed in the liquid detergent, and must dissolve or disintegrate properly when the liquid detergent is used to form a cleaning solution. If the particles do not dissolve or disintegrate properly, they may leave residue on the laundry after washing.

[0003] For example, Patent Document 1 describes a technique for imparting thixotropy to a liquid detergent using a crystalline fatty acid glyceride. Patent Document 2 describes a technique for suspending particles in a liquid detergent using a structuring agent having a specific viscosity. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-147934 [Patent Document 2] Special Publication No. 2007-500268 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although Patent Document 1 describes that capsule particles containing a fragrance composition or the like can be incorporated into a liquid detergent without separation, it does not actually evaluate whether the capsule particles are uniformly dispersed. Therefore, the technology described in Patent Document 1 still has room for improvement in the dispersion stability of the particles. Furthermore, Patent Document 1 does not consider whether the particles remain on the washed items after washing. Furthermore, in the technology described in Patent Document 2, the particles may dissolve during storage of the liquid detergent. Therefore, the technology described in Patent Document 2 still has room for improvement in terms of maintaining the particle appearance without dissolving in the liquid detergent (stability of particle appearance).

[0006] The present invention aims to provide a liquid detergent that improves the appearance stability of the liquid detergent and the dispersion stability of the particles, and that can maintain the dispersion stability of the particles even after storage, that can maintain the appearance stability of the particles without the particles dissolving in the liquid detergent, and that can prevent particles from remaining on the washed items after washing. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] Component (A): one or more structuring agents selected from bacterial cellulose, non-bacterial cellulose, and compounds represented by the following general formula (1), (B) component: particles with a volume average particle diameter of 100 μm or more; A liquid cleaning agent comprising: When 150 mL of water and 0.4 g of the component (B) are placed in a 200 mL beaker at room temperature and stirred at 500 rpm for 10 minutes using a 4 cm stirrer, the particle size after stirring becomes smaller than the particle size before stirring, A liquid detergent having a water content of less than 30% by mass relative to the total mass of the liquid detergent. [ka] In formula (1), Z1 ~Z 3 are each independently a hydrogen atom, a hydroxy group, or a carboxy group. 1 ~Z 3 may be the same or different. In formula (1), a+b=7 to 19, c+d=7 to 19, and e+f=7 to 19. [2] The liquid detergent according to [1], wherein the component (B) is a coated particle having a core and a coating covering part or all of the surface of the core. [3] The liquid detergent described in [2], wherein the coating portion contains one or more selected from the group consisting of hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose, hydroxyethyl cellulose, polyacrylic acid, salts of polyacrylic acid, acrylic acid-maleic acid copolymer, salts of acrylic acid-maleic acid copolymer, fatty acid, salts of fatty acid, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, and calcium carbonate. [4] The liquid detergent according to any one of [1] to [3], wherein the component (B) comprises one or more selected from the group consisting of water-soluble inorganic compounds and enzymes. [5] The liquid detergent described in [2], wherein the core contains one or more selected from the group consisting of sodium chloride, sodium carbonate, and an enzyme preparation. [6] The liquid detergent according to [3], wherein the coating contains one or more selected from the group consisting of polyacrylic acid, salts of polyacrylic acid, acrylic acid-maleic acid copolymers, and salts of acrylic acid-maleic acid copolymers, and one or more selected from the group consisting of sodium sulfate and calcium carbonate. [7] The liquid detergent according to any one of [1] to [6], further comprising a surfactant as component (C). [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a liquid detergent that can improve the appearance stability of the liquid detergent and the dispersion stability of the particles, and can maintain the dispersion stability of the particles even after storage, so that the particles do not dissolve in the liquid detergent and the appearance stability of the particles can be maintained, and the particles can be prevented from remaining on the washed items after washing. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. The liquid detergent of the present invention contains the following components (A) and (B). The liquid detergent preferably further contains the following component (C): The liquid detergent may contain components other than components (A), (B), (C) and water. (Optional components) may be contained. In this specification, the stability and beauty of the appearance of particles existing in a solid state in a liquid detergent is also collectively referred to as "appearance stability."

[0010] <Liquid cleaning agent> In the liquid detergent of the present invention, component (B) is dispersed in a liquid portion in which component (A) is dissolved. <Component (A)> Component (A) is one or more structuring agents selected from bacterial cellulose, non-bacterial cellulose, and compound (1) described below. When the liquid detergent contains component (A), the dispersion stability of component (B) is improved. In the present invention, "structuring" refers to a state in which the viscosity changes before and after the application of force.

[0011] Bacterial cellulose is cellulose produced by fermentation of bacteria of the genus Acetobacter. Examples of bacterial cellulose include so-called reticulated bacterial cellulose, in which water-insoluble fibers are branched in a reticulated pattern and interdigitate with each other to form a network.

[0012] At least a portion of the bacterial cellulose may be coated with or mixed with a thickening agent. Examples of thickening agents include carboxymethylcellulose (CMC), modified CMC, xanthan products, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, gum ghatti, karaya gum, gum tragacanth, tamarind gum, and locust bean gum. The thickener may be used alone or in combination of two or more.

[0013] Commercially available bacterial cellulose can be used, for example, CELLULON (registered trademark) manufactured by CPKelco US.

[0014] Non-bacterial cellulose is cellulose obtained from plants such as vegetables, fruits, and wood, and is also called cellulose fiber.

[0015] As the non-bacterial cellulose, commercially available products can be used, such as "Avicel (registered trademark)" manufactured by FMC Corporation, "Citri-Fi" manufactured by Fiberstar, and "Betafib" manufactured by Cosun.

[0016] Compound (1) is a compound (triglyceride component) represented by the following general formula (1).

[0017] [ka]

[0018] In formula (1), Z 1 ~Z 3 are each independently a hydrogen atom, a hydroxy group, or a carboxy group. 1 ~Z 3 may be the same or different. In formula (1), a+b=7 to 19, c+d=7 to 19, and e+f=7 to 19, preferably a+b=11 to 15, c+d=11 to 15, and e+f=11 to 15, and more preferably a+b=13 to 15, c+d=13 to 15, and e+f=13 to 15. When a+b, c+d, and e+f are each 7 or greater, the volume of the hydrophobic group moiety becomes sufficiently bulky, enhancing application and cleaning power. On the other hand, when a+b, c+d, and e+f are each 19 or less, the risk of solidification due to the increased volume of the hydrophobic group moiety is reduced.

[0019] Compound (1) includes Z 1 ~Z 3 Compound (1-1) in which Z is a hydroxy group; 1 ~Z 3 is a hydrogen atom, and the like. As the compound (1-1), hydrogenated castor oil is particularly preferred, and as the compound (1-2), hydrogenated palm oil is particularly preferred. Examples of hydrogenated castor oil include glycerides, particularly triglycerides, containing an alkyl or alkenyl group having 10 to 22 carbon atoms and a hydroxyl group, such as trihydroxystearin and dihydroxystearin. Hydrogenated castor oil is obtained by hydrogenating castor oil to convert double bonds that may be present in the starting oil as ricinoleyl moieties (heptadecadienylcarbonyloxy groups) into saturated hydroxyalkyl moieties, such as hydroxystearyl groups. The hydrogenated castor oil can be processed in any suitable starting form, including but not limited to, it can be used in a solid state, a melt state, or a mixture thereof.

[0020] As the hydrogenated castor oil, commercially available products can be used, such as "THIXCIN (registered trademark)" manufactured by Rheox, Inc. and "Castarwax A Flake" manufactured by NOF Corporation. As the hardened palm oil, commercially available products can be used, for example, "Extremely Hardened Palm Oil A" manufactured by New Japan Chemical Co., Ltd.

[0021] As component (A), bacterial cellulose and non-bacterial cellulose are preferred, with bacterial cellulose being more preferred, because even a small amount can sufficiently enhance the dispersion stability of component (B) and it is easy to obtain a highly transparent liquid appearance.

[0022] The content of component (A) is preferably 0.02 to 2% by mass, more preferably 0.04 to 1.5% by mass, and even more preferably 0.05 to 1.0% by mass, based on the total mass of the liquid detergent. For example, when a bacterial cellulose preparation such as the commercially available product "CELLULON (registered trademark)" is used as component (A), the content of component (A) as is in the product is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and even more preferably 2.5 to 7% by mass, based on the total mass of the liquid detergent. If the content of component (A) is equal to or greater than the lower limit, the dispersion stability of component (B) is improved. If the content of component (A) is equal to or less than the upper limit, the viscosity of the liquid detergent is reduced, improving usability.

[0023] <(B) component> Component (B) is a particle having a volume average particle diameter of 100 μm or more. Component (B) may be a primary particle or a secondary particle formed by aggregation of primary particles. The liquid detergent of the present invention may contain one particle or multiple particles. (B) Component is such that when 150 mL of water and 0.4 g of particles are placed in a 200 mL beaker at room temperature and stirred at 500 rpm for 10 minutes using a 4 cm stirrer, the particle size after stirring is smaller than the particle size before stirring. When the component (B) has the above characteristics, it becomes easier to prevent the component (B) from remaining on the washed items after washing. Here, the phrase "the particle size after stirring is smaller than the particle size before stirring" also includes a state in which the particles are dissolved in water. It is preferable that component (B) is such that when 150 mL of water and 0.4 g of particles are placed in a 200 mL beaker at room temperature and stirred at 500 rpm for 5 minutes using a 4 cm stirrer, the particle size after stirring is smaller than the particle size before stirring. Component (B) may be uncoated particles (hereinafter also referred to as "component (B1)"), which have no surface coating, or may be coated particles (hereinafter also referred to as "component (B2)"), which have a core and a coating that covers part or all of the surface of the core.

[0024] ((B1) component) Examples of the component (B1) include bleaching agents, bleach activators, alkali agents, pearling agents, pigments, mica, clay, water-soluble inorganic compounds, enzymes, detergent compositions, and fragrances. The component (B1) may be in the form of a solid, a gel, or a mixture thereof, as long as it is in particulate form in the liquid detergent. The component (B1) may be a solid (granular) granulated product. It is also possible to use a granulation product prepared by a conventional granulation method using the components exemplified above as component (B1) and an organic or inorganic compound, such as a stabilizer, filler, extender, brightener, binder, or coating agent. When granulating two or more types of component (B1), they may be granulated separately, or the (B1)s may be mixed together to form the same granule. The granulation method for component (B1) is not particularly limited, and any known method can be used.

[0025] A water-soluble inorganic compound is an inorganic compound whose solubility in ion-exchanged water at 25°C (hereinafter sometimes simply referred to as "solubility") is 0.1 g / 100 g or more. The solubility of a water-soluble inorganic compound is preferably 1 g / 100 g or more, more preferably 2 g / 100 g or more. The definition of a water-soluble inorganic compound is based on "Chemical Handbook" compiled by the Chemical Society of Japan, etc. Any inorganic compound can be suitably used as long as it is such a water-soluble inorganic compound, but preferred inorganic compounds include those generally used as detergent builders.

[0026] The water-soluble inorganic compound can be determined taking into consideration the desired function of component (B). Examples of the water-soluble inorganic compound include carbonates, hydrogen carbonates, sesquicarbonates, silicates, sulfates, sulfites, nitrates, nitrites, chlorides, and phosphates. Examples of carbonates include sodium carbonate and potassium carbonate. Examples of hydrogen carbonates include sodium hydrogen carbonate and potassium hydrogen carbonate. Examples of sesquicarbonates include sodium sesquicarbonate. Examples of silicates include sodium metasilicate, sodium orthosilicate, layered sodium silicate, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, No. 4 sodium silicate, No. 5 sodium silicate, No. 1 potassium silicate, No. 2 potassium silicate, and the like. Examples of sulfates include sodium sulfate, potassium sulfate, and magnesium sulfate. Nitrite salts include sodium nitrite and potassium nitrite. Examples of nitrates include sodium nitrate, potassium nitrate, calcium nitrate, and magnesium nitrate. Examples of chlorides include sodium chloride, potassium chloride, and magnesium chloride. Examples of phosphates include orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, and phytates. Among these, from the viewpoint of enhancing the detergency of the liquid detergent, preferred water-soluble inorganic compounds are carbonates, bicarbonates, sesquicarbonates, and silicates, with carbonates and silicates being more preferred. As carbonates, sodium carbonate and potassium carbonate are more preferred, with sodium carbonate being particularly preferred, because they rapidly dissolve in a cleaning solution obtained by diluting the liquid detergent with water, thereby increasing the pH of the cleaning solution and further improving detergency. As silicates, sodium silicate and potassium silicate are preferred, with sodium silicate being more preferred. As sodium silicates, sodium metasilicate, sodium orthosilicate, layered sodium silicate, No. 1 sodium silicate, and No. 2 sodium silicate are preferred, because they can further increase the pH of the cleaning solution. Sodium metasilicate, sodium orthosilicate, No. 1 sodium silicate, and No. 2 sodium silicate are more preferred, with sodium metasilicate, sodium orthosilicate, No. 1 sodium silicate, and No. 2 sodium silicate being more preferred, with sodium metasilicate, sodium orthosilicate, and No. 1 sodium silicate being even more preferred, and sodium metasilicate and sodium orthosilicate being particularly preferred. These water-soluble inorganic compounds increase the pH of the cleaning solution, thereby further improving detergency. The water-soluble inorganic particles may be used alone or in combination of two or more kinds.

[0027] Examples of enzymes include proteases, amylases, lipases, cellulases, mannanases, and pectinases. Examples of proteases include protease preparations available from Novozymes under the trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Savinase Evity 16L, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Liquanase Evity 3.5L, Coronase 48L, Coronase Evity 48L, Progress Uno 100L, Progress Excel 101L, Deozyme, Savinase Evity 12T, and Kannase Evity 24T; and products available from DuPont under the trade names EFFECTENZ P150 and EFFECTENZ Examples include P100 and PREFERENZ P100. Examples of amylase include amylase preparations available from Novozymes under the trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, Amplify 12L, Amplify Prime 100L, and Stainzyme Plus 12T; available from DuPont under the trade name EFFECTENZ S100; available from Amano Enzyme Co., Ltd. under the trade name Pullulanase Amano; and available from Seikagaku Corporation under the trade name DB-250. Examples of lipase include lipase preparations available from Novozymes under the trade names Lipex 100L, Lipolase 100L, and Lipex 100T. Examples of cellulases include cellulase preparations available from Novozymes under the trade names Carezyme Premium 4500L, Celluclean 5000L, and Celluclean 4500T, and those available from DuPont under the trade name REVITALENTZ 2000. Examples of mannanase include mannanase preparations available from Novozymes under the trade names Mannaway 4L, Mannaway 200L, and Mannaway 4.0T. Examples of pectinase include a pectinase preparation available from Novozymes under the trade name Xpect 1000L. Examples of multi-enzymes containing two or more enzymes include Medley Core 210L, Medley Core 200L, Medley Boost 300L, Medley Advance 200T, Medley Glow 200L, Medley Brilliant 100L, Medley Essential 200L, Medleyey Core 200T, Medley CleanR, Medley Essential 200T, Medley SmartR, Medley Advance 200T, Medley Boost 200L, Medley Boost 200T, and Medley SuperioR 100T. The enzymes may be used singly or in combination of two or more. The enzyme may be a solid (granular) enzyme preparation. As a solid enzyme preparation, a granulated product containing a stabilizer, filler, extender, brightener, binder, coating agent, etc., based on a conventional granulation method can also be used. When granulating two or more types of enzymes, the enzymes may be granulated separately, or the enzymes may be mixed and granulated into the same product. There are no particular limitations on the method for granulating the enzyme, and any known method can be used.

[0028] ((B2) component) Component (B2) is a coated particle having a core and a coating that covers part or all of the surface of the core. The core may contain particles, for example, the above-mentioned component (B1) (hereinafter, particles contained in the core may also be referred to as "particles within the core"). The content of component (B1) in the core particles is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the core particles.

[0029] The number of particles in the core per component (B2) may be one or two or more.

[0030] <Coated part> The coating portion is formed from a coating agent. The coating portion allows the component (B2) to have a slower dissolution rate in the liquid portion.

[0031] The coating agent is preferably one that is poorly soluble in liquid detergent and easily adheres to the core, but quickly dissolves, swells, disintegrates, or disperses in a cleaning solution prepared by diluting the liquid detergent with water, and is easily detached from the core. Examples of the coating agent include salt-sensitive polymers, such as polymers having units derived from acrylic acid (hereinafter also referred to as "acrylic acid polymers"), polymers having units derived from maleic acid (hereinafter also referred to as "maleic acid polymers"), polymers having units derived from acrylic acid and units derived from maleic acid (hereinafter also referred to as "MA polymers"), polymers having units derived from olefin and units derived from maleic acid or salts thereof (hereinafter also referred to as "maleic acid olefin copolymers"), polyvinyl alcohol, modified polyvinyl alcohol, polysaccharides, and other polymers; inorganic compounds (however, different from the water-soluble inorganic compounds contained in the core); fatty acids or salts thereof; and the like. Examples of the MA polymer include an acrylic acid-maleic acid copolymer or a salt thereof. The mass average molecular weight of the MA polymer is preferably 10,000 to 200,000, more preferably 4,000 to 100,000, and even more preferably 8,000 to 80,000. The mass average molecular weight is a value measured by gel permeation chromatography or the like. Examples of polysaccharides include hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl methylcellulose, pullulan, xanthan gum, starch, and modified starch. The viscosity of an aqueous solution of the polysaccharide is preferably 1 to 5000 mPa·s, more preferably 1 to 2500 mPa·s, even more preferably 1 to 1000 mPa·s, and particularly preferably 1 to 500 mPa·s. The viscosity of the aqueous solution of the polysaccharide is the value of a 2% by mass aqueous solution at 20°C. The fatty acids include fatty acids having carbon atoms of 12 to 18. The fatty acid salts include sodium salts, potassium salts, calcium salts, and the like. Examples of inorganic compounds include polyvalent chlorides such as calcium chloride, calcium nitrate, magnesium chloride, and aluminum chloride; polyvalent sulfates such as magnesium sulfate and aluminum sulfate; polyvalent nitrates such as calcium nitrate and magnesium nitrate; polyvalent organic acid salts such as calcium acetate and calcium citrate; calcium oxide; calcium hydroxide; and salts such as sodium tetraborate. The volume average particle size of the inorganic compound is preferably smaller than the volume average particle size of the core, more preferably 10 to 2000 μm, and even more preferably 50 to 1500 μm. Among these, from the viewpoint of slowing down the dissolution rate of component (B2) in the liquid portion and maintaining the particle shape in the liquid detergent, acrylic acid polymers, maleic acid polymers, maleic acid-olefin copolymers or salts thereof, MA polymers, maleic acid-olefin copolymers or salts thereof, polyacrylic acid or salts thereof, polysaccharides, polyvinyl alcohol, inorganic compounds, and combinations thereof are preferred, and acrylic acid polymers, maleic acid polymers, acrylic acid-maleic acid copolymers or salts thereof, polyacrylic acid or salts thereof, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose, hydroxyethyl cellulose, hydroxyethyl methylcellulose, polyvinyl alcohol, calcium chloride, calcium nitrate, calcium acetate, sodium sulfate are preferred. , calcium carbonate are more preferred, hydroxypropyl methylcellulose, acrylic acid polymers, maleic acid polymers, acrylic acid-maleic acid copolymers or salts thereof, maleic acid olefin copolymers or salts thereof, polyvinyl alcohol, calcium chloride, calcium nitrate, and calcium acetate are even more preferred, and combinations of hydroxypropyl methylcellulose, acrylic acid polymers, maleic acid polymers, acrylic acid-maleic acid copolymers or salts thereof with at least one selected from the group consisting of calcium chloride, calcium nitrate, and calcium acetate, combinations of maleic acid olefin copolymers or salts thereof with at least one selected from the group consisting of calcium chloride, calcium nitrate, and calcium nitrate, and polyvinyl alcohol are particularly preferred. The coating agent may be used alone or in combination of two or more.

[0032] The coverage of component (B2) is preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, particularly preferably 90% or more, and may be 100%. If the coverage is equal to or greater than the lower limit, the dissolution rate of component (B2) in the liquid portion is slowed, and component (B2) can exist in a better state as particles in the liquid detergent. The coverage is the ratio of the area of ​​the coated portion to the total area of ​​the (B2) component in a planar view when observing the (B2) component. The coverage can be determined, for example, by observing the (B2) component coated with a colored coating agent and calculating the ratio of the area of ​​the colored coated portion to the total area of ​​the (B2) component in a planar view. The coverage is the average value of the coverages of 100 arbitrary particles of the (B2) component. Any commercially available colorant can be used as the colorant. Examples of colorants include Green No. 3 (trade name, manufactured by Kishi Kasei Co., Ltd.). A colorant concentration of 0.001% by mass to 5% by mass in an aqueous solution containing the coating agent can color the core particles, making it easier to observe the coated portion in the above-mentioned method for measuring coverage.

[0033] The mass of the coating agent in component (B2) is preferably 0.1 to 15 mass% and more preferably 1 to 13 mass% based on the total mass of component (B2). If the mass of the coating agent is equal to or greater than the lower limit, the coverage is sufficiently increased, the dissolution rate of component (B2) into the liquid portion is slowed, and the presence of component (B2) in the liquid detergent is more easily visible. If the mass of the coating portion is equal to or less than the upper limit, the solubility of component (B2) in the detergent is improved.

[0034] The amount of core particles in component (B2) is preferably 50 to 99% by mass, more preferably 60 to 98% by mass, and particularly preferably 70 to 97% by mass, based on the total mass of component (B2). When the amount of core particles is within the above lower limit, the effects of the core particles (e.g., increasing the pH of the cleaning solution and improving the detergency of the liquid detergent) are easily achieved when a liquid detergent containing component (B2) is diluted with water to form a cleaning solution. When the amount of core particles is within the above upper limit, the amount of coating agent is sufficient, further slowing the dissolution rate of component (B2) in the liquid.

[0035] When a salt-sensitive polymer is used as the coating agent, the amount of the inorganic compound is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on the total mass of component (B2). If the amount of the inorganic compound is equal to or greater than the lower limit, it reacts sufficiently with the salt-sensitive polymer to form a crosslinked structure, further slowing the dissolution rate of component (B2) into the liquid. If the amount of the inorganic compound is equal to or less than the upper limit, the amount of core particles in component (B2) is not reduced, and the various effects of the core particles in the cleaning solution (e.g., improved detergency) can be more reliably achieved.

[0036] When a salt-sensitive polymer is used as the coating agent, the ratio of the salt-sensitive polymer to the inorganic compound (salt-sensitive polymer / inorganic compound) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 80 / 20, and particularly preferably 30 / 70 to 70 / 30. When the ratio of the salt-sensitive polymer to the inorganic compound is within the above range, the salt-sensitive polymer can react sufficiently with the inorganic compound, and the dissolution rate of component (B2) in the liquid portion can be further slowed.

[0037] The term "salt-sensitive polymer" as used herein refers to a polymer that increases in viscosity, gels, or forms a film in response to an inorganic compound. Such polymers preferably have anionic reactive groups such as carboxyl groups or sulfate groups, and react with polyvalent metal ions to crosslink. Examples of such salt-sensitive polymers include polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymers, alginic acid, carrageenan, cellulose sulfide, and alkali metal salts thereof, as well as polymers of monoalkali metal salts of ethylene-containing alkyl phosphate esters. Examples of polymers without anionic reactive groups include polyvinyl alcohol, which gels in response to sodium tetraborate.

[0038] When a salt-sensitive polymer, such as polyacrylic acid, having anionic reactive groups, such as carboxyl or sulfate groups, is used as the coating agent, the amount of coating agent is preferably 0.1 to 15 mass% of the mass of component (B2), more preferably 1 to 13 mass%, and particularly preferably 2 to 10 mass%. When the amount of coating agent containing a polymer having anionic reactive groups, such as carboxyl or sulfate groups, is equal to or greater than the lower limit, the coverage rate is sufficiently increased, the dissolution rate of component (B2) into the liquid is slowed, and the presence of component (B2) in the liquid detergent is easily visible. When the amount of coating agent is equal to or less than the upper limit, the solubility of component (B2) in the cleaning solution is likely to be good.

[0039] When a salt-sensitive polymer without an anionic reactive group, such as polyvinyl alcohol, is used as the coating agent, the mass of the coating agent is preferably 0.1 to 15 mass% of the total mass of component (B2), more preferably 1 to 10 mass%, and particularly preferably 3 to 8 mass%. When the amount of coating agent containing a polymer without an anionic reactive group, such as polyvinyl alcohol, is equal to or greater than the lower limit, the coverage is sufficiently increased, the dissolution rate of component (B2) into the liquid is slowed, and the presence of component (B2) in the liquid detergent is easily visible. When the amount of coating agent is equal to or less than the upper limit, the solubility of component (B2) in the detergent tends to be good.

[0040] When a polysaccharide is used as the coating agent, the mass of the coating agent is preferably 1 to 15 mass% of the total mass of component (B2), more preferably 3 to 13 mass%, and particularly preferably 5 to 10 mass%. If the amount of polysaccharide coating agent is equal to or greater than the above lower limit, the coverage rate is sufficiently increased, the dissolution rate of component (B2) into the liquid can be slowed, and the presence of component (B2) in the liquid detergent can be easily visually recognized. If the amount of coating agent is equal to or less than the above upper limit, the solubility of component (B2) in the detergent tends to be good.

[0041] The content of component (B) is preferably 0.01 to 15 mass% of the total mass of the liquid detergent, more preferably 0.1 to 13 mass%, even more preferably 0.5 to 10 mass%, and particularly preferably 1.0 to 8 mass%. If the content of component (B) is equal to or greater than the lower limit, more of component (B2) can be visually recognized, resulting in an excellent appearance of the liquid detergent. If the content of component (B) is equal to or less than the upper limit, the dispersion stability of the particles is further improved.

[0042] The volume average particle size of component (B) is 100 μm or more, preferably 100 to 2000 μm, more preferably 130 to 1500 μm, and even more preferably 150 to 1000 μm. When the volume average particle size of component (B) is at least the above lower limit, the dissolution rate is easily controlled and the particle appearance is excellent. When the particle size of component (B) is at most the above upper limit, the dissolution rate in water is improved. Considering use in washing machines and automatic dispensers with automatic detergent dispensing functions, the volume average particle diameter of component (B) is preferably less than 350 μm, more preferably 200 μm or less. If the volume average particle diameter of component (B) is equal to or less than the above upper limit, component (B) dissolves quickly when the liquid detergent is diluted with water. Furthermore, solid component (B) is less likely to remain in the washing machine inlet or on washed clothes.

[0043] The mass ratio of component (A) to component (B) (hereinafter also referred to as "A / B ratio") is preferably 0.01 to 30, more preferably 0.1 to 25, more preferably 1 to 20, and even more preferably 5 to 15. When the A / B ratio is equal to or greater than the above lower limit, the thixotropy is improved, and the dispersion stability of component (B) is further improved. When the A / B ratio is equal to or less than the above upper limit, the usability of the liquid detergent is further improved.

[0044] <(C) component> Component (C) is a surfactant. If the liquid cleaner contains a surfactant, it will have better cleaning power. The surfactant is not particularly limited as long as it is a surfactant used in conventional liquid detergents, and examples thereof include nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, and semi-polar surfactants. One type of surfactant may be used, or two or more types of surfactants may be used in combination. From the viewpoint of further enhancing detergency, it is preferable to contain a nonionic surfactant and a non-soap anionic surfactant. A nonionic surfactant, a non-soap anionic surfactant, and one or more surfactants selected from the group consisting of cationic surfactants, amphoteric surfactants, and semi-polar surfactants may be used in combination.

[0045] Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides. The nonionic surfactants may be used alone or in combination of two or more. As the nonionic surfactant, polyoxyalkylene-type nonionic surfactants are preferred, and among them, in particular, a compound represented by the following general formula (2) (hereinafter also referred to as "compound (2)") and a compound represented by the following general formula (3) (hereinafter also referred to as "compound (3)") are more preferred, with compound (2) being even more preferred.

[0046] R 11 -O-[(EO) s / (A 11 O) t ]-(EO) u -R 12 ···(2) (In general formula (2), R11 R is a straight or branched chain hydrocarbon group having 8 to 22 carbon atoms. 12 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. s is a number from 3 to 25 indicating the average number of EO repeats. A 11 O represents at least one of PO (oxypropylene group) and BO (oxybutylene group). 11 is a number between 0 and 6 that indicates the average number of repeats of O. u is a number between 0 and 20 that indicates the average number of repeats of EO.

[0047] R 13 -X-[(EO) p / (A 12 O) q ]-(EO) r -R 14 ···(3) (In general formula (3), R 13 is a hydrocarbon group having 7 to 21 carbon atoms. -X- is -COO- or -CONH-. R 14 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. p is a number from 3 to 25 that indicates the average number of EO repeats. A 12 represents at least one of PO (oxypropylene group) and BO (oxybutylene group). 12 is a number between 0 and 6 that indicates the average number of repeats of O. r is a number between 0 and 20 that indicates the average number of repeats of EO.

[0048] The content of the nonionic surfactant is preferably 5 to 70 mass % relative to the total mass of the liquid detergent, more preferably 10 to 50 mass %, and even more preferably 15 to 40 mass %.

[0049] Examples of non-soap anionic surfactants include carboxylic acid-type anionic surfactants such as linear alkylbenzenesulfonic acid or its salt (LAS), α-olefinsulfonic acid or its salt (AOS), linear or branched alkyl sulfate ester or its salt (AS), polyoxyalkylene alkyl(alkenyl) ether sulfate ester or its salt (AES), alkyl group-containing alkanesulfonic acid or its salt, α-sulfofatty acid ester or its salt, internal olefinsulfonic acid or its salt (IOS), hydroxyalkanesulfonic acid or its salt (HAS), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, and acylaminocarboxylic acid or its salt; and phosphate ester-type anionic surfactants such as alkyl phosphate ester or its salt, polyoxyalkylene alkyl phosphate ester or its salt, polyoxyalkylene alkylphenyl phosphate ester or its salt, and glycerin fatty acid ester monophosphate ester or its salt. Examples of salt forms of non-soap anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). The non-soap anionic surfactants may be used alone or in combination of two or more. Preferred non-soap anionic surfactants are LAS, AOS, AS, AES, IOS, and HAS, with LAS, AES, and IOS being more preferred from the viewpoint of enhancing detergency. Liquid detergents preferably contain at least AES, and more preferably contain both LAS and AES.

[0050] The polyoxyalkylene alkyl(alkenyl) ether sulfate or its salt (AES) is represented by the following general formula (4). R 15 -O-[(EO) m / (PO) n ]-SO3 -M + ···(4) (In general formula (4), R 15 is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms. EO is an oxyethylene group. PO is an oxypropylene group. m is a number of 0.1 or more representing the average number of repetitions of EO. n is a number of 0 to 6 representing the average number of repetitions of PO. [(EO) m / (PO) n ] indicates that there is no restriction on the order of EO and PO, and M + is the countercation.)

[0051] Internal olefin sulfonic acid or its salt (IOS) is a mixture of an alkene sulfonic acid represented by the following formula (5) (hereinafter also referred to as "compound (5)") and a hydroxyalkane sulfonic acid represented by the following formula (6) (hereinafter also referred to as "compound (6)"). The internal olefin refers to an olefin in which the double bond is located inside the 2-position.

[0052] R 16 -CH=CH(CH2) x CH(SO3M)-R 17 ···(5) (In formula (5), R 16 is an alkyl group, and R 17 is an alkyl group having 1 to 5 carbon atoms, and the total number of carbon atoms is 8 to 24. x is a number from 0 to 4, and M represents a counter ion.

[0053] The number of carbon atoms in compound (5) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. When the number of carbon atoms is equal to or greater than the lower limit, the lipophilicity of IOS is increased, and its function as a surfactant is enhanced. When the number of carbon atoms is equal to or less than the upper limit, the hydrophilicity of IOS is increased, and its function as a surfactant is enhanced.

[0054] R in equation (5) 16 represents an alkyl group. 16 The number of carbon atoms is preferably 1 to 21, more preferably 3 to 17, and even more preferably 7 to 15. R in equation (5) 17 represents an alkyl group having 1 to 5 carbon atoms. 17 The number of carbon atoms is preferably 1 to 3. In formula (5), x is 0 to 4, and preferably 0 to 2. When x is equal to or greater than the lower limit, the cleaning power is further increased. When x is equal to or less than the upper limit, the appearance stability of the liquid portion is further increased. Examples of M in the formula (5) include sodium ion, potassium ion, magnesium ion, and ammonium ion.

[0055] R 18 -CH(OH)(CH2) y CH(SO3M)-R 19 ···(6) (In formula (6), R 18 is an alkyl group, and R 19 is an alkyl group having 1 to 5 carbon atoms, and the total number of carbon atoms is 8 to 24; y is a number from 0 to 4; and M represents a counter ion.

[0056] Compound (6) is a hydroxy compound of compound (5). The number of carbon atoms in compound (6) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. When the number of carbon atoms is equal to or greater than the lower limit, the lipophilicity of IOS is increased, and its function as a surfactant is enhanced. When the number of carbon atoms is equal to or less than the upper limit, the hydrophilicity of IOS is increased, and its function as a surfactant is enhanced.

[0057] R in equation (6) 18 represents an alkyl group. 18 The number of carbon atoms is preferably 2 to 22, more preferably 4 to 18, and even more preferably 8 to 16. R in equation (6) 19 represents an alkyl group having 1 to 5 carbon atoms. 19 The number of carbon atoms is preferably 1 to 3. In formula (6), y is 0 to 4, preferably 0 to 2. When y is equal to or greater than the lower limit, the cleaning power is further increased. When y is equal to or less than the upper limit, the appearance stability of the liquid portion is further increased. Examples of M in the formula (6) include sodium ion, potassium ion, magnesium ion, and ammonium ion.

[0058] The mass ratio ((IO-2S) / (IO-1S) ratio) of IOS in which sulfonic acid groups are present at positions 2 to 4 ((IO-1S) component) to IOS in which sulfonic acid groups are present at positions 5 or higher ((IO-2S) component) is preferably 0.3 to 5, more preferably 1 to 3. When the (IO-2S) / (IO-1S) ratio is equal to or greater than the lower limit, the slipperiness of the object to be cleaned is further improved. When the (IO-2S) / (IO-1S) ratio is equal to or less than the upper limit, the appearance stability of the liquid portion is further improved. The (IO-1S) component is R in formula (5). 17 , R in Equation (6) 19 The (IO-2S) component is an IOS having 1 to 3 carbon atoms. 17 , R in Equation (6) 19 is an IOS having 4 or more carbon atoms.

[0059] IOS is obtained by sulfonating an internal olefin. The total number of carbon atoms in the internal olefin is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. Internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. Sulfonation of internal olefins quantitatively produces β-sultone, and a portion of the β-sultone is converted to γ-sultone and olefin sulfonic acid. These are then converted to compound (5) and compound (6) in a neutralization hydrolysis step (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)). The hydroxy group of the resulting compound (6) is located within the alkane chain, and the double bond of compound (5) is located within the olefin chain. The resulting product is primarily a mixture of these compounds, and some of these may contain trace amounts of hydroxyalkanesulfonates having a hydroxy group at the end of the carbon chain or α-olefinsulfonates having a double bond at the end of the carbon chain. In this specification, these products and their mixtures are collectively referred to as IOS.

[0060] The mass ratio of compound (5) / compound (6) (compound (5) / compound (6) ratio) relative to 100 mass% of IOS is preferably 1 / 99 to 50 / 50, more preferably 1 / 99 to 30 / 70, even more preferably 5 / 95 to 20 / 80, and particularly preferably 10 / 90 to 15 / 85. When the compound (5) / compound (6) ratio is equal to or greater than the lower limit, the appearance stability of the liquid portion is further improved. When the compound (5) / compound (6) ratio is equal to or less than the upper limit, the detergency is further improved.

[0061] The content of the non-soap anionic surfactant is preferably 5 to 35 mass %, more preferably 10 to 40 mass %, based on the total mass of the liquid detergent. The mass ratio of the non-soap anionic surfactant to the mass of the nonionic surfactant, i.e., the mass ratio expressed as nonionic surfactant / non-soap anionic surfactant, is preferably 0.05 to 8, more preferably 0.2 to 5, and even more preferably 0.3 to 4. When the mass ratio is within the above range, a liquid detergent having excellent fluidity and high appearance stability can be obtained even in a composition with a low water content.

[0062] Examples of cationic surfactants include long-chain aliphatic amidoalkyl tertiary amines or salts thereof, such as caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, and oleic acid dimethylaminopropylamide; aliphatic ester alkyl tertiary amines or salts thereof, such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine; palmitic acid diethanolaminopropylamide; and quaternized compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts. Examples of salt forms of cationic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). The cationic surfactants may be used alone or in combination of two or more.

[0063] The content of the cationic surfactant is preferably 0.1 to 5 mass %, more preferably 0.2 to 3 mass %, based on the total mass of the liquid detergent. When the content of the cationic surfactant is within the above range, it can improve softness of clothes and enhance antibacterial and deodorizing effects.

[0064] Examples of amphoteric surfactants include alkylbetaine type, alkylamidebetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactants. The amphoteric surfactants may be used alone or in combination of two or more.

[0065] Examples of the semi-polar surfactant include alkylamine oxide and alkylamidopropyldimethylamine oxide. The semi-polar surfactants may be used singly or in combination of two or more.

[0066] The content of component (C) is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, and even more preferably 30 to 60% by mass, based on the total mass of the liquid detergent. When the content of component (C) is equal to or greater than the lower limit, the detergency is further enhanced. When the content of component (C) is equal to or less than the upper limit, the fluidity of the liquid detergent can be maintained.

[0067] The mass ratio of non-soap anionic surfactant to nonionic surfactant (hereinafter also referred to as "anionic / nonionic ratio") is preferably 0.01 to 5, more preferably 0.1 to 3, and even more preferably 0.3 to 2. When the anionic / nonionic ratio is equal to or greater than the above lower limit, the thixotropy is improved, and the dispersion stability of component (B) is further improved. When the anionic / nonionic ratio is equal to or less than the above upper limit, the detergency is further enhanced.

[0068] <Water> Examples of water that can be used include purified water, ion-exchanged water, distilled water, and tap water. The water content is less than 30% by mass, preferably 25% by mass or less, and more preferably 20% by mass or less, based on the total mass of the liquid detergent. The water content is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total mass of the liquid detergent. That is, the water content is preferably 3% by mass or more but less than 30% by mass, more preferably 5 to 25% by mass, even more preferably 5 to 20% by mass, and most preferably 8 to 20% by mass, based on the total mass of the liquid detergent. When the water content is equal to or less than the upper limit, component (B) is less likely to dissolve in the liquid detergent, the particle appearance (particle number, particle size, etc.) can be maintained well, and the appearance stability of component (B) is improved. When the water content is equal to or greater than the lower limit, the liquid portion has excellent appearance stability, the liquid detergent is less likely to ignite, and the usability is excellent. The liquid detergent may be substantially free of water. Here, "substantially free of water" means that water is not intentionally blended in, except for unintentional inclusion.

[0069] <Optional ingredients> The liquid detergent of the present invention may or may not contain optional ingredients. Optional components include water-miscible organic solvents, thickeners other than component (A), chelating agents, pH adjusters, viscosity reducers and solubilizers, liquid enzymes, antibacterial agents, builder components other than component (B), higher fatty acids or salts thereof, preservatives, antioxidants, inorganic reducing agents, enzyme stabilizers, texture improvers, fluorescent brighteners, dye transfer inhibitors, soiling inhibitors, colorants, emulsifiers, discoloration inhibitors, hydrotropes, bleaches, fluorescent agents, pearlescent agents, fragrances, extracts of natural products and the like, water-insoluble inorganic compounds, and particles smaller than component (B). The optional components may be used alone or in combination of two or more.

[0070] A water-miscible organic solvent is an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25°C. Examples of water-miscible organic solvents include alcohols such as ethanol, glycerin, 1-propanol, 2-propanol, 1-butanol, and 3-methoxy-3-methyl-1-butanol (Solfit, trade name); glycols such as propylene glycol (PG), butylene glycol, and hexylene glycol; polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a molecular weight of approximately 200 to 1000, and dipropylene glycol; and alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and diethylene glycol dimethyl ether. Among these, ethanol, glycerin, 3-methoxy-3-methyl-1-butanol, propylene glycol, polyethylene glycols having a molecular weight of approximately 200 to 1000, and diethylene glycol monobutyl ether (butyl carbitol) are preferred from the standpoints of low odor, availability, and fluidity of the liquid detergent. The water-miscible organic solvents may be used alone or in combination of two or more.

[0071] The content of the water-miscible organic solvent is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass, based on the total mass of the liquid detergent. If the content of the water-miscible organic solvent is within the above range, it is easy to ensure the stability of the appearance of the liquid portion.

[0072] Builder components other than component (B) (hereinafter also referred to as "other builder components") include, for example, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, ammonium chloride, ammonium sulfate, sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, sodium hydroxide, potassium hydroxide, aluminosilicates (e.g., zeolite, etc.), and the like. The other builder components may be used alone or in combination of two or more. Other builder ingredients may be dissolved in the liquid detergent or may be present in solid form. The content of other builder components is preferably 20% by mass or less, more preferably 0.5 to 10% by mass, based on the total mass of the liquid detergent.

[0073] The chelating agent is preferably, for example, a chelating agent having a trivalent or tetravalent carboxylic acid group or a salt thereof. Specific examples include citric acid or a salt thereof, and aminocarboxylic acid chelating agents or a salt thereof. An aminocarboxylic acid refers to a compound containing at least one primary, one secondary, or one tertiary amino group and at least one carboxyl group per molecule, and an aminocarboxylic acid chelating agent refers to a chelating agent that is an aminocarboxylic acid. The aminocarboxylic acid chelating agent may be any known in the field of detergents. Specific examples include methylglycine diacetate (MGDA), methylglycine diacetate, L-glutamic acid diacetate (GLDA), L-glutamic acid diacetate, diethylenetriamine pentaacetic acid (DTPA), diethylenetriamine pentaacetate, ethylenediamine succinic acid (EDDS), ethylenediamine succinate, 3-hydroxy-2,2'-iminodisuccinic acid (HIDS), 3-hydroxy-2,2'-iminodisuccinate, L-aspartic acid-N,N-diacetic acid (ASDA), and L-aspartic acid-N,N-diacetate. Among these, citric acid or its salts, and MGDA or its salts are preferred, with trisodium methylglycine diacetate being more preferred. The chelating agent may be used alone or in combination of two or more. The content of the chelating agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on the total mass of the liquid detergent. When the content of the chelating agent is equal to or greater than the above-mentioned lower limit, the effects of improving detergency, improving storage stability, and preventing discoloration are easily achieved.

[0074] Examples of pH adjusters include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, isopropanolamine, and diisopropanolamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; basic amino acids such as arginine and lysine; ammonia; and acid agents such as sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid. Among these, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, sodium hydroxide, sulfuric acid, and hydrochloric acid are preferred. The pH adjusters may be used alone or in combination of two or more. The amount of pH adjuster added may be determined appropriately so as to adjust the liquid detergent to a predetermined pH.

[0075] Examples of viscosity reducers and solubilizers include aromatic sulfonic acids and their salts. Specific examples include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and their salts. Examples of aromatic sulfonic acid salts include sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, and alkanolamine salts. The viscosity reducing agent and the solubilizing agent may be used alone or in combination of two or more. The content of the viscosity reducer and solubilizer is preferably 0.1 to 15% by mass relative to the total mass of the liquid detergent.

[0076] Examples of antibacterial agents include diclosan, triclosan, and quaternary ammonium salts (benzalkonium chloride, etc.). The antibacterial agent may be used alone or in combination of two or more. The content of the antibacterial agent is preferably 0.001 to 10 mass %, more preferably 0.01 to 3 mass %, and even more preferably 0.03 to 2 mass %, relative to the total mass of the liquid detergent.

[0077] Examples of thickeners other than component (A) (hereinafter also referred to as "other thickeners") include acrylic polymers, xanthan gum, and carrageenan. Commercially available acrylic polymers include the Carbopol (registered trademark) series manufactured by Lubrizol Corp. Examples of the Carbopol series include Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultrez 20, Carbopol Ultrez 21, and Carbopol Aqua 30. The other thickeners may be used alone or in combination of two or more. The content of the other thickeners is preferably 6% by mass or less, more preferably 0.2 to 4% by mass, based on the total mass of the liquid detergent.

[0078] If a liquid detergent contains a higher fatty acid or its salt, it will have improved defoaming properties. "Defoaming properties" refers to the ability of a liquid detergent to suppress foaming. Examples of higher fatty acids or salts thereof include single fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, and behenic acid, and mixed fatty acids such as coconut oil fatty acid and beef tallow fatty acid. The higher fatty acid or salt thereof may be used alone or in combination of two or more. In particular, the combined use of two or more types further enhances the defoaming properties. The content of the higher fatty acid or its salt is preferably 0.5 to 10 mass %, more preferably 1 to 8 mass %, and even more preferably 1 to 5 mass %, based on the total mass of the liquid detergent. If the content of the higher fatty acid or its salt is equal to or greater than the lower limit, the defoaming ability is enhanced, while if it is equal to or less than the upper limit, the appearance stability of the liquid part at low temperatures is improved.

[0079] Examples of preservatives include 2-bromo-2-nitropropane-1,3-diol, 3-iodopropynyl butylcarbamate, zinc pyrithione, sodium pyrithione, octylisothiazolin-3-one, 1,2-benzisothiazolin-3-one (BIT), 5-chloro-2-methylisothiazolin-3-one (CMIT), 2-methylisothiazolin-3-one (MIT), ethoxylated cocoamine, octanediol, benzyl alcohol, phenoxyethanol, and sodium benzoate. The preservatives may be used alone or in combination of two or more. The content of the preservative is preferably 0.001 to 2% by mass relative to the total mass of the liquid detergent.

[0080] If a liquid detergent contains an antioxidant, it can suppress absorption of oxygen in the headspace of the container in which the liquid detergent is stored, and also suppress fading and discoloration due to light and heat. Examples of antioxidants include monophenol-based antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenol-based antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol); and polymeric phenolic antioxidants such as dl-α-tocopherol. Of these, monophenol-based antioxidants and polymeric antioxidants are preferred. Of the monophenol-based antioxidants, dibutylhydroxytoluene is particularly preferred. Of the polymeric phenolic antioxidants, dl-α-tocopherol is particularly preferred. The antioxidants may be used alone or in combination of two or more. The content of the antioxidant is preferably 0.01 to 2% by mass relative to the total mass of the liquid detergent.

[0081] If the liquid detergent contains an inorganic reducing agent, it can prevent fading and discoloration due to light and heat. Examples of inorganic reducing agents include sulfites such as sodium sulfite and potassium sulfite, pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite, and bisulfites such as sodium hydrogensulfite and potassium hydrogensulfite. Among these, sodium sulfite is preferred from the viewpoint of excellent storage stability. The inorganic reducing agent may be used alone or in combination of two or more. The content of the inorganic reducing agent is preferably 0.01 to 3 mass %, more preferably 0.02 to 1 mass %, and even more preferably 0.05 to 0.5 mass %, based on the total mass of the liquid detergent. If the content of the inorganic reducing agent is equal to or greater than the lower limit, the effect of suppressing coloration due to light is easily obtained, while if it is equal to or less than the upper limit, the appearance stability of the liquid part is improved.

[0082] Examples of enzyme stabilizers include boric acid, borax, formic acid or a salt thereof, lactic acid or a salt thereof, calcium salts such as calcium chloride and calcium sulfate. The enzyme stabilizers may be used alone or in combination of two or more. The content of the enzyme stabilizer is preferably 2% by mass or less based on the total mass of the liquid detergent.

[0083] Examples of the feel improver include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone. The texture improver may be used alone or in combination of two or more. The content of the texture improver is preferably 5% by mass or less based on the total mass of the liquid detergent.

[0084] Examples of the fluorescent brightening agent include distyrylbiphenyl type fluorescent brightening agents, etc. The fluorescent brightening agents may be used alone or in combination of two or more. The content of the fluorescent whitening agent is preferably 1% by mass or less based on the total mass of the liquid detergent.

[0085] Examples of dye transfer inhibitors include polyvinylpyrrolidone, carboxymethyl cellulose, and polyalkyleneamine. The dye transfer inhibitor may be used alone or in combination of two or more. The content of the dye transfer inhibitor is preferably 3% by mass or less based on the total mass of the liquid detergent.

[0086] Examples of anti-redeposition agents include water-soluble polymers having at least one repeating unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one repeating unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. Specific examples of such water-soluble polymers include those sold under the trade name "TexCare SRN-100" (manufactured by Clariant, mass-average molecular weight 2000 to 3000), "TexCare SRN-300" (manufactured by Clariant, mass-average molecular weight 7000), "Repel-O-Tex Crystal" (manufactured by Rhodia), and "Repel-O-Tex QC" (manufactured by Rhodia). Among these, TexCare SRN-100 is preferred due to its high solubility in water and excellent storage stability. Furthermore, due to its excellent handleability, it is preferred to use TexCare SRN-170 (manufactured by Clariant), which is a 70% aqueous solution of TexCare SRN-100, as the anti-redeposition agent. In addition to the above, other anti-redeposition agents that can be used include, for example, alkylene oxide adducts of polyalkyleneimines and alkylene oxide adducts of polyalkyleneamines, and specific examples thereof include the product name "Sokalan HP20" (manufactured by BASF). The anti-redeposition agents may be used alone or in combination of two or more. The content of the anti-redeposition agent is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent.

[0087] The colorant is not particularly limited, and examples thereof include dyes described in the "Legal Dyes Handbook" (Japan Cosmetic Industry Association) and dyes in which the end of the chromophore structure is chemically modified with a water-soluble polymer or the like. Specifically, CI Acid Red 138, CI Acid Red 260, CI Acid Red 106, Acid Yellow 203 (Yellow No. 203), Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Levanyl® Violet (Levanyl® Violet), Liquitint® BLUE SE (Liquitint® Blue SE), Liquitint® BLUE HP (Liquitint® Blue HP), Liquitint® BLUE MC (Liquitint® Blue MC), Liquitint® VIOLET CT (Liquitint® Violet CT), Liquitint® VIOLET LS (Liquitint® Violet LS), Liquitint® VIOLET DD (Liquitint® Violet DD), Liquitint® GREEN SA, Liquitint® Bright Yellow, Liquitint® YELLOW SY, Liquitint® YELLOW LP, Liquitint® BRILLIANT ORANGE, Liquitint® PINK AL, Liquitint® RED ST, Liquitint® RED MX MX), CI77007 (Pigment Blue 29, L-280BLUEU), CI74160 (Pigment Blue 15), CIExamples of suitable pigments include general-purpose dyes and pigments such as CI 77346 (Pigment Blue 28), CI 77343 (Pigment Blue 36), CI 74260 (Pigment Green 7), CI 74265 (Pigment Green 36), WA-S Color Green, CI 21090 (Pigment Yellow 12, Yellow No. 205), CI 56110 (Pigment Red 254), CI 12490 (Pigment Red 5), Labracol 040(F) Red, and PIGMOSOL (registered trademark). Note that, in this specification, "CI" stands for Color Index. The colorant may be used alone or in combination of two or more. The content of the colorant is preferably 0.00005 to 1.0% by mass, more preferably 0.00005 to 0.01% by mass, based on the total mass of the liquid detergent. If the content of the colorant is equal to or greater than the lower limit, the liquid detergent can be sufficiently colored, while if the content is equal to or less than the upper limit, pigmentation on the washed items is unlikely to occur, making it easier to obtain a liquid detergent with excellent dispersion stability.

[0088] Examples of the emulsifier include polystyrene emulsion and polyvinyl acetate emulsion, and emulsions with a solid content of 30 to 50% by mass are usually used. Specific examples include polystyrene emulsion (product name: Saivinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Industry Co., Ltd.), Opulyn 301, and Acusol OP 301. The emulsifier may be used alone or in combination of two or more. The content of the emulsifier is preferably 0.001 to 0.5% by mass relative to the total mass of the liquid detergent.

[0089] Examples of flavoring agents include those described in "Synthetic Fragrances: Chemistry and Product Knowledge" by Genichi Indo, published by The Chemical Daily in 1996, and "Perfume and Flavor Chemicals" by Stephen Arctander, published by Montclair, NJ in 1969. More specific examples include synthetic fragrances, natural fragrances derived from animals or plants, blended fragrances containing natural fragrances and / or synthetic fragrances, and fragrance components described in JP-A No. 2002-146399. The flavoring agent may be incorporated as a capsule flavoring encapsulated in a capsule formed of a polymer compound. The flavoring agent may be used alone or in combination of two or more. The content of the fragrance is preferably 0.01 to 2% by mass relative to the total mass of the liquid detergent.

[0090] Particles smaller than component (B) are particles with a volume average particle diameter of less than 100 μm. Examples include particles with a volume average particle diameter of less than 100 μm that contain bleaching agents, bleach activators, alkali agents, pearlescent agents, pigments, mica, clay, water-soluble inorganic compounds, enzymes, detergent compositions, fragrances, etc. These may be coated particles having a particle-containing core and a coating that covers part or all of the surface of the core.

[0091] Examples of water-insoluble inorganic compounds include zeolites; natural or synthetic smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, sauconite, hectorite, and stevensite; vermiculite; and synthetic fluorine mica (e.g., sodium-type synthetic mica and lithium-type synthetic mica). Examples of water-insoluble inorganic compounds include highly metal ion-substituted clay minerals obtained by ion-exchanging the clay minerals to improve their swelling power. Among these, zeolites and bentonite are preferred as water-insoluble inorganic compounds because of their chelating effect. Zeolite is a general term for aluminosilicates, and aluminosilicates may be either crystalline or amorphous (amorphous). From the viewpoint of cation exchange capacity, crystalline aluminosilicates are preferred as zeolites. Examples of crystalline aluminosilicates include A-type, X-type, Y-type, and P-type zeolites, and any of these can be used. Bentonite is a substance whose main component is montmorillonite.

[0092] <Physical properties> (pH) The pH of the liquid detergent at 25°C is preferably 6 to 12, more preferably 7 to 11. The pH of the liquid detergent can be adjusted, if necessary, by adding a pH adjuster. The pH of the liquid detergent is measured at 25°C using a pH meter (manufactured by DKK-TOA Corporation, product name "HM-30G").

[0093] The pH of a diluted solution obtained by diluting 10 g of the liquid detergent in 30 L of water at 25°C is preferably 7.5 to 11, more preferably 7.8 to 10.5, and even more preferably 8.0 to 10. When component (B) is a base, component (B) in the liquid detergent dissolves during dilution, allowing the pH of the diluted solution to fall within the range of 7.5 to 11.

[0094] (viscosity) The viscosity of the liquid detergent at 25°C, measured under the following conditions, is preferably 100 to 2000 mPa·s, more preferably 150 to 1500 mPa·s, and even more preferably 300 to 1000 mPa·s. If the viscosity of the liquid detergent falls within the above range, the liquid detergent can be easily measured out using a measuring cap or the like. Furthermore, when used for application cleaning, the liquid detergent can be easily applied to textile products and the like. The viscosity of a liquid detergent is measured using a viscometer (for example, TVB-25L) after adjusting the sample to 25° C. An example of viscosity measurement conditions is shown below. <<Example of measurement conditions>> Rotor: Rotor No. 2. -Rotation speed: 60 rpm ·Measurement temperature: 25℃. Viscosity reading: 5 minutes after rotor starts rotating.

[0095] The viscosity of the liquid detergent at 25°C, measured under the following conditions, is preferably 500 to 10,000 mPa·s, more preferably 1,000 to 7,000 mPa·s, and even more preferably 1,500 to 5,500 mPa·s. If the viscosity of the liquid detergent falls within the above range, the liquid detergent can be easily measured using a measuring cap or the like. Furthermore, when used for application cleaning, the liquid detergent can be easily applied to textile products and the like. The viscosity of a liquid detergent is measured using a viscometer (for example, TVB-25L) after adjusting the sample to 25° C. An example of viscosity measurement conditions is shown below. <<Example of measurement conditions>> Rotor: Rotor No. 2. Rotation speed: 6 rpm ·Measurement temperature: 25℃. Viscosity reading: 5 minutes after rotor starts rotating.

[0096] (TI value) The thixotropy index (TI value) of the liquid detergent is preferably more than 1 and not more than 10, more preferably 1.5 to 8, and even more preferably 2 to 5. When the TI value is not less than the above lower limit, the dispersion stability and usability of component (B) are excellent, and when the TI value is not more than the above upper limit, the fluidity of the liquid detergent is less likely to be impaired. The TI value of a liquid detergent is calculated using the following formula (i). TI value = (viscosity after 5 minutes at 6 rpm) / (viscosity after 5 minutes at 60 rpm) (i) The viscosity is measured (mPa·s) by adjusting the measurement object to 25°C and using a viscometer (e.g., TVB-25L) with rotor No. 2.

[0097] <<How liquid detergents are manufactured>> The method for producing the liquid detergent is not particularly limited, and the liquid detergent can be produced in accordance with a conventional method. For example, a liquid detergent can be produced by mixing the above-mentioned component (A), a portion of water, and optionally the component (C), and optional components other than the pH adjuster, adjusting the pH to a desired level using a pH adjuster as needed, and then mixing the remaining water and component (B). Note that if the liquid detergent contains an enzyme and the pH is adjusted to a desired level using a pH adjuster, it is preferable to add the enzyme after adjusting the pH. Component (B) may be coated in advance with a coating agent to form coated particles. The liquid cleaner is preferably packaged in a transparent container to form a liquid cleaner product.

[0098] <How to use liquid cleaner> Methods for using liquid detergents include, for example, putting the liquid detergent into the liquid detergent inlet of a washing machine and then running the washing machine, adding the liquid detergent to water together with the items to be washed when washing, immersing the items to be washed in a cleaning solution prepared by dissolving the liquid detergent in water in advance, or applying the liquid detergent directly to the items to be washed and leaving it for, for example, 3 minutes to 24 hours, and then washing as usual.

[0099] It is also preferable to use a washing machine equipped with an automatic detergent dispensing function, which has recently become practical. This function automatically dispenses detergent from a tank containing the detergent into the washing tub via a dust filter at the bottom of the tank and a dispensing pipe. A measuring device such as a syringe pump is installed in the dispensing pipe, allowing a fixed amount of detergent, set according to the amount of laundry, to be transferred from the tank to the washing tub. Using the automatic detergent dispensing function not only saves you the trouble of measuring the detergent, but also prevents liquid detergent from getting on your hands when measuring it, or from spilling and soiling the washing machine or surrounding area.

[0100] It is also preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. When using an automatic dispenser, it is possible to accurately measure even a small amount of liquid detergent, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse. Some automatic dispensers on the market use infrared sensors to automatically dispense liquid detergent without touching a switch, etc. By using such an automatic dispenser, the user can measure out the liquid detergent simply by holding the container in one hand, which significantly reduces the burden on the user.

[0101] When using an automatic dispenser, it is also preferable to receive the dispensed liquid detergent in a soft container and then place the soft container directly into the washing machine, thereby ensuring that the entire amount of dispensed liquid detergent is dissolved in the cleaning liquid. Examples of materials for the soft container that can be directly put into the washing machine include silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, polyurethane, and the like.

[0102] Examples of items to be washed include textile products such as clothing, dishcloths, towels, sheets, curtains, etc. The material of the textile products is not particularly limited, and may be any of natural fibers such as cotton, silk, wool, etc., and chemical fibers such as polyester, polyamide, etc. When the liquid detergent is used by dissolving it in water, it is preferably diluted, for example, 5 to 6000 times (by volume). The liquor ratio, which is the amount of water per amount of clothes (mass of washing liquid / mass of clothes during washing), is preferably 5 or more for drum-type washing machines and 10 or more for vertical washing machines. The liquid detergent is suitable as a detergent for textile products. In particular, if the liquid detergent contains an uncoated component (B) and the particle size of the component (B) is less than 200 μm, more preferably less than 100 μm, it is suitable for use in washing machines and automatic dispensers with an automatic detergent dispensing function.

[0103] <Liquid cleaning products> The liquid detergent may be enclosed in a container made of a water-soluble film to form a liquid detergent article. In this specification, the term "water-soluble film" refers to a film that has the property of completely dissolving within 120 seconds when a 30 mm square water-soluble film test piece is placed in 300 mL of water at 25°C and stirred.

[0104] 1 shows an example of a liquid detergent article 10. The internal space formed by the water-soluble films 3 and 4 contains the liquid detergent 1 of the present invention, and particles 2 are dispersed in the liquid detergent 1 in a state that is visible from the outside of the water-soluble films 3 and 4.

[0105] FIG. 2 shows a liquid detergent article 20 having multiple internal spaces. The liquid detergent article 20 has one larger internal space 5 and two smaller internal spaces 6 and 7. The liquid detergent of the present invention may be contained in internal space 5, or in internal space 6 or 7. Particles are dispersed in the liquid detergent in a manner that is visible from the outside of the water-soluble film (not shown). The number of smaller internal spaces is not particularly limited and may be one or two or more. Internal spaces other than the internal space containing the liquid detergent may contain components other than the liquid detergent of the present invention. The components other than the liquid detergent of the present invention are not particularly limited and may be in the form of a liquid, solid, gel, or a mixture thereof.

[0106] <Water-soluble film> Examples of resins constituting the water-soluble film that constitutes the container include polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polycarboxylic acid or its salt, polyamino acid or peptide, polyamide, polyacrylamide, copolymer of maleic acid and acrylic acid, polysaccharides including starch and gelatin, natural rubbers such as xanthan or carrageenan, etc. Among these materials, polyvinyl alcohol is preferred.

[0107] The water-soluble film contains a plasticizer, which may be one or more of polyhydric alcohols such as glycerin, diglycerin, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, pentaerythritol, or 1,3-butanediol, polyethers such as polyethylene glycol or polypropylene glycol, polyvinylamides such as polyvinylpyrrolidone, phenol derivatives such as bisphenol A or bisphenol S, amide compounds such as N-methylpyrrolidone or dimethylacetamide, compounds in which ethylene oxide is added to polyhydric alcohols such as glycerin, pentaerythritol, or sorbitol, or water.

[0108] For the purpose of improving water solubility, it is preferable to use glycerin, diglycerin, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, polyethylene glycol, or polyvinylpyrrolidone, and in particular, from the viewpoint of the effect of suppressing a decrease in water solubility of the film due to bleed-out of the plasticizer, it is particularly preferable to use glycerin, diglycerin, trimethylolpropane, polyethylene glycol, or polyvinylpyrrolidone.

[0109] The content of the plasticizer contained in the water-soluble film is preferably 1 to 50 mass % relative to the mass of the polyvinyl alcohol, and more preferably 20 to 40 mass %. When the content of the plasticizer contained in the water-soluble film is within the above-mentioned preferred range, the container can be given appropriate flexibility.

[0110] The water-soluble film may contain additives, as needed, such as inorganic fillers (e.g., silica, heavy, light, or surface-treated calcium carbonate, aluminum hydroxide, aluminum oxide, titanium oxide, diatomaceous earth, barium sulfate, calcium sulfate, zeolite, zinc oxide, silicic acid, silicates, mica, magnesium carbonate, kaolin, clays such as halloysite, pyrophyllite, and sericite, and talc), colorants, fragrances, extenders, antifoaming agents, release agents, UV absorbers, surfactants, and water-soluble polymers such as carboxymethylcellulose, polyacrylamide, polyacrylic acid or a salt thereof, methylcellulose, and hydroxymethylcellulose.

[0111] Examples of commercially available water-soluble films include those sold by Monosol LLC (Merrillville, Indiana, USA) under the trade names Monosol M8310, M8312, M8630, M7061, and M8900.

[0112] <Method for manufacturing liquid detergent article> The liquid detergent article is manufactured, for example, as follows using a mold having a plurality of recesses each having a rectangular shape in plan view. A water-soluble film is placed so as to cover the opening of the recess. The pressure inside the recess is reduced, and the water-soluble film is drawn into the recess to form a storage section with an open top. The size of one storage section is about 20 to 30 mL. Next, the liquid detergent is filled into the storage section. After that, another wet water-soluble film is placed to cover and seal the opening of the storage section. Then, by cutting out the product individually, liquid detergent articles in which the liquid detergent is filled in a container made of a water-soluble film can be obtained.

[0113] <How to use liquid cleaning products> When the liquid detergent article is used as a laundry detergent, there is no need to measure out the detergent as in the past, and it is sufficient to simply add one liquid detergent article to the washing machine tub.

[0114] <Action and effect> The liquid detergent of the present invention described above enhances the appearance stability of the liquid portion and the dispersion stability of the particles, and can maintain the dispersion stability of the particles even after storage.The particles do not dissolve in the liquid detergent, and the appearance stability of the particles can be maintained, thereby preventing particles from remaining on the washed items after washing. Furthermore, the liquid detergent of the present invention can maintain component (B) at a visible size, thereby imparting aesthetic appeal to the liquid detergent. When the liquid detergent is used for washing, it is diluted with water, and the component (B) gradually dissolves in the washing liquid, allowing the component (B) to exert its function. Furthermore, the liquid detergent article of the present invention does not require measuring out detergent, and only requires that one liquid detergent article be placed in the washing machine tub, thereby demonstrating high simplicity and convenience. [Example]

[0115] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. The raw materials used in this example are as follows:

[0116] "Raw materials used" The following compounds were used as component (A). A-1: Hydrogenated castor oil (manufactured by NOF Corporation, product name "Castarwax A Flakes"). A-2: Bacterial cellulose (manufactured by CPKelco US, trade name "CELLULON (registered trademark) L27"). A-3: Carbopol AQUA30 (manufactured by Lubrizol) (comparison product with component (A)).

[0117] The following compounds were used as component (B). B-1: Coated particles containing sodium chloride. Sodium chloride: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Sodium Chloride". B-2: Coated particles containing sodium carbonate. Sodium carbonate: soda ash (granular ash), volume average particle diameter (median diameter) 330 μm, manufactured by Soda Ash Japan Co., Ltd. The volume-average particle size is a volume-based median diameter measured by a laser diffraction scattering method using a particle size distribution analyzer (for example, product name "LS 13 320" manufactured by Beckman Coulter, Inc.) The particle size may be measured by a dry method in which the particle group to be measured is measured as is, or by a wet method in which the particle group to be measured is dispersed in a solvent and then measured. B-3: Protease preparation (manufactured by Novozymes Japan Co., Ltd., trade name "Savinase Evity 12T", a green-colored enzyme granule preparation). Particle size (median diameter) 650 μm.

[0118] The following compounds were used as coating agents for component (B) (excluding B-3 above). The content is stated as the content in the product or diluted solution. MA agent: Maleic acid-acrylic acid copolymer, AQUALIC TL-400 (trade name), manufactured by Nippon Shokubai Co., Ltd. ·CaCl2: Calcium chloride (manufactured by Kanto Chemical Co., Ltd.) diluted with ion-exchanged water to 40% by mass. Note that CaCl2 is a sensitive salt.

[0119] <Coating of component (B): Stirring granulation> Air was supplied to the fluidization chamber of a fluidized bed granulator (manufactured by Powrex Corporation, product name "FD-MP-01D / SPC") at 80°C, and the exhaust temperature was set to 40°C (preheating). According to the composition shown in Table 1 and the manufacturing conditions shown in Table 2, 600 g of water-soluble inorganic particles were placed in a fluidization tank. After that, air was supplied to the fluidization tank at 80°C, and after confirming that the powder had fluidized, an aqueous dispersion of the MA agent was sprayed from above onto the fluidized powder bed using a two-fluid nozzle (primary granulation). After that, an aqueous dispersion of CaCl2 was sprayed from above onto the fluidized powder bed using a two-fluid nozzle (secondary granulation). Granulation was carried out while adjusting the air velocity within the fluidization bed to maintain the fluidized state. After the secondary granulation, 80°C air was sent into the fluidization tank for about 30 minutes to adjust the moisture content of the coated particles to 5 to 9% by mass (drying step). After that, air was sent into the fluidization tank at room temperature to cool the granules to room temperature (25°C). The obtained granules were classified using a sieve with 1000 μm openings, and the particles passing through the sieve with 1000 μm openings were taken as a group of coated particles. The volume average particle diameter (median diameter) of the obtained coated particles was measured, and was 380 μm for B-1 and 430 μm for B-2.

[0120] [Table 1]

[0121] [Table 2]

[0122] <Evaluation of solubility of component (B)> For B-1 to B-3, 150 mL of water (25°C) and 0.4 g of the above particles were placed in a 200 mL beaker and stirred at 500 rpm for 5 minutes using a 4 cm stirrer. It was visually confirmed that the particle size after stirring was smaller than the particle size before stirring.

[0123] The following compounds were used as component (C). C-1: AE7. Polyoxyethylene alkyl ether (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Rheox CL-70"), in general formula (2), 11 is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), and R bonded to the oxygen atom 11 The carbon atom in is a primary carbon atom, and R 12 is a hydrogen atom, s is 7, t is 0, and u is 0 (compound (2)). R 11 -O-[(EO)s / (A 11 O)t]-(EO)uR 12 ···(2) (In general formula (2), R 11 R is a straight or branched chain hydrocarbon group having 8 to 22 carbon atoms. 12is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. s is a number from 3 to 25 indicating the average number of EO repeats. A 11 O represents at least one of PO (oxypropylene group) and BO (oxybutylene group). t represents the average repeat number of A11O and is a number from 0 to 6. u represents the average repeat number of EO and is a number from 0 to 20. C-2: AE15. A natural alcohol to which 15 moles of ethylene oxide have been added. In the general formula (2), R 11 = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, s=15, q=0, r=0. Synthesized by the following synthesis method. 565.78 g of CO-1214 (trade name) manufactured by Procter & Gamble Co. and 2.5 g of a 30% by weight aqueous solution of NaOH were charged into a pressure-resistant reactor, and the atmosphere inside the reactor was replaced with nitrogen. Next, dehydration was carried out for 30 minutes at a temperature of 100°C and a pressure of 2.0 kPa or less, and then the temperature was raised to 160°C. Next, 1933.5 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring. Ethylene oxide was added through a sparging tube, adjusting the addition rate so that the reaction temperature did not exceed 180°C. After the addition of ethylene oxide was completed, the mixture was aged for 30 minutes at a temperature of 180°C and a pressure of 0.3 MPa or less, and then unreacted ethylene oxide was distilled off for 10 minutes at a temperature of 180°C and a pressure of 6.0 kPa or less. Next, after cooling to a temperature of 100° C. or less, the reaction product was neutralized by adding 70% by mass of p-toluenesulfonic acid so that the pH of a 1% by mass aqueous solution of the reaction product became about 7, thereby obtaining C-2. C-3: A block-added product of 8 moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide to a natural alcohol (mass ratio of 12 carbon atoms to 14 carbon atoms = 7 / 3). In the general formula (2), R 11 = alkyl groups having 12 carbon atoms and alkyl groups having 14 carbon atoms, s=8, t=2, u=8. C-4: LAS. Linear alkylbenzene sulfonic acid having an alkyl group with 10 to 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipon (registered trademark) LH-200"). C-5: AES. Polyoxyalkylene alkyl ether sulfate (in general formula (4), R 15 are a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), m is 1, n is 0, M is sodium, and the proportion of compounds in which m is 0 and n is 0 relative to the total AES is 43 mass%. Compound (4) synthesized by the following synthesis method. C-6: IOS. Sodium internal olefin sulfonate synthesized by the following synthesis method. Hydroxy compound content is 85% by mass. Synthesized by the following synthesis method.

[0124] (Synthesis of C-5) Into a 4 L autoclave were charged 400 g of Procter & Gamble's CO1270 alcohol (a mixture of a carbon number 12 alcohol and a carbon number 14 alcohol in a mass ratio of 75 / 25) as the raw material alcohol and 0.8 g of potassium hydroxide catalyst as the reaction catalyst, and the atmosphere inside the autoclave was replaced with nitrogen, and then the temperature was raised while stirring. Subsequently, 91 g of ethylene oxide was introduced while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less, and the reaction was carried out to obtain an alcohol ethoxylate. Analysis using a gas chromatograph: Hewlett-Packard GC-5890, a detector: a flame ionization detector (FID), and a column: Ultra-1 (HP, L 25 m × φ 0.2 mm × T 0.11 μm) revealed that the average number of moles of ethylene oxide added in the obtained alcohol ethoxylate was 1.0. In addition, the amount of compounds to which ethylene oxide had not been added (those that ultimately became component (b-0)) was 43 mass% of the total amount of the obtained alcohol ethoxylate. Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after purging with nitrogen, 96 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40°C. After the addition was completed, stirring was continued for 1 hour (sulfation reaction), and polyoxyethylene alkyl ether sulfate was obtained. This was then neutralized with aqueous sodium hydroxide solution to obtain C-5.

[0125] (Synthesis of C-6) The internal olefin used was an internal olefin mixture containing 2.0 mass% of paraffin components, with a total ratio of double bonds at the 2-position of 26 mass%, a cis / trans mass ratio of 27 / 73, and 3 mass% of C14 or lower, 33 mass% of C15, 39 mass% of C16, 24 mass% of C17, and 1 mass% of C18 or higher. Using this internal olefin mixture, a sulfonation reaction was carried out in a conventional manner using a glass thin-film sulfonation apparatus with an inner diameter of 6 mm and a length of 1.2 m, using nitrogen-diluted SO3 gas (SO3 concentration: 5% by volume) at a reactor temperature of 10°C and a molar ratio of SO3 / internal olefin of 1.1, to obtain internal olefin sulfonic acid. The resulting reaction product, internal olefin sulfonic acid, was aged at 5°C for 1 hour, and then 1.11 times the molar amount (relative to the internal olefin sulfonic acid) of a 15% aqueous solution of sodium hydroxide was added and the mixture was stirred at 30°C for 30 minutes to carry out a neutralization reaction, yielding a neutralized product. This neutralized product was then heated in an autoclave at 160°C for 40 minutes and hydrolyzed to yield C-6.

[0126] Water and the compounds shown below were used as optional components. Water: Ion-exchanged water. Ash (dissolved): Sodium carbonate (manufactured by Soda Ash Japan Co., Ltd., product name "granular ash"). Monoethanolamine: Manufactured by Nippon Shokubai Co., Ltd., product name "Monoethanolamine." Propylene glycol: Manufactured by The Dow Chemical Company under the trade name "Propylene Glycol." Glycerin: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Glycerin". Ethanol: Manufactured by Japan Alcohol Sales Co., Ltd., product name: "Specific Alcohol 95% Synthetic." Palm fatty acids: Manufactured by NOF Corporation, product name "Palm Fatty Acids." Dichrosan: BASF Corporation, product name "Tinosan HP100". Protease: Novozymes Japan Co., Ltd., product name "Progress Uno 100L", enzyme liquid preparation. Sodium sulfite: Manufactured by Mitsui Chemicals, Inc., trade name "Sodium sulfite." Antioxidant: Dibutylhydroxytoluene (manufactured by Wako Pure Chemical Industries, Ltd., trade name "Dibutylhydroxytoluene"). Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399. Capsule fragrance: cosmic caps 1 / manufactured by Givaudan. ·Pigment: Manufactured by Kinmi Kasei Co., Ltd., product name "Green No. 3". pH adjuster: sulfuric acid (manufactured by Toagosei Co., Ltd.), sodium hydroxide (manufactured by Toagosei Co., Ltd.).

[0127] <Preparation of liquid detergent> In a 500 mL beaker, component (A), component (C), water, a portion of the glycerin, and optional components other than the pH adjuster were added according to the formulations shown in Tables 3 to 6, and the mixture was thoroughly stirred using a Three-One Motor Stirrer (manufactured by AS ONE Corporation). An appropriate amount of pH adjuster was then added so that the pH at 25°C would be the value shown in Tables 3 to 6. The resulting liquid mixture was evaluated for appearance stability (appearance stability of the liquid portion). The results are shown in Tables 3 to 6. Next, the amount of component (B) added to the liquid mixture was adjusted so that the content of component (B) relative to the total mass of the liquid detergent would be the value shown in Tables 3 to 6. The remaining glycerin was added to make the total mass 100% to obtain a liquid detergent. In the resulting liquid detergent, a portion of component (B) was present in a solid state. The resulting liquid detergent was evaluated for particle dispersion stability and particle appearance stability. The results are shown in Tables 3 to 6.

[0128] "Measurement and evaluation methods" (Appearance stability evaluation of liquid part (room temperature, 1 month)) 100 g of each liquid detergent was filled into a transparent glass bottle, which was then sealed with a lid and stored at room temperature for one month. After this storage, the appearance of the liquid portion was visually observed, and the stability of the appearance of the liquid portion was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 3 to 6. [Judgment criteria] ○: The whole was uniform. ×: Separation was observed.

[0129] (Evaluation of particle dispersion stability (initial stage)) 100 g of each liquid detergent was filled into a transparent glass bottle and sealed with a lid. The appearance of the liquid was visually observed, and the particle dispersion stability was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 3 to 6. [Judgment criteria] ◯: Particles are dispersed almost uniformly and stably. △: The particles have settled slightly, and the upper layer of the liquid detergent is somewhat sparse. ×: Particles have completely settled.

[0130] (Evaluation of particle dispersion stability (50°C, 2 weeks)) 100 g of each liquid detergent was filled into a transparent glass bottle, which was then sealed with a lid and stored at 50°C for two weeks. After this storage, the appearance of the liquid was visually observed, and the dispersion stability of the particles was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 3 to 6. [Judgment criteria] ◯: Compared to before storage, there was almost no change and the dispersion was uniform and stable. △: Compared to before storage, the particles have settled slightly and the upper layer of the liquid detergent has become slightly sparse. ×: Particles have completely settled.

[0131] (Particle appearance stability evaluation (50°C, 2 weeks)) 100 g of each liquid detergent was filled into a transparent glass bottle, which was then sealed with a lid and stored at 50°C for two weeks. After this storage, the appearance of the particles was visually observed, and the stability of the appearance of the particles was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 3 to 6. [Judgment criteria] ○: The appearance of the particles has hardly changed compared to before storage. △: The particles have slightly dissolved compared to before storage. ×: Compared to before storage, 70% or more of the particles appear to have dissolved.

[0132] (Residue assessment) 150 mL of water (25°C) and 1 g of each liquid cleaning agent were placed in a 200 mL beaker and stirred at 500 rpm for 10 minutes using a 4 cm stirrer. The contents of the beaker were then visually inspected and the post-cleaning residue was evaluated according to the following criteria. The evaluation results are shown in Tables 3 to 6. [Judgment criteria] ○: The particles are clearly smaller than before stirring, or the particles are no longer visible. ×: No change in particles was observed compared to before stirring.

[0133] (Viscosity (rotation speed: 60 rpm, measurement temperature: 25°C)) For each liquid detergent example, the sample was adjusted to 25° C., and the viscosity was measured under the following measurement conditions using a viscometer (for example, TVB-25L). The evaluation results are shown in Tables 3 to 6. <<Measurement conditions>> Rotor: Rotor No. 2. -Rotation speed: 60 rpm ·Measurement temperature: 25℃. Viscosity reading: 5 minutes after rotor starts rotating.

[0134] (Viscosity (rotation speed: 6 rpm, measurement temperature: 25°C)) For each liquid detergent example, the sample was adjusted to 25° C., and the viscosity was measured under the following measurement conditions using a viscometer (for example, TVB-25L). The evaluation results are shown in Tables 3 to 6. <<Measurement conditions>> Rotor: Rotor No. 2. Rotation speed: 6 rpm ·Measurement temperature: 25℃. Viscosity reading: 5 minutes after rotor starts rotating.

[0135] (TI value) The thixotropy index (TI value) of each liquid detergent was calculated using the following formula (i). The results are shown in Tables 3 to 6. TI value = (viscosity after 5 minutes at 6 rpm) / (viscosity after 5 minutes at 60 rpm) (i) The viscosity is measured (mPa·s) by adjusting the measurement object to 25°C and using a viscometer (e.g., TVB-25L) with rotor No. 2.

[0136] [Table 3]

[0137] [Table 4]

[0138] [Table 5]

[0139] [Table 6]

[0140] In Tables 3 to 6, the blending amount (mass %) of each component other than B-1 is the ratio to the total mass of the liquid detergent, and unless otherwise specified, is shown as a pure content value. "Appropriate amount" means that the pH adjuster is blended so that the pH of the liquid detergent at 25°C is the value shown in Tables 3 to 6. Also, a blank space for the blending amount means that the component is not blended (blended amount 0 mass %). A "-" in the evaluation result means that measurement or evaluation was not performed.

[0141] As is clear from Tables 3 to 6, the liquid detergents obtained in each Example had excellent particle dispersion stability and particle appearance stability. Furthermore, the particle dispersion stability could be maintained even after storage, and the particles did not dissolve in the liquid detergent, maintaining the particle appearance stability. Furthermore, it was found that the particles exhibited sufficient solubility in water, preventing particles from remaining on the washed items after washing. On the other hand, as is clear from Table 6, the comparative example in which the water content was 30 mass % 2 The liquid detergent of the present invention was inferior in the stability of the appearance of particles present in the solid state. Comparative example not containing component (A) 3 The liquid detergent of the present invention had poor appearance stability of the liquid part.

Claims

1. Component (A): one or more structuring agents selected from bacterial cellulose, non-bacterial cellulose, and compounds represented by the following general formula (1), Component (B): coated particles having a core and a coating covering a part or all of the surface of the core, the coating having a volume average particle diameter of 100 μm or more and comprising one or more compounds selected from the group consisting of water-soluble inorganic compounds and enzymes, the coating comprising a combination of a salt-sensitive polymer and an inorganic compound (however different from the water-soluble inorganic compound), the salt-sensitive polymer comprising one or more compounds selected from the group consisting of hydroxypropyl methylcellulose, polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymer, maleic acid olefin copolymer, and salts thereof, and the inorganic compound comprising one or more compounds selected from the group consisting of calcium chloride, calcium nitrate, and calcium acetate; A liquid cleaning agent comprising: When 150 mL of water and 0.4 g of the component (B) are placed in a 200 mL beaker at room temperature and stirred at 500 rpm for 10 minutes using a 4 cm stirrer, the particle size after stirring becomes smaller than the particle size before stirring, A liquid detergent having a water content of 20 mass% or less relative to the total mass of the liquid detergent. 【Chemistry 1】 In formula (1), Z １ ~Z ３ are each independently a hydrogen atom, a hydroxy group, or a carboxy group. １ ~Z ３ may be the same or different. In formula (1), a+b=7 to 19, c+d=7 to 19, and e+f=7 to 19.

2. The liquid detergent according to claim 1, wherein the ratio (salt-sensitive polymer / inorganic compound) of the salt-sensitive polymer to the inorganic compound (different from the water-soluble inorganic compound) is 10 / 90 to 90 / 10.

3. the component (B) contains the water-soluble inorganic compound (however, different from the inorganic compound), 3. The liquid detergent according to claim 1, wherein the water-soluble inorganic compound comprises at least one selected from the group consisting of carbonates and silicates.

4. A liquid cleaning agent according to any one of claims 1 to 3, wherein the mass of the coating agent constituting the coating portion in the coated particles of component (B) is 0.1 to 15 mass% relative to the total mass of component (B).

5. The liquid detergent according to any one of claims 1 to 4, wherein the coverage of the coated particles with component (B) is 30% or more.

6. Further comprising a surfactant including a nonionic surfactant and a non-soap anionic surfactant, The liquid detergent according to any one of claims 1 to 5, wherein the mass ratio of nonionic surfactant to non-soap anionic surfactant is 0.05 to 8.

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