Liquid detergent

Abstract

A liquid detergent containing: component (A): an inorganic base agent; and component (B): one or more structuring agents selected from the group consisting of bacterial cellulose, non-bacterial cellulose, and a compound represented by the following general formula (1), wherein at least a part of the component (A) exists in a solid state in the liquid detergent, and the water content is less than 30% by mass based on the total mass of the liquid detergent. [Chemical 1] (In formula (1), Z 1 ~Z 3 are each independently a hydrogen atom, a hydroxyl group, or a carboxyl group, a + b = 7 to 19, c + d = 7 to 19, and e + f = 7 to 19).

Description

Technical Field

[0001] The present invention relates to a liquid detergent.

[0002] This application claims priority based on Japanese Patent Application No. 2020-136509 filed in Japan on August 12, 2020, the content of which is incorporated herein by reference. Background Art

[0003] As detergents for fiber products for washing fabrics and the like, there are generally two types: powder detergents and liquid detergents. Since liquid detergents do not have the concern of dissolution residue and can be applied to fabrics and the like, their demand is gradually increasing.

[0004] However, generally speaking, the detergency of liquid detergents tends to be lower than that of powder detergents. This is because it is impossible to sufficiently incorporate the alkali agents used in powder detergents into liquid detergents. As the alkali agents incorporated into liquid detergents, there are water-soluble inorganic alkali agents and organic alkali agents. When incorporating an aqueous inorganic alkali agent into a liquid detergent, if the incorporation amount is small, it dissolves in the liquid detergent, but due to the small amount, there is a tendency for poor detergency. When incorporating an inorganic alkali agent into a liquid detergent in an amount exceeding the solubility, precipitation occurs, resulting in non-uniform components and problems in stability. In addition, ethanolamine-based compounds are sometimes incorporated as water-soluble organic alkali agents, but when incorporating an amount that can improve the detergency in a liquid detergent, problems such as the liquid detergent turning yellow and generating a strong base odor from the ethanolamine-based compounds may occur.

[0005] Therefore, liquid cleaning agents in which a part of the water-soluble inorganic alkali agent exists in a solid state in the composition have been proposed (for example, Patent Documents 1 to 4).

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 2-240200

[0009] Patent Document 2: Japanese Patent Laid-Open No. 2003-27100

[0010] Patent Document 3: Japanese Patent Laid-Open No. 2004-155937

[0011] Patent Document 4: Japanese Patent Application Publication No. 2019-508539 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] However, in liquid detergents, there is still room for improvement in the dispersion stability of the inorganic alkali agent existing in a solid state.

[0014] In addition, from the perspective of appearance, it is also required that the inorganic base agent existing in a solid state does not dissolve in the liquid detergent and can maintain the particle appearance (appearance stability).

[0015] An object of the present invention is to provide a liquid detergent having excellent dispersion stability, particle appearance stability and aesthetics of an inorganic base agent existing in a solid state, and strong detergency.

[0016] Technical solutions for solving the problems

[0017] The present invention has the following aspects:

[0018] [1] A liquid detergent containing:

[0019] (A) component: an inorganic base agent; and

[0020] (B) component: one or more structuring agents selected from the group consisting of bacterial cellulose, non-bacterial cellulose, and compounds represented by the following general formula (1),

[0021] In the liquid detergent, at least a part of the (A) component exists in a solid state,

[0022] The content of water is less than 30% by mass based on the total mass of the liquid detergent.

[0023] [Chemical formula 1]

[0024]

[0025] In formula (1), Z 1 ~Z 3 are each independently a hydrogen atom, a hydroxyl group or a carboxyl group, a + b = 7 - 19, c + d = 7 - 19, and e + f = 7 - 19.

[0026] [2] The liquid detergent according to [1] above, wherein in the liquid detergent, the surface of the (A) component existing in a solid state is coated with a coating agent or modified by a coating agent, or coated and modified by the coating agent.

[0027] [3] The liquid detergent according to [2] above, wherein the coating agent is 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 acids, salts of fatty acids, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate, surfactants, aluminosilicates, calcium chloride, and calcium nitrate.

[0028] [4] The liquid detergent according to [1] above, wherein in the liquid detergent, the particle size of the component (A) present in a solid state is 10 to 2000 μm.

[0029] [5] The liquid detergent according to any one of [1] to [4] above, which further contains a component (C): a surfactant.

[0030] [6] The liquid detergent according to any one of [1] to [5] above, wherein, relative to the total mass of the liquid detergent, the content of the component (A) is preferably 0.5 to 20% by mass, more preferably 1 to 18% by mass, and still more preferably 2.5 to 15% by mass.

[0031] [7] The liquid detergent according to any one of [1] to [6] above, wherein, relative to the total mass of the liquid detergent, the content of the component (B) is preferably 0.02 to 2% by mass, more preferably 0.04 to 1.5% by mass, and still more preferably 0.05 to 1.0% by mass.

[0032] [8] The liquid detergent according to any one of [1] to [7] above, which is used for fibrous products.

[0033] [9] The liquid detergent according to any one of [1] to [8] above, wherein, relative to the total mass of the component (A), the proportion of the component (A) present in a solid state is preferably 20 to 100% by mass, more preferably 30 to 98% by mass, and still more preferably 40 to 95% by mass.

[0034]

[10] The liquid detergent according to any one of [1] to [9] above, wherein the particle size of the component (A) present in a solid state is more preferably 100 to 1500 μm, and still more preferably 200 to 1000 μm.

[0035]

[11] The liquid detergent according to any one of [1] to

[10] above, wherein the viscosity of the liquid detergent at 25°C is preferably 100 to 2000 mPa·s, and more preferably 150 to 1000 mPa·s.

[0036]

[12] The liquid detergent according to any one of [1] to

[11] above, wherein the component (A) is at least one selected from the group consisting of sodium carbonate, potassium carbonate, sodium metasilicate, and layered sodium silicate.

[0037]

[13] The liquid detergent according to any one of [1] to

[12] above, wherein the component (B) is at least one selected from the group consisting of bacterial cellulose and hydrogenated castor oil.

[0038]

[14] The liquid detergent according to any one of [1] to

[13] further contains a surfactant as component (C), and component (C) includes a nonionic surfactant and a non-soap anionic surfactant.

[0039]

[15] The liquid detergent according to any one of [1] to

[14] further contains water. The content of water is preferably 3% by mass or more and less than 30% by mass, more preferably 5 - 25% by mass, and further preferably 5 - 20% by mass based on the total mass of the liquid detergent.

[0040]

[16] The liquid detergent according to any one of [1] to

[15] further contains at least one selected from the group consisting of a water-miscible organic solvent, an auxiliary component other than component (A), a chelating agent, a pH regulator, a viscosity reducer, a solubilizer, an enzyme, an antibacterial agent, a thickener other than component (B), a higher fatty acid, a salt of a higher fatty acid, a preservative, an antioxidant, an inorganic reducing agent, an enzyme stabilizer, a hand feel improver, a fluorescent brightening agent, a color transfer inhibitor, a recontamination inhibitor, a colorant, an opacifier, a color change inhibitor, a water-soluble auxiliary, a bleaching agent, a fluorescent agent, a pearlescent agent, a fragrance, and an extract of a natural product.

[0041]

[17] For the dilution obtained by diluting 10 g of the liquid detergent in 30 L of tap water, the pH at 25°C is preferably 7.5 - 11, more preferably 7.8 - 10.5, and further preferably 8.0 - 10 according to any one of [1] to

[16] .

[0042] Effects of the Invention

[0043] According to the present invention, a liquid detergent can be provided which has excellent dispersion stability, particle appearance stability and aesthetics of an inorganic base agent present in a solid state, and strong detergency. Detailed Description of the Invention

[0044] Hereinafter, the present invention will be described in detail.

[0045] The liquid detergent of the present invention contains component (A) and component (B) as described below. The liquid detergent preferably further contains component (C) as described below. The liquid detergent may further contain water. The liquid detergent may contain components other than component (A), component (B), component (C) and water (optional components).

[0046] It should be noted that in this specification, the stability and aesthetics of the particle appearance of the inorganic base agent present in a solid state in the liquid detergent are collectively referred to as "appearance stability".

[0047] <(A) Component>

[0048] Component (A) is an inorganic base agent.

[0049] The component (A) is a component that imparts detergency to the liquid detergent, particularly detergency against sebum stains (sebum detergency).

[0050] In the liquid detergent, at least a part of the component (A) exists in a solid state. That is, in the component (A), there is a component dissolved in the liquid detergent and a component that does not dissolve and exists in a solid state, and the liquid detergent contains an amount of the component (A) exceeding the solubility. Hereinafter, in this specification, the component (A) dissolved in the liquid detergent in the component (A) is also referred to as the “component (A1)”, and the component (A) existing in a solid state in the liquid detergent is also referred to as the “component (A2)”.

[0051] The entire amount of the component (A) can be directly incorporated into the liquid detergent, or an amount not exceeding the solubility in the entire amount of the component (A) can be incorporated into the liquid detergent and dissolved, and then the remaining amount can be incorporated into the liquid detergent.

[0052] The inorganic base agent refers to a component that is wholly or partly dissolved in water to exhibit alkalinity and has a pH of 8 or more in a 1 mass% aqueous solution at 25°C.

[0053] Specific examples of such components include carbonates such as sodium carbonate, sodium hydrogen carbonate, double salts of sodium carbonate and sodium hydrogen carbonate (sodium sesquicarbonate), potassium carbonate, and potassium hydrogen carbonate; silicates such as sodium metasilicate and layered sodium silicate; sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, sodium hydroxide, potassium hydroxide, etc. Among these, from the viewpoint of further improving detergency, sodium carbonate, potassium carbonate, sodium metasilicate, and layered sodium silicate are preferred.

[0054] The inorganic base agent can be used alone or in combination of two or more.

[0055] The particle size of the component (A) is preferably 10 to 2000 μm, more preferably 100 to 1500 μm, and still more preferably 200 to 1000 μm. If the particle size of the component (A) is at or above the above lower limit value, the dissolution rate is easily controlled and the appearance of the particles is excellent in beauty. If the particle size of the component (A) is at or below the above upper limit value, the dissolution rate in water is increased.

[0056] On the other hand, when it is not necessary to control the dissolution rate of component (A) etc., the particle size of component (A) is preferably 200 μm or less, more preferably 100 μm or less. In particular, the particle size of the uncoated component (A) is preferably less than 200 μm, more preferably less than 100 μm. If the particle size of component (A) is below the above upper limit value, when the liquid detergent is diluted with water, component (A2) dissolves rapidly. In addition, it is difficult for the solid component (A2) to remain on the detergent dispenser of the washing machine and the washed clothes. Therefore, if the particle size of component (A) is 200 μm or less, it is suitable for use in washing machines and automatic dispensers equipped with an automatic detergent dispensing function.

[0057] It should be noted that the particle size of component (A) and the particle size of the coated alkali agent described later are volume-based median particle sizes obtained using a particle size distribution measuring device (for example, manufactured by Beckman Coulter, product name “LS 13 320”) and the laser diffraction scattering method. The measurement of the particle size can be a dry method of measuring component (A) or the coated alkali agent as it is, or a wet method of dispersing component (A) or the coated alkali agent in a solvent for measurement.

[0058] Relative to the total mass of the liquid detergent, the content of component (A) is preferably 0.5 to 20% by mass, more preferably 1 to 18% by mass, and further preferably 2.5 to 15% by mass. If the content of component (A) is above the above lower limit value, sufficient detergency and the aesthetic appearance of the particles can be obtained. If the content of component (A) is below the above upper limit value, the fluidity of the liquid detergent and the aesthetic appearance of the particles can be obtained.

[0059] In addition, relative to the total mass of component (A), the proportion of component (A2) is preferably 20 to 100% by mass, more preferably 30 to 98% by mass, and further preferably 40 to 95% by mass.

[0060] The surface of component (A2) is preferably coated or modified with a coating agent, or coated and modified with the above coating agent. That is, a coating layer can be formed on the surface of component (A2), the surface of component (A2) can be modified, or a coating layer can be formed on the modified surface of component (A2) whose surface has been modified. It should be noted that in this specification, an inorganic base agent having a coating layer formed on its surface is also referred to as a “coated base agent”, and an inorganic base agent whose surface has been modified is also referred to as a “modified base agent”.

[0061] If the surface of the component (A2) is coated with a coating agent, or the surface of the component (A2) is modified, or the surface of the component (A2) is coated with the above coating agent and modified, then the component (A2) does not dissolve, and the particle appearance (number of particles, particle size, etc.) can be well maintained, and the appearance stability is further improved. Moreover, the component (A2) is difficult to precipitate, and the dispersion stability is further improved. Moreover, the dissolution rate of the component (A2) can be controlled.

[0062] As the coating agent, it is difficult to dissolve in liquid detergents, and it is easy to adhere to inorganic alkali agents. However, it is preferably a coating agent that is easy to dissolve, swell, disintegrate, and disperse in a laundry detergent obtained by diluting a liquid detergent with water and is easy to detach from the inorganic alkali agent. As the coating agent, for example, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose, hydroxyethyl cellulose, polyacrylic acid or its salts, acrylic acid-maleic acid copolymer or its salts, fatty acids or their salts, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate, aluminosilicate (such as zeolite), titanium oxide, surfactants, etc. Among these, from the viewpoints of controlling solubility in liquid detergents and maintaining particle appearance, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose, hydroxyethyl cellulose, polyacrylic acid or its salts, acrylic acid-maleic acid copolymer or its salts, fatty acids or their salts, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate are preferred, and hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose, polyacrylic acid or its salts, acrylic acid-maleic acid copolymer or its salts, sodium sulfate are more preferred.

[0063] The coated alkali agent is obtained by the following methods: a fluidized bed granulation method in which a coating agent is sprayed while fluidizing an inorganic alkali agent for granulation / coating; a stirring granulation method in which a coating agent is sprayed / added to an inorganic alkali agent and stirred with a stirring blade for granulation / coating; an immersion stirring granulation method in which an inorganic alkali agent is immersed / stirred in a coating agent and the solvent is distilled off to obtain a granulated product / coated product; an extrusion granulation method in which a coating agent is added to an inorganic alkali agent, kneaded, and extruded with an extruder; a rolling granulation method in which a coating agent is sprayed while rolling an inorganic alkali agent for granulation / coating; a spray drying type granulation method in which a slurry containing an inorganic alkali agent and a coating agent is spray-dried, etc.

[0064] The coating agent can be dissolved or dispersed in any solvent and used in the form of a solution.

[0065] Moreover, in the granulated product obtained by the above method, a salt (responsive salt) that causes the coating agent to respond can be added and mixed using any machine such as a mixer, granulator, or fluidized bed to produce a coated alkali agent.

[0066] Here, the "salt that causes the coating agent to respond" refers to a salt that increases the viscosity of the coating agent, causes gelation, or forms a film. Preferred examples of such responsive salts include: polyvalent chlorides such as calcium chloride, 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; sodium tetraborate, etc.

[0067] The responsive salt can be used alone or in combination of two or more.

[0068] Part of the coating agent may dissolve in the liquid detergent, but by using the responsive salt, the coating agent exists without dissolving in the liquid detergent.

[0069] Relative to 100 parts by mass of the component (A2), the proportion of the coating layer is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass, and further preferably 5 to 40 parts by mass. If the proportion of the coating layer is above the above lower limit value, the effect of coating the surface of the component (A2) can be fully obtained. If the proportion of the coating layer is below the above upper limit value, the coating layer can dissolve, swell, disintegrate, and disperse rapidly in the laundry detergent, preventing the component (A2) from remaining dissolved. Moreover, the amount of the component (A2) per unit weight can be increased.

[0070] The particle size of the coated alkali agent is preferably 10 to 2000 μm, more preferably 100 to 1500 μm, and further preferably 200 to 1000 μm. If the particle size of the coated alkali agent is above the above lower limit value, the dissolution rate is easily controlled and the appearance of the particles is excellent in aesthetics. If the particle size of the coated alkali agent is below the above upper limit value, the dissolution rate in water is increased.

[0071] On the other hand, when it is not necessary to control the dissolution rate of the coated alkali agent, etc., the particle size of the coated alkali agent is preferably 200 μm or less, more preferably 100 μm or less.

[0072] The modified alkali agent is an inorganic alkali agent that has been subjected to treatments other than the above coating. As treatments other than coating, for example, calcination treatment can be cited. It should be noted that in the present invention, sodium carbonate containing sodium bicarbonate and sesquicarbonate is also used as the modified alkali agent. The modified alkali agent can include inorganic alkali agents without hydrates.

[0073] In addition, after modifying the surface of the component (A2), the surface can be further coated with a coating agent.

[0074] <Component (B)>

[0075] (B) component is one or more structuring agents selected from the group consisting of bacterial cellulose, non-bacterial cellulose, and the following compound (1).

[0076] The dispersion stability of the (A2) component is improved by the liquid detergent containing the (B) component.

[0077] It should be noted that in the present invention, "structuring" refers to a state in which the viscosity changes before and after the application of force.

[0078] Bacterial cellulose is cellulose produced by the fermentation of bacteria belonging to the genus Acetobacter.

[0079] Examples of bacterial cellulose include: water-insoluble fibers that branch into a network and intertwine with each other to form a network-like grid-like bacterial cellulose, etc.

[0080] At least a part of the bacterial cellulose can also be coated or mixed with a thickener.

[0081] Examples of thickeners include: carboxymethyl cellulose (CMC), modified CMC, xanthan gum products, pectin, alginate, carrageenan, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, tamarind (TAMARINDUS INDICA) seed gum, locust bean gum, etc.

[0082] The thickener can be used alone or in combination of two or more.

[0083] As bacterial cellulose, commercially available products can be used. For example, products with the trade name "CELLULON (registered trademark)" manufactured by CPKelco USA Inc. can be cited.

[0084] Non-bacterial cellulose is cellulose extracted from plants such as vegetables, fruits, and wood, also known as cellulose fiber.

[0085] As non-bacterial cellulose, commercially available products can be used. For example, products with the trade name "Avicel (registered trademark)" manufactured by FMC Corporation, products with the trade name "Citri-Fi" manufactured by Fiberstar, and products with the trade name "Betafib" manufactured by Cosun can be cited.

[0086] Compound (1) is a compound (triglyceride component) represented by the following general formula (1).

[0087] [Chemical formula 2]

[0088]

[0089] In formula (1), Z 1 ~Z 3 are each independently a hydrogen atom, a hydroxyl group, or a carboxyl group. Z 1 ~Z 3 may be the same or different.

[0090] 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. More preferably, a + b = 13 to 15, c + d = 13 to 15, and e + f = 13 to 15. If a + b, c + d, and e + f are each 7 or more, the volume of the hydrophobic group portion sufficiently increases, and the coating detergency becomes high. On the other hand, if a + b, c + d, and e + f are each 19 or less, the risk of increased volume and curing of the hydrophobic group portion is reduced.

[0091] Examples of compound (1) include: Z 1 ~Z 3 Compound (1-1) in which is a hydroxyl group, Z 1 ~Z 3 Compound (1-2) in which is a hydrogen atom, etc.

[0092] Particularly preferred as compound (1-1) is hydrogenated castor oil. In addition, particularly preferred as compound (1-2) is hydrogenated palm oil.

[0093] Examples of hydrogenated castor oil include: triglycerides containing an alkyl or alkenyl moiety having 10 to 22 carbon atoms with a hydroxyl group. Specifically, examples include: trihydroxystearin, etc.

[0094] Hydrogenated castor oil is obtained by hydrogenating castor oil and converting the double bonds that can exist as the castor oil moiety in the starting oil into single bonds. By the conversion of double bonds to single bonds, the castor oil moiety is converted into a saturated hydroxyalkyl moiety, such as a hydroxystearyl group.

[0095] Hydrogenated castor oil can be used in a solid state, a molten state, or a mixture of these states, but it can be processed in any preferred starting form not limited to these.

[0096] As hydrogenated castor oil, commercially available products can be used. For example, examples include: the product named "THIXCIN (registered trademark)" manufactured by Rheox, Inc., the product named "CASTER WAX A FLAKE" manufactured by NOF Corporation, etc.

[0097] As hydrogenated palm oil, commercially available products can be used. For example, examples include: the product named "Palm Super Hydrogenated Oil A" manufactured by Shin Nippon Rika Co., Ltd., etc.

[0098] As component (B), since even a small amount can sufficiently improve the dispersion stability of component (A2) and easily obtain a liquid appearance with high transparency, bacterial cellulose and non-bacterial cellulose are preferred, and bacterial cellulose is more preferred.

[0099] The content of component (B) is preferably 0.02 to 2% by mass, more preferably 0.04 to 1.5% by mass, and still more preferably 0.05 to 1.0% by mass, relative to the total mass of the liquid detergent.

[0100] In addition, for example, when using a bacterial cellulose preparation such as "CELLULON (registered trademark)" as a commercially available product as component (B), the content of component (B) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably 2.5 to 7% by mass in the form of the content of the commercial product, relative to the total mass of the liquid detergent.

[0101] If the content of component (B) is above the above lower limit value, the dispersion stability of component (A2) is further improved. If the content of component (B) is below the above upper limit value, the viscosity of the liquid detergent becomes lower, and the usability and storage stability are further improved.

[0102] <Component (C)>

[0103] Component (C) is a surfactant.

[0104] If the liquid detergent contains a surfactant, the detergency is further improved.

[0105] As the surfactant, there is no particular limitation as long as it is a surfactant used in existing liquid detergents. For example, nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, semi-polar surfactants, etc. can be cited.

[0106] As component (C), one surfactant can be used, or two or more surfactants can be combined.

[0107] From the viewpoint of further improving the detergency, component (C) preferably contains a nonionic surfactant and a non-soap anionic surfactant.

[0108] As component (C), a nonionic surfactant and a non-soap anionic surfactant can be used in combination with one or more of a cationic surfactant, an amphoteric surfactant, and a semi-polar surfactant.

[0109] Examples of the nonionic surfactant 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, polyol fatty acid esters or their alkylene oxide adducts, polyol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, etc.

[0110] One type of nonionic surfactant can be used alone, or two or more types can be used in combination.

[0111] As the nonionic surfactant, a polyoxyalkylene type nonionic surfactant is preferred. 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, and compound (2) is further preferred.

[0112] R 11 -O-[(EO) s / (A 11 O) t -(EO) u -R 12 …(2)

[0113] (In general formula (2), R 11 is a linear or branched hydrocarbon group having 8 to 22 carbon atoms. R 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 oxyethylene. s is a number from 3 to 25 representing the average repeating number of EO. A 11 O represents at least one of PO (oxypropylene) and BO (oxybutylene). t is a number from 0 to 6 representing the average repeating number of A 11 O. u is a number from 0 to 20 representing the average repeating number of EO.)

[0114] R 13 -X-[(EO) p / (A 12 O) q -(EO) r -R 14 …(3)

[0115] (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 oxyethylene. p is a number from 3 to 25 representing the average repeating number of EO. A 12 represents at least one of PO (oxypropylene) and BO (oxybutylene). q is a number from 0 to 6 representing the average repeating number of A 12 O. r is a number from 0 to 20 representing the average repeating number of EO.)

[0116] The content of the nonionic surfactant is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass based on the total mass of the liquid detergent.

[0117] As non-soap anionic surfactants, for example, there may be mentioned: linear alkylbenzene sulfonic acid or its salts (LAS), α-olefin sulfonic acid or its salts (AOS), linear or branched alkyl sulfates or their salts (AS), polyoxyalkylene (alkenyl) ether sulfates or their salts (AES), alkane sulfonic acids having an alkyl group or their salts, α-sulfo fatty acid esters or their salts, internal olefin sulfonic acids or their salts (IOS), hydroxyalkane sulfonic acids or their salts (HAS), alkyl ether carboxylic acids or their salts, polyoxyalkylene ether carboxylic acids or their salts, alkylamide ether carboxylic acids or their salts, alkenylamide ether carboxylic acids or their salts, acylamino carboxylic acids or their salts, etc., which are carboxylic acid type anionic surfactants; alkyl phosphates or their salts, polyoxyalkylene phosphates or their salts, polyoxyalkylene alkylphenyl phosphates or their salts, glycerol fatty acid monophosphates or their salts, etc., which are phosphate type anionic surfactants, etc.

[0118] As the salt forms of non-soap anionic surfactants, for example, there may be mentioned: alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.).

[0119] Non-soap anionic surfactants can be used alone or in combination of two or more.

[0120] As non-soap anionic surfactants, LAS, AOS, AS, AES, IOS, and HAS are preferred. Among them, from the viewpoint of further improving detergency, LAS, AES, and IOS are more preferred. The liquid detergent preferably contains at least AES, and more preferably contains both LAS and AES.

[0121] Polyoxyalkylene alkyl (alkenyl) ether sulfate or its salt (AES) is represented by the following general formula (4).

[0122] R 15 -O-[(EO) m / (PO) n -SO 3 - M + …(4)

[0123] (In the 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 oxyethylene. PO is oxypropylene. m is a number of 0.1 or more representing the average repeating number of EO. n is a number of 0 to 6 representing the average repeating number of PO. [(EO) m / (PO) n indicates that the arrangement order of EO and PO is not limited, and M + is a counter cation.)

[0124] Internal olefin sulfonic acid or its salt (IOS) is a mixture of olefin sulfonic acid represented by the following formula (5) (hereinafter, also referred to as "compound (5)") and hydroxyalkane sulfonic acid represented by the following formula (6) (hereinafter, also referred to as "compound (6)"). An internal olefin refers to an olefin having a double bond inside starting from the 2-position.

[0125] R 16 -CH=CH(CH 2 ) x CH(SO 3 M)-R 17 …(5)

[0126] (In formula (5), R 16 is an alkyl group, 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.)

[0127] Compound (5) has 8 to 24 carbon atoms, preferably 10 to 20, more preferably 12 to 18, and further preferably 14 to 18. If the number of carbon atoms is above the lower limit value, the lipophilicity of IOS increases and the surfactant function is enhanced. If the number of carbon atoms is below the upper limit value, the hydrophilicity of IOS increases and the surfactant function is enhanced.

[0128] R in formula (5) 16 represents an alkyl group. The number of carbon atoms of R 16 is preferably 1 to 21, more preferably 3 to 17, and further preferably 7 to 15.

[0129] R in formula (5) 17 represents an alkyl group having 1 to 5 carbon atoms. The number of carbon atoms of R 17 is preferably 1 to 3.

[0130] In formula (5), x is from 0 to 4, preferably from 0 to 2. If x is above the lower limit value, the detergency is further improved. If x is below the upper limit value, the liquid stability is further improved.

[0131] Examples of M in formula (5) include: sodium ion, potassium ion, magnesium ion, ammonium ion, etc.

[0132] R 18 -CH(OH)(CH 2 ) y CH(SO 3 M)-R 19 …(6)

[0133] (In formula (6), R 18is an alkyl group, 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.)

[0134] Compound (6) is the hydroxyl form of compound (5).

[0135] Compound (6) has 8 to 24 carbon atoms, preferably 10 to 20, more preferably 12 to 18, and further preferably 14 to 18. If the number of carbon atoms is above the lower limit value, the lipophilicity of IOS increases and the surfactant function is enhanced. If the number of carbon atoms is below the upper limit value, the hydrophilicity of IOS increases and the surfactant function is enhanced.

[0136] R in formula (6) 18 represents an alkyl group. R 18 preferably has 2 to 22 carbon atoms, more preferably 4 to 18 carbon atoms, and further preferably 8 to 16 carbon atoms.

[0137] R in formula (6) 19 represents an alkyl group having 1 to 5 carbon atoms. R 19 preferably has 1 to 3 carbon atoms.

[0138] y in formula (6) is from 0 to 4, preferably from 0 to 2. If y is above the lower limit value, the detergency is further improved. If y is below the upper limit value, the liquid stability is further improved.

[0139] Examples of M in formula (6) include sodium ion, potassium ion, magnesium ion, ammonium ion, etc.

[0140] In IOS, the mass ratio of the IOS ((IO-1S) component) in which the sulfonic acid group is present at the 2nd or higher and 4th or lower positions to the IOS ((IO-2S) component) in which the sulfonic acid group is present at the 5th or higher position, i.e., ((IO-2S) / (IO-1S) ratio), is preferably 0.3 to 5, more preferably 1 to 3.

[0141] If the (IO-2S) / (IO-1S) ratio is above the lower limit value, the smoothness of the object to be washed is further improved. If the (IO-2S) / (IO-1S) ratio is below the upper limit value, the liquid stability is further improved.

[0142] It should be noted that the (IO-1S) component is the IOS in which R in formula (5) 17 and R in formula (6) 19 have 1 to 3 carbon atoms. The (IO-2S) component is the IOS in which R in formula (5) 17 and R in formula (6) 19 have 4 or more carbon atoms.

[0143] IOS is obtained by sulfonating internal olefins. The total number of carbon atoms of the internal olefins is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and further preferably 14 to 18.

[0144] The internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. When the internal olefins are sulfonated, β-sultones are quantitatively produced, and a part of the β-sultones is converted into γ-sultones and olefin sulfonic acids, and then they are converted into compound (5) and compound (6) in the neutralization and hydrolysis step (for example, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxyl group of the obtained compound (6) is located inside the alkane chain, and the double bond of compound (5) is located inside the olefin chain. In addition, the obtained product is mainly a mixture thereof, and sometimes a small amount of hydroxyalkanesulfonate having a hydroxyl group at the end of the carbon chain or α-olefinsulfonate having a double bond at the end of the carbon chain is contained in a part thereof. In this specification, these respective products and their mixtures are collectively referred to as IOS.

[0145] The mass ratio represented by compound (5) / compound (6) (compound (5) / compound (6) ratio) is preferably 1 / 99 to 50 / 50, more preferably 1 / 99 to 30 / 70, further preferably 5 / 95 to 20 / 80, and particularly preferably 10 / 90 to 15 / 85 with respect to 100% by mass of IOS. If the compound (5) / compound (6) ratio is at or above the above lower limit value, the liquid stability is further improved. If the compound (5) / compound (6) ratio is at or below the above upper limit value, the detergency is further improved.

[0146] The content of the non-soap anionic surfactant is preferably 5 to 35% by mass, more preferably 10 to 40% by mass, based on the total mass of the liquid detergent.

[0147] In addition, the mass ratio of the non-soap anionic surfactant to the mass of the nonionic surfactant, that is, the mass ratio represented by non-soap anionic surfactant / nonionic surfactant is preferably 0.05 to 8, more preferably 0.2 to 5, and further preferably 0.3 to 4. If the above mass ratio is within the above range, a liquid detergent having excellent fluidity and high stability can be obtained even in a composition with a small amount of water.

[0148] Examples of the cationic surfactant include: long-chain aliphatic amide alkyl tertiary amines or their salts such as dimethylaminopropyl octanamide, dimethylaminopropyl decanamide, dimethylaminopropyl lauramide, dimethylaminopropyl myristamide, dimethylaminopropyl palmitamide, dimethylaminopropyl stearamide, dimethylaminopropyl behenamide, dimethylaminopropyl oleamide; aliphatic ester alkyl tertiary amines or their salts such as propyldimethylamine palmitate, propyldimethylamine stearate; dimethylolaminopropyl palmitamide, dimethylolaminopropyl stearamide; quaternary ammonium compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, etc.

[0149] Examples of the salt form of the cationic surfactant include: alkali metal salts (such as sodium salt, potassium salt, etc.), alkaline earth metal salts (such as magnesium salt, etc.), alkanolamine salts (such as monoethanolamine salt, diethanolamine salt, etc.).

[0150] The cationic surfactant can be used alone or in combination of two or more.

[0151] Relative to the total mass of the liquid detergent, the content of the cationic surfactant is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass. If the content of the cationic surfactant is within the above range, the softness imparting property, antibacterial property and deodorizing effect of the laundry can be improved.

[0152] Examples of the amphoteric surfactant include: alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, phosphoric acid type amphoteric surfactants, etc.

[0153] The amphoteric surfactant can be used alone or in combination of two or more.

[0154] Examples of the semi-polar surfactant include: alkylamine oxide, alkyldimethylamine oxide propionamide, etc.

[0155] The semi-polar surfactant can be used alone or in combination of two or more.

[0156] Relative to the total mass of the liquid detergent, the content of component (C) is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, and further preferably 30 to 60% by mass. If the content of component (C) is above the above lower limit value, the detergency is further improved. If the content of component (C) is below the above upper limit value, the fluidity of the liquid detergent can be maintained.

[0157] <Water>

[0158] As the water, purified water, ion-exchanged water, distilled water, tap water, etc. can be used.

[0159] The water content is less than 30% by mass, preferably 25% by mass or less, more preferably 20% by mass or less, relative to the total mass of the liquid detergent. In addition, the water content is preferably 3% by mass or more, more preferably 5% by mass or more, relative to the total mass of the liquid detergent. That is, the water content is preferably 3% by mass or more and less than 30% by mass, more preferably 5 - 25% by mass, and further preferably 5 - 20% by mass, relative to the total mass of the liquid detergent. If the water content is below the above upper limit value, the component (A2) is difficult to dissolve in the liquid detergent, and the particle appearance (number of particles, particle size, etc.) can be well maintained, and the appearance stability of the component (A2) is improved. If the water content is above the above lower limit value, the liquid detergent becomes less flammable.

[0160] It should be noted that the liquid detergent may also be substantially free of water. Here, "substantially free of" means that no water is actively added except for the unintentionally contained water.

[0161] <Optional component>

[0162] Examples of the optional component include: water-miscible organic solvents, auxiliary components other than the component (A), chelating agents, pH regulators, viscosity reducers and solubilizers, enzymes, antibacterial agents, thickeners other than the component (B), higher fatty acids or their salts, preservatives, antioxidants, inorganic reducing agents, enzyme stabilizers, feel improvers, fluorescent brighteners, color transfer inhibitors, anti-redeposition agents, colorants, opacifiers, anti-discoloration agents, water-soluble aids, bleaching agents, fluorescent agents, pearlescent agents, fragrance agents, extracts of natural products, etc.

[0163] The optional component can be used alone or in combination of two or more.

[0164] A water-miscible organic solvent refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25°C.

[0165] Examples of the water-miscible organic solvent include: alcohols such as ethanol, glycerol, 1-propanol, 2-propanol, 1-butanol, 3-methoxy-3-methyl-1-butanol (Solfit, trade name); diols such as propylene glycol (PG), butylene glycol, hexylene glycol; polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a molecular weight of about 200 - 1000, dipropylene glycol; alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, etc. Among these, from the viewpoints of less odor, easy availability, fluidity of the liquid detergent, etc., ethanol, glycerol, 3-methoxy-3-methyl-1-butanol, propylene glycol, polyethylene glycol with a molecular weight of about 200 - 1000, diethylene glycol monobutyl ether (butyl carbitol) are preferred.

[0166] The water-miscible organic solvents can be used alone or in combination of two or more.

[0167] Relative to the total mass of the liquid detergent, the content of the water-miscible organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

[0168] As the auxiliary component other than the component (A) (hereinafter, also referred to as "other auxiliary components"), for example, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium sulfite, potassium sulfite, sodium bisulfite, ammonium chloride, ammonium sulfate, aluminosilicate (such as zeolite, etc.) can be cited.

[0169] The other auxiliary components can be used alone or in combination of two or more.

[0170] The other auxiliary components can be dissolved in the liquid detergent or exist in a solid state.

[0171] Relative to the total mass of the liquid detergent, the content of the other auxiliary components is preferably 20% by mass or less, more preferably 0.5 to 10% by mass.

[0172] As the chelating agent, a chelating agent having a carboxylic acid group or its salt with a valence of 3 to 4 is preferably used. As specific examples, citric acid or its salt, amino carboxylic acid-based chelating agent or its salt can be cited. Amino carboxylic acid refers to a compound containing at least one primary amino group, secondary amino group or tertiary amino group and at least one carboxyl group in one molecule, and an amino carboxylic acid-based chelating agent refers to a chelating agent of amino carboxylic acid.

[0173] The amino carboxylic acid-based chelating agent can be a substance well-known in the field of detergents. As specific examples, methylglycine diacetic acid (MGDA), methylglycine diacetate, L-glutamic acid diacetic acid (GLDA), L-glutamic acid diacetate, diethylenetriaminepentaacetic acid (DTPA), diethylenetriaminepentaacetate, 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), L-aspartic acid-N,N-diacetate, etc. can be cited. Among these, citric acid or its salt, MGDA or its salt are preferred, and trisodium methylglycine diacetate is more preferred.

[0174] The chelating agent can be used alone or in combination of two or more.

[0175] The content of the chelating agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, relative to the total mass of the liquid detergent. If the content of the chelating agent is above the above lower limit value, it is easy to sufficiently obtain the effects of improving detergency, improving storage stability, and preventing discoloration.

[0176] Examples of the pH adjuster 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; 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.

[0177] The pH adjuster can be used alone or in combination of two or more.

[0178] The addition amount of the pH adjuster can be appropriately set as long as it is an amount for adjusting the liquid detergent to a specified pH.

[0179] Examples of the viscosity reducer and solubilizer include aromatic sulfonic acid or its salts. Specifically, toluenesulfonic acid, xylenesulfonic acid, isopropylbenzenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid or their salts can be cited. Examples of the salts of aromatic sulfonic acid include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, or alkanolamine salt.

[0180] The viscosity reducer and solubilizer can be used alone or in combination of two or more.

[0181] 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.

[0182] If the liquid detergent contains an enzyme, the detergency against sebum stains and protein stains can be further improved.

[0183] As the enzyme, a liquid enzyme preparation or a solid (granular) enzyme preparation can be used. In the case of using a solid enzyme preparation, a part or all of its amount exists in the liquid detergent in a solid state, which is preferred from the viewpoint of enzyme stability.

[0184] Examples of the enzyme include: protease, amylase, lipase, cellulase, mannanase, etc.

[0185] Examples of proteases include: Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Savinase Evity 16L, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, AlcalaseUltra 2.5L, Liquanase 2.5L, Liquanase Ultra2.5L, Liquanase Ultra 2.5XL, Coronase48L, Progress Uno 100L, Deozyme, Savinase Evity12T, Kannase Evity 24T, which are protease preparations available from Novozymes; Purafect L, Purafect OX, Properase L, etc., which are available from Genencor.

[0186] Examples of amylases include: Termamyl300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, Amplify 12L, Amplify Prime 100L, Stainzyme Plus 12T, which are amylase preparations available from Novozymes; Maxamyl, which is available from Genencor; Pullulanase AMANO, which is available from Amano Enzyme Inc.; DB-250, which is available from Seikagaku Corporation.

[0187] Examples of lipases include: Lipex100L, Lipolase 100L, Lipex 100T, etc., which are lipase preparations available from Novozymes.

[0188] Examples of cellulases include: Endolase5000L, Celluzyme 0.4L, Carezyme 4500L, Celluclean 4500T, etc., which are cellulase preparations available from Novozymes.

[0189] Examples of mannanases include: Mannaway 4L, Mannaway 4.0T, etc., which are mannanase preparations available from Novozymes.

[0190] Examples of the multi-enzyme 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 150L, Medlyey Core 200T, Medley CleanR, Medley Essential 200T, Medley SmartR, Medley Advance 200T, Medley Boost 200L, Medley SuperioR 100T, etc.

[0191] Enzymes can be used alone or in combination of two or more.

[0192] Relative to the total mass of the liquid detergent, the content of the enzyme is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, and still more preferably 0.4 to 2.5% by mass.

[0193] Examples of the antibacterial agent include: diclosan, triclosan, quaternary ammonium salts (benzalkonium chloride, etc.).

[0194] The antibacterial agent can be used alone or in combination of two or more.

[0195] Relative to the total mass of the liquid detergent, the content of the antibacterial agent is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, and still more preferably 0.03 to 2% by mass.

[0196] Examples of the thickener other than the component (B) (hereinafter also referred to as "other thickener") include: acrylic polymers, xanthan gum, carrageenan, etc.

[0197] Examples of commercially available products of acrylic polymers include: Carbopol (registered trademark) series products manufactured by Lubrizol. Examples of the Carbopol series include: Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultrez20, Carbopol Ultrez21, Carbopol Aqua 30, etc.

[0198] Other thickeners can be used alone or in combination of two or more.

[0199] The content of other thickeners is preferably 6% by mass or less, more preferably 0.2 - 4% by mass, relative to the total mass of the liquid detergent.

[0200] If the liquid detergent contains a higher fatty acid or its salt, the defoaming property is improved. It should be noted that the "defoaming property" refers to the property of suppressing the foaming of the liquid detergent.

[0201] Examples of the higher fatty acid or its salt include: single fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, behenic acid, etc., and mixed fatty acids such as coconut oil fatty acid and beef tallow fatty acid.

[0202] The higher fatty acid or its salt can be used alone or in combination of two or more. In particular, if two or more are used in combination, the defoaming property is further improved.

[0203] The content of the higher fatty acid or its salt is preferably 0.5 - 10% by mass, more preferably 1 - 8% by mass, and further preferably 1.5 - 6% by mass, relative to the total mass of the liquid detergent. If the content of the higher fatty acid or its salt is above the above lower limit value, the defoaming property is further improved, and if it is above the above upper limit value, the liquid stability at low temperature is improved.

[0204] Examples of the preservative include: 2 - bromo - 2 - nitropropane - 1,3 - diol, 3 - iodopropynyl butylcarbamate, zinc pyrithione, sodium pyrithione, octyl isothiazolin - 3 - one, 1,2 - benzisothiazolin - 3 - one (BIT), 5 - chloro - 2 - methylisothiazolin - 3 - one (CMIT), 2 - methylisothiazolin - 3 - one (MIT), ethoxylated cocoamine, octylene glycol, benzyl alcohol, phenoxyethanol, sodium benzoate, etc.

[0205] The preservative can be used alone or in combination of two or more.

[0206] The content of the preservative is preferably 0.001 - 2% by mass, relative to the total mass of the liquid detergent.

[0207] If the liquid detergent contains an antioxidant, it can inhibit the absorption of oxygen in the headspace of the container containing the liquid detergent. Moreover, it can inhibit fading and discoloration caused by light and heat.

[0208] As antioxidants, for example, the following can be mentioned: monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenolic antioxidants such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol); polymeric phenolic antioxidants such as dl-α-tocopherol, etc. Among these, monophenolic antioxidants and polymeric antioxidants are preferred. Among the monophenolic antioxidants, dibutylhydroxytoluene is particularly preferred. Among the polymeric phenolic antioxidants, dl-α-tocopherol is particularly preferred.

[0209] The antioxidant can be used alone or in combination of two or more.

[0210] Relative to the total mass of the liquid detergent, the content of the antioxidant is preferably 0.01 to 2% by mass.

[0211] If the liquid detergent contains an inorganic reducing agent, fading and discoloration caused by light and heat can be inhibited.

[0212] As the inorganic reducing agent, for example, the following can be mentioned: sulfites such as sodium sulfite and potassium sulfite; metabisulfites such as sodium metabisulfite and potassium metabisulfite; bisulfites such as sodium bisulfite and potassium bisulfite, etc. Among these, from the viewpoint of excellent storage stability, sodium sulfite is preferred.

[0213] The inorganic reducing agent can be used alone or in combination of two or more.

[0214] Relative to the total mass of the liquid detergent, the content of the inorganic reducing agent is preferably 0.01 to 3% by mass, more preferably 0.02 to 1% by mass, and further preferably 0.05 to 0.5% by mass. If the content of the inorganic reducing agent is above the above lower limit value, the effect of inhibiting light coloring can be easily obtained sufficiently, and if it is above the above upper limit value, the storage stability is improved.

[0215] As the enzyme stabilizer, for example, the following can be mentioned: boric acid, borax, formic acid or its salts, lactic acid or its salts, calcium salts such as calcium chloride and calcium sulfate, etc.

[0216] The enzyme stabilizer can be used alone or in combination of two or more.

[0217] Relative to the total mass of the liquid detergent, the content of the enzyme stabilizer is preferably 2% by mass or less.

[0218] As the feel improver, for example, the following can be mentioned: silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone.

[0219] The feel improver can be used alone or in combination of two or more.

[0220] Relative to the total mass of the liquid detergent, the content of the feel improver is preferably 5% by mass or less.

[0221] As a fluorescent brightening agent, examples include: fluorescent brightening agents of the stilbenyl biphenyl type, etc.

[0222] The fluorescent brightening agent can be used alone or in combination of two or more.

[0223] Relative to the total mass of the liquid detergent, the content of the fluorescent brightening agent is preferably 1% by mass or less.

[0224] As an anti-color transfer agent, examples include: polyvinylpyrrolidone, carboxymethyl cellulose, polyalkyleneamine, etc.

[0225] The anti-color transfer agent can be used alone or in combination of two or more.

[0226] Relative to the total mass of the liquid detergent, the content of the anti-color transfer agent is preferably 3% by mass or less.

[0227] As an anti-redeposition agent, examples 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 alkylene oxide units and polyalkylene oxide units, etc. As such water-soluble polymers, specifically, examples include: trade name "TexCare SRN-100" (manufactured by Clariant, weight average molecular weight 2000 - 3000), trade name "TexCare SRN-300" (manufactured by Clariant, weight average molecular weight 7000), trade name "Repel-O-Tex Crystal" (manufactured by Rhodia), trade name "Repel-O-Tex QC" (manufactured by Rhodia), etc. Among these, from the viewpoints of high solubility in water and excellent storage stability, TexCare SRN-100 is preferred. In addition, from the viewpoint of excellent operability, a 70% aqueous solution of the above TexCare SRN-100, sold under the trade name TexCare SRN-170 (manufactured by Clariant), is preferably used as the anti-redeposition agent.

[0228] As an anti-redeposition agent, in addition to the above, for example, alkylene oxide adducts of polyalkyleneimine, alkylene oxide adducts of polyalkyleneamine, etc. can also be used. Specifically, examples include: trade name "Sokalan HP20" (manufactured by BASF Corporation), etc.

[0229] The anti-redeposition agent can be used alone or in combination of two or more.

[0230] Relative to the total mass of the liquid detergent, the content of the anti-redeposition agent is preferably 0.01 - 5% by mass.

[0231] As the colorant, there is no particular limitation. For example, it may include: pigments described in the "Legal Pigment Handbook" (Japan Cosmetic Industry Federation), substances obtained by chemically modifying water-soluble polymers, etc. at the structural end of the chromophore. Specifically, it may include: C.I. Acid Red 138, C.I. Acid Red 260, C.I. Acid Red 106, Acid Yellow 203 (Yellow No. 203), Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Levanyl (registered trademark) Violet (Levanyl (registered trademark) purple), Liquitint (registered trademark) BLUE SE (Liquitint (registered trademark) blue SE), Liquitint (registered trademark) BLUE HP (Liquitint (registered trademark) blue HP), Liquitint (registered trademark) BLUE MC (Liquitint (registered trademark) blue MC), Liquitint (registered trademark) VIOLET CT (Liquitint (registered trademark) purple CT), Liquitint (registered trademark) VIOLET LS (Liquitint (registered trademark) purple LS), Liquitint (registered trademark) VIOLET DD (Liquitint (registered trademark) purple DD), Liquitint (registered trademark) GREEN SA (Liquitint (registered trademark) green SA), Liquitint (registered trademark) Bright Yellow (Liquitint (registered trademark) bright yellow), Liquitint (registered trademark) YELLOW SY (Liquitint (registered trademark) yellow SY), Liquitint (registered trademark) YELLOW LP (Liquitint (registered trademark) yellow LP), Liquitint (registered trademark) BRILLIANT ORANGE (Liquitint (registered trademark) bright orange), Liquitint (registered trademark) PINK AL (Liquitint (registered trademark) pink AL), Liquitint (registered trademark) RED ST (Liquitint (registered trademark) red ST), Liquitint (registered trademark) RED MX (Liquitint (registered trademark) red MX), L-280BLUE U, WA-S Color Green, Labracol 040(F) Red, PIGMOSOL (registered trademark) and other commonly used pigments and dyes. It should be noted that in this specification, "C.I." is the abbreviation of Color Index.

[0232] The colorant can be used alone or in combination of two or more.

[0233] The content of the colorant is preferably 0.00005 to 1.0 mass %, more preferably 0.00005 to 0.01 mass %, relative to the total mass of the liquid detergent. If the content of the colorant is above the lower limit, the liquid detergent can be sufficiently colored, and if it is above the upper limit, the laundry is less likely to be pigmented, and a liquid detergent with excellent dispersion stability can be easily obtained.

[0234] As the opacifier, for example, polystyrene emulsion, polyvinyl acetate emulsion, etc. are mentioned, and it is usually preferred to use an emulsion with a solid content of 30 to 50% by mass. As specific examples, polystyrene emulsion (trade name: Saivinol (registered trademark) RPX-196PE-3, solid content 40% by mass, manufactured by Saiden Chemical Co., Ltd.), Opulyn 301, Acusol OP 301, etc. are mentioned.

[0235] The opacifier may be used alone or in combination of two or more.

[0236] The content of the opacifier is preferably 0.001 to 0.5% by mass relative to the total mass of the liquid detergent.

[0237] As the flavoring agent, for example, there can be mentioned the flavors described in "Synthetic Flavor Chemistry and Product Knowledge" by Motokazu Indo, published by Chemical Industry Daily in 1996, and "Perfume and Flavor Chemicals" by STEFFEN ARCTANDER, published in Montclair, NJ in 1969. More specifically, there can be mentioned the flavoring agents including synthetic flavors, natural flavors derived from animals or plants, natural flavors, synthetic flavors, or blended flavors of both natural flavors and synthetic flavors, and the flavoring ingredients described in, for example, Japanese Patent Application Laid-Open No. 2002-146399.

[0238] The flavoring agent can be formulated as an encapsulated flavor encapsulated in a capsule formed of a polymer compound.

[0239] The flavoring agents may be used alone or in combination of two or more.

[0240] The content of the fragrance agent is preferably 0.01 to 2% by mass relative to the total mass of the liquid detergent.

[0241] <Physical Properties>

[0242] (pH)

[0243] The pH of the liquid detergent at 25°C is preferably 6 to 12, more preferably 7 to 11.

[0244] The pH of the liquid detergent can be adjusted as needed by adding a pH regulator.

[0245] The pH of the liquid detergent is the value measured at 25 °C using a pH meter (manufactured by Toa DKK Corporation, product name “HM-30G”) with the measurement object being the liquid detergent.

[0246] In addition, the pH of the dilution obtained by diluting 10 g of the liquid detergent in 30 L of tap water at 25 °C is preferably 7.5 to 11, more preferably 7.8 to 10.5, and still more preferably 8.0 to 10.

[0247] By dissolving the component (A2) in the liquid detergent upon dilution, the pH of the dilution can be brought within the range of 7.5 to 11.

[0248] (Viscosity)

[0249] The viscosity of the liquid detergent at 25 °C is preferably 100 to 2000 mPa·s, more preferably 150 to 1000 mPa·s. If the viscosity of the liquid detergent is within the above range, it is easy to measure the liquid detergent with a metering cap, etc. In addition, when used for coating and washing, it is easy to apply the liquid detergent to fibrous products, etc.

[0250] The viscosity of the liquid detergent represents the value measured using a viscometer (e.g., TVB-25L) with the sample adjusted to 25 °C. An example of the measurement conditions for viscosity is shown below.

[0251] <<An example of the measurement conditions>>

[0252] · Rotor: No. 2 rotor.

[0253] · Rotation speed: 60 rpm.

[0254] · Measurement temperature: 25 °C.

[0255] · Reading of viscosity: 5 minutes after the rotor starts rotating.

[0256] (TI value)

[0257] The thixotropic index (TI value) of the liquid detergent is preferably 1.5 to 5.0, more preferably 1.8 to 4.0. If the TI value is at least the above lower limit value, it has excellent thixotropy and the dispersion stability of the solid component (A) is further improved. If the TI value is at most the above upper limit value, the fluidity of the liquid detergent is less likely to be impaired.

[0258] The TI value of the liquid detergent is calculated by the following formula (i).

[0259] TI value = (viscosity after 5 minutes at 6 rpm) / (viscosity after 5 minutes at 60 rpm) … (i)

[0260] The viscosity is the value (mPa·s) measured at 25°C for the object to be measured using a viscometer (such as TVB-25L) with rotor No. 2.

[0261] <Manufacturing method>

[0262] There is no particular limitation on the manufacturing method of the liquid detergent, and the liquid detergent can be manufactured based on conventional methods.

[0263] For example, the liquid detergent can be manufactured by mixing the above-mentioned component (A), component (B), a part of water, component (C) as needed, any component other than the pH regulator, adjusting to a specified pH using a pH regulator as needed, and then mixing the remaining water. It should be noted that when the liquid detergent contains an enzyme and is adjusted to a specified pH using a pH regulator, it is preferably formulated with the enzyme after adjusting the pH.

[0264] Component (A) can be pre-coated with a coating agent to form a coated basic agent.

[0265] <Usage method>

[0266] As a usage method of the liquid detergent, for example, there can be cited: a method of putting the liquid detergent into the liquid detergent inlet of a washing machine and then running the washing machine; a method of putting the liquid detergent and the object to be washed into water during washing; a method of immersing the object to be washed in a washing solution prepared by previously dissolving the liquid detergent in water; a method of directly applying the liquid detergent onto the object to be washed, leaving it for, for example, 3 minutes to 24 hours, and then performing normal washing, etc.

[0267] In addition, it is also preferable to use a washing machine with an automatic detergent dispensing function that has been put into practical use in recent years.

[0268] The automatic detergent dispensing function is a function of automatically dispensing the detergent from a tank containing the detergent through a filter for dust removal provided at the bottom of the tank and a dispensing pipe into the washing tub.

[0269] A metering unit such as an injection pump is provided in the middle of the dispensing pipe, and a fixed amount set according to the amount of laundry, etc. can be sent from the tank to the washing tub.

[0270] If the automatic detergent dispensing function is utilized, not only can the metering time be saved, but also it is possible to avoid the liquid detergent adhering to the hand or overflowing during metering and polluting the washing machine or the surroundings.

[0271] In addition, it is also preferable to use an automatic dispenser that can automatically discharge a specified amount of liquid. Even when using an automatic dispenser, since even a small amount of liquid cleaning agent can be accurately metered, it is easy to exert sufficient detergency, and it is also possible to avoid waste caused by overuse, so it is preferable.

[0272] In automatic dispensers, commercially available automatic dispensers that automatically discharge using non-contact switches such as infrared sensors are available. If such an automatic dispenser is used, the liquid detergent can be measured only by holding out a container held in one hand, and the effect of reducing the burden on the user is good.

[0273] In addition, when using an automatic dispenser, it is also preferable to receive the discharged liquid detergent in a soft container and directly put the soft container into the washing machine. Thereby, all of the discharged liquid detergent can be reliably dissolved in the washing liquid.

[0274] Examples of the soft container material that can be directly put into the washing machine include, for example: silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, polyurethane, etc.

[0275] Examples of the articles to be washed include, for example: fibrous products such as clothing (fabric), dishcloths, towels, sheets, curtains, etc. The raw material of the fibrous product is not particularly limited, and any of natural fibers such as cotton, silk, wool, and chemical fibers such as polyester and polyamide.

[0276] When using the liquid detergent by dissolving it in water, for example, it is preferably diluted 5 to 6000 times (based on volume).

[0277] The bath ratio (the mass of the washing liquid during laundry / the mass of the clothing) of the amount of water per unit clothing amount is preferably 5 or more for a drum washing machine and preferably 10 or more for a vertical washing machine.

[0278] The liquid detergent is suitable as a detergent for fibrous products. In particular, if the liquid detergent contains an uncoated component (A) and the particle size of the component (A) is less than 200 μm, more preferably less than 100 μm, it is suitable for use in washing machines and automatic dispensers equipped with an automatic detergent dispensing function.

[0279] <Function and effect>

[0280] At least a part of the component (A) in the liquid detergent of the present invention described above exists in a solid state, and the liquid detergent contains an amount of the component (A) that exceeds the solubility. Therefore, the liquid detergent of the present invention has strong detergency.

[0281] In addition, the dispersion stability of the component (A) existing in a solid state is excellent, and it is not easily dissolved in the liquid detergent, and the particle appearance can be maintained, and the appearance stability is also excellent.

[0282] When using a liquid detergent for laundry, since the liquid detergent is diluted with water, the component (A) existing in a solid state gradually dissolves in the laundry detergent, the concentration around the component (A) becomes concentrated, and it acts on stains and fiber products at a high concentration, enabling high detergency to be exerted.

[0283] Examples

[0284] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

[0285] The raw materials used in this example are as follows.

[0286] "Raw materials used"

[0287] As the component (A), the following compounds are used.

[0288] · A-1: Sodium carbonate (manufactured by Soda Ash Japan Co., Ltd., trade name "Granular Ash").

[0289] · A-2: Sodium silicate (manufactured by Tokuyama Corporation, trade name "Purifeed").

[0290] · A-3: The particles obtained by pulverizing A-1 and sieving with a sieve having a mesh size of 100 μm and passing through the sieve.

[0291] · A-4: The particles obtained by sieving the coating base agent 1 described later with a sieve having a mesh size of 1000 μm and passing through the sieve.

[0292] · A-5: The particles obtained by sieving the coating base agent 2 described later with a sieve having a mesh size of 1000 μm and passing through the sieve.

[0293] As the coating agent for the component (A), the following compounds are used.

[0294] · TL-400: Sodium acrylate-maleate copolymer (manufactured by Nippon Catalyst Co., Ltd., trade name "AQUALIC TL-400", 40 mass% aqueous solution of pure component).

[0295] · CaCl 2 : Calcium chloride (manufactured by Kanto Chemical Co., Inc.).

[0296] · HPMC: Hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "METOLOS60SH-06").

[0297] · Sodium sulfate: Sodium sulfate (manufactured by Shikoku Chemicals Corporation, trade name "Sodium Sulfate Anhydride").

[0298] · LAS-H: Linear alkylbenzene sulfonic acid with an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Specialty Chemical Co., Ltd., trade name “LYPON (registered trademark) LH-200”).

[0299] · Acrylic acid-maleic acid copolymer: Sodium acrylate-maleate copolymer (manufactured by Nippon Catalyst Co., Ltd., trade name “AQUALIC TL-400”, 40 mass% aqueous solution of pure component).

[0300] · Zeolite: (Manufactured by Thai Silicate Chemical Co., Ltd., trade name “Zeolite Na-4A”).

[0301] · Calcium nitrate: (Manufactured by Yoneyama Chemical Co., Ltd., trade name “Calcium Nitrate”).

[0302] It should be noted that CaCl 2 and calcium nitrate are responsive salts.

[0303] As component (B), the following compounds are used.

[0304] · B-1: Bacterial cellulose (manufactured by CP Kelco U.S., Inc., trade name “CELLULON (registered trademark) L27”).

[0305] · B-2: Hydrogenated castor oil (manufactured by NOF Corporation, trade name “Castor Wax A Flake”).

[0306] As component (C), the following compounds are used.

[0307] · C-1: Polyoxyethylene alkyl ether (manufactured by Lion Specialty Chemical Co., Ltd., trade name “LEOX CL-70”. In general formula (2), R 11 is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (C12:C14 = 75:25 by mass ratio), the carbon atom of R 11 bonded to the oxygen atom is a primary carbon atom, R 12 is a hydrogen atom, s is 7, t is 0, and u is 0 in compound (2)).

[0308] · C-2: Polyoxyethylene alkyl ether (manufactured by Lion Specialty Chemical Co., Ltd., trade name “LEOX CL-90”. In (2), R 11 is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (C12:C14 = 75:25 by mass ratio), the carbon atom of R 11 bonded to the oxygen atom is a primary carbon atom, R 12It is a compound (2) where the hydrogen atom, s is 9, t is 0, and u is 0).

[0309] ·C-3: Polyoxyethylene alkyl ether (manufactured by Aoki Yushi Kogyo Co., Ltd., trade name “BLAUNON CH-308”). In general formula (2), R 11 is a straight-chain alkyl group with 16 carbon atoms, and the carbon atom of R bonded to the oxygen atom 11 is a primary carbon atom, R 12 is a hydrogen atom, s is 8, t is 0, and u is 0 of the compound (2)).

[0310] ·C-4: MEE. For coconut fatty acid methyl ester (a mixture of methyl laurate / methyl myristate = 8 / 2 by mass ratio), a compound obtained by adding 15 moles equivalent of ethylene oxide using an alkoxylation catalyst. In general formula (3), R 13 is an alkyl group with 11 carbon atoms and an alkyl group with 13 carbon atoms, R 14 is a methyl group, p is 15, q is 0, r is 0, and the narrow ratio is 33% of the compound (3). It is synthesized by the following synthesis method.

[0311] ·C-5: Linear alkylbenzene sulfonic acid having an alkyl group with 10 to 14 carbon atoms (manufactured by Lion Specialty Chemical Co., Ltd., trade name “LYPON (registered trademark) LH-200”).

[0312] ·C-6: Polyoxyalkylene ether sulfate (in general formula (4), R 15 is a straight-chain alkyl group with 12 carbon atoms (C12) and a straight-chain alkyl group with 14 carbon atoms (C14) (C12:C14 = 75:25 by mass ratio), m is 1, n is 0, M is sodium, and the proportion of the compound where m is 0 and n is 0 relative to all of AES is 43% by mass of the compound (4). It is synthesized by the following synthesis method.).

[0313] ·C-7: IOS. Sodium internal olefin sulfonate synthesized by the following synthesis method, and the content of the hydroxyl form is 85% by mass. It is synthesized by the following synthesis method.

[0314] (Synthesis of C-4)

[0315] Synthesis is based on the synthesis method described in Japanese Patent Laid-Open No. 2000-144179. The composition is 2.5MgO·Al 2 O 3 ·wH 2Magnesium aluminum hydroxide of O (KYOWAAD 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) was calcined at 600 °C for 1 hour in a nitrogen atmosphere to obtain a calcined magnesium aluminum hydroxide (unmodified) catalyst. 2.2 g of the calcined magnesium aluminum hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of methyl laurate, and 70 g of methyl myristate were charged into an autoclave, and the modification of the catalyst was carried out in a 4L autoclave. Then, after purging the inside of the autoclave with nitrogen, while maintaining the temperature at 180 °C and the pressure at 0.3 MPa, 1052 g of ethylene oxide was introduced and reacted with stirring. The resulting reaction solution was cooled to 80 °C, 159 g of water, 5 g of activated clay as a filter aid, and 5 g of diatomaceous earth were added and mixed, and then the catalyst was filtered off to obtain C-4.

[0316] (Synthesis of C-6)

[0317] 400 g of a commercially available alcohol CO1270 (a mixture of an alcohol with 12 carbon atoms and an alcohol with 14 carbon atoms in a mass ratio of 75 / 25) manufactured by Procter & Gamble Co., Ltd. as a raw material alcohol and 0.8 g of a potassium hydroxide catalyst as a reaction catalyst were charged into a 4L autoclave. After purging the inside of the autoclave with nitrogen, the temperature was raised with stirring.

[0318] Then, while maintaining the temperature at 180 °C and the pressure below 0.3 MPa, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.

[0319] The results of analysis using a gas chromatograph: GC-5890 manufactured by Hewlett-Packard Company, detector: hydrogen flame ionization detector (FID), and chromatographic column: Ultra-1 (manufactured by Hewlett-Packard Company, L25m × φ0.2mm × T0.11μm) showed that the average number of moles of ethylene oxide added to the obtained alcohol ethoxylate was 1.0. In addition, the amount of the compound that did not add ethylene oxide (the compound that ultimately became component (b-0)) was 43% by mass relative to the total amount of the obtained alcohol ethoxylate.

[0320] Next, 237 g of the above-obtained alcohol ethoxylate was placed in a 500 mL flask equipped with a stirring device. 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) to obtain polyoxyethylene alkyl ether sulfate. Then, by neutralizing it with an aqueous sodium hydroxide solution, C-6 was obtained.

[0321] (Synthesis of C-7)

[0322] An internal olefin mixture is used as an internal olefin. The total proportion of double bonds present at the 2-position in the internal olefin mixture is 26% by mass, and the cis / trans mass ratio is 27 / 73. It contains 2.0% by mass of a paraffin component. This internal olefin is an internal olefin mixture composed of 3% by mass of C14 or less, 33% by mass of C15, 39% by mass of C16, 24% by mass of C17, and 1% by mass of C18 or more. Using this internal olefin mixture and a glass film sulfonation apparatus with an inner diameter of 6 mmφ and a length of 1.2 m, by using SO 3 gas (SO 3 concentration: 5% by volume), under the conditions of a reactor temperature of 10°C and a molar ratio of SO 3 / internal olefin of 1.1, the sulfonation reaction is carried out according to the conventional method to obtain internal olefin sulfonic acid. The internal olefin sulfonic acid of the obtained reaction product is aged at 5°C for 1 hour, and then 1.11 times the molar amount (relative to internal olefin sulfonic acid) of a 15% aqueous sodium hydroxide solution is added, and the mixture is stirred at 30°C for 30 minutes for the neutralization reaction to obtain a neutralized product. Then, the neutralized product is heated in an autoclave at 160°C for 40 minutes and hydrolyzed to obtain C-7.

[0323] As water and optional components, the following compounds are used.

[0324] · Water: Ion-exchanged water.

[0325] · Protease 1: Manufactured by Novozymes Japan Co., Ltd., trade name "Progress Uno 100L", enzyme liquid preparation.

[0326] · Protease 2: Manufactured by Novozymes Japan Co., Ltd., trade name "Savinase 12T", enzyme granule preparation.

[0327] · Monoethanolamine: Manufactured by Nippon Shokubai Co., Ltd., trade name "Monoethanolamine".

[0328] · Ethanol: Manufactured by Nippon Alcohol Sales Co., Ltd., trade name "Specified Alcohol 95 Degrees Synthetic".

[0329] · Glycerol: Manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "Glycerol".

[0330] · Propylene glycol: Manufactured by Dow Chemical Company, trade name "Propylene Glycol".

[0331] · Coconut fatty acid: Manufactured by NOF Corporation, trade name "Coconut Fatty Acid".

[0332] · Sokalan HP20: Manufactured by BASF SE, trade name "Sokalan HP20".

[0333] · Sokalan CP9: Manufactured by BASF SE, trade name "Sokalan CP9".

[0334] · Trisodium citrate dihydrate: Manufactured by Ichifangsha Oil & Fat Industry Co., Ltd., trade name "Liquid Citric Acid".

[0335] · Sodium benzoate: Manufactured by Toagosei Co., Ltd., trade name "Sodium Benzoate".

[0336] · Antioxidant: Butylated hydroxytoluene (manufactured by Wako Pure Chemical Industries, Ltd., trade name "Butylated Hydroxytoluene").

[0337] · Triclosan: Manufactured by BASF SE, trade name "Tinosan HP100".

[0338] · Sodium sulfite: Manufactured by Mitsui Chemicals, Inc., trade name "Sodium Sulfite".

[0339] · Fragrance: Fragrance composition A described in Tables 11 to 18 of Japanese Patent Laid-Open No. 2002-146399.

[0340] · Pigment: Manufactured by Kisuika Kasei Co., Ltd., trade name "Green No. 3".

[0341] · pH adjuster: Sulfuric acid (manufactured by Toagosei Co., Ltd.), sodium hydroxide (manufactured by Toagosei Co., Ltd.).

[0342] "Measurement / Evaluation Method"

[0343] (Measurement of particle size)

[0344] Using a particle size distribution measuring device (manufactured by Beckman Coulter, product name "LS 13 320"), the particle size (volume-based median particle size) of the coated base agent or component (A) is measured by the laser diffraction scattering method.

[0345] (Evaluation of dispersion stability)

[0346] The liquid detergent is allowed to stand and stored at 50°C for 1 week. Visually confirm the appearance of the liquid detergent after storage, and evaluate the dispersion stability of the inorganic base agent or coated base agent present in a solid state in the liquid detergent based on the following evaluation criteria.

[0347] ◎: Compared with before storage, there is basically no change, and the inorganic base agent or coated base agent is uniformly and stably dispersed.

[0348] 〇: Compared with before storage, the inorganic base agent or coated base agent has slightly settled, and the inorganic base agent or coated base agent in the upper part of the liquid detergent has become slightly sparser.

[0349] △: Compared with before storage, there is some sedimentation of the inorganic base agent or the coated base agent, and the inorganic base agent or the coated base agent in the upper part of the liquid detergent becomes somewhat sparser.

[0350] ×: The inorganic base agent or the coated base agent has completely sedimented.

[0351] (Evaluation of Appearance Stability)

[0352] Store the liquid detergent in the same way as for the evaluation of dispersion stability. Visually confirm the appearance of the liquid detergent after stirring during storage, and evaluate the appearance stability of the inorganic base agent or the coated base agent present in solid state in the liquid detergent based on the following evaluation criteria.

[0353] ◎: Compared with before storage, the appearance of the inorganic base agent or the coated base agent has basically not changed.

[0354] 〇: Compared with before storage, the inorganic base agent or the coated base agent has slightly dissolved.

[0355] △: Compared with before storage, the inorganic base agent or the coated base agent has dissolved somewhat.

[0356] ×: Compared with before storage, more than 70% of the visible inorganic base agent or the coated base agent has dissolved.

[0357] (Evaluation of Sebum Detergency)

[0358] Cut the artificial soil cloth (manufactured by the General Incorporated Foundation for Washing Science) impregnated with artificial soil in the Oil Chemical Association cloth (unstained cloth) into 5 cm × 5 cm as the contaminated cloth.

[0359] As the soil removal testing machine, use the Terg-O-tometer (manufactured by UNITED STATES TESTING COMPANY).

[0360] As the washing liquid, use the washing liquid prepared by adding the liquid detergent to 900 mL of water (15 °C, 3 °DH) to make it 333 ppm and stirring for 30 seconds.

[0361] Put the washing liquid, 10 pieces of the above-mentioned contaminated cloth, and the washing knitted cloth into the soil removal testing machine, and wash at 120 rpm and 15 °C for 10 minutes with a bath ratio (laundry water / total mass of the object to be washed) of 20 times.

[0362] Then, transfer it to a twin-tub washing machine (manufactured by Mitsubishi Electric Corporation, product name CW-C30A1-H1), dehydrate for 1 minute, wash in 30 L of water for 3 minutes, and air dry.

[0363] For the stain-free cloth and the contaminated cloth before and after washing, the reflectance was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE7700 type"), and the washing rate (%) was calculated by the following formula (ii). The evaluation criteria for sebum detergency are as follows: when the washing rate (%) is 60% or more, it is recorded as "◎"; when it is 55% or more and less than 60%, it is recorded as "〇"; when it is less than 55%, it is recorded as "×".

[0364] Washing rate (%) = (K / S of the contaminated cloth before washing - K / S of the contaminated cloth after washing) / (K / S of the contaminated cloth before washing - K / S of the stain-free cloth) × 100…(ii)

[0365] where "K / S" is the value obtained from (1 - R / 100) 2 / (2R / 100) (R represents the reflectance (%) of the stain-free cloth and the contaminated cloth before and after washing).

[0366] "Examples 1 to 15, 17 to 19, 25, Comparative Examples 2 to 3"

[0367] <Coating of Component (A): Stirring Granulation>

[0368] Adjust the Loedige mixer (manufactured by MATSUBO Co., Ltd., M20 type) equipped with a sickle-shaped shovel and a gap of 5 mm between the shovel and the wall surface to 45°C, add 5.6 kg of Component (A) of the type shown in Tables 1 to 4 heated to 45°C, and start stirring at 200 rpm of the main shaft. Note that the chopper is stopped. After 10 seconds from the start of stirring, TL-400 heated to 60°C is added according to the dosage amounts described in Tables 1 to 4. After the addition is completed, an aqueous solution of CaCl 2 with a solid component concentration of 41% by mass is added according to the dosage amounts described in Tables 1 to 4. Dry the granulated product as needed. Then, cool the granulated product to room temperature (25°C) to obtain the granulated product. Note that the dosage amounts of the coating agent and the responsive salt shown in Tables 1 to 4 are amounts (mass%) relative to the total mass of the liquid detergent.

[0369] The obtained granulated product was screened using a sieve with a mesh size of 1000 μm, and the particles passing through the 1000-μm sieve were used as the coated alkali agent with the surface of Component (A) coated with the coating agent.

[0370] The particle size (median particle size) of the obtained coated alkali agent was measured. The results are shown in Tables 1 to 4.

[0371] <Preparation of Liquid Detergent>

[0372] In a 500 mL beaker, according to the components formulated in Tables 1 to 4, add component (B), component (C), water, a part of glycerol, and any components other than the pH regulator, and stir well with a Three-One Motor stirrer (manufactured by AS ONE Corporation). Then, add an appropriate amount of the pH regulator to adjust the pH at 25 °C to 6.5 - 7.5, and then add the coating base agent and stir. It should be noted that the addition amount of the coating base agent is adjusted so that the content of component (A) relative to the total mass of the liquid detergent is the value shown in Tables 1 to 4. Add the remaining glycerol to make the total amount 100% by mass to obtain the liquid detergent.

[0373] In the obtained liquid detergent, a part of component (A) exists in a solid state.

[0374] For the obtained liquid detergent, evaluate the dispersion stability, appearance stability, and sebum detergency. The results are shown in Tables 1 to 4.

[0375] "Example 16"

[0376] <Coating of component (A): Stirring granulation>

[0377] Adjust the Loedige mixer (manufactured by MATSUBO Corporation, model M20) equipped with a sickle-shaped shovel and a 5-mm gap between the shovel and the wall surface to 45 °C, add 4 kg of component (A) of the type shown in Table 2 heated to 45 °C and 1.6 kg of sodium sulfate, and start stirring at 200 rpm of the main shaft. It should be noted that the chopper is stopped. After 10 seconds from the start of stirring, add TL-400 heated to 60 °C according to the formulation amounts recorded in Table 2. After the addition is completed, add an aqueous solution of the solid component of CaCl with a concentration of 41% by mass heated to 60 °C according to the formulation amounts recorded in Table 2. Dry the granulated product as needed. Then, cool the granulated product to room temperature (25 °C) to obtain the granulated product. It should be noted that the formulation amounts of the coating agent and the responsive salt shown in Table 2 are amounts (mass%) relative to the total mass of the liquid detergent. 2 The granulated product obtained is sieved using a sieve with a mesh of 1000 μm, and the particles passing through the 1000-μm sieve are used as the coating base agent with the surface of component (A) coated with the coating agent.

[0378] Measure the particle size (median particle size) of the obtained coating base agent. The results are shown in Table 2.

[0379] <Preparation of liquid detergent>

[0380]

[0381] ​In a 500 mL beaker, according to the composition shown in Table 2, add component (B), component (C), water, a part of glycerol, and any component other than the pH regulator, and stir well with a Three-One Motor stirrer (manufactured by AS ONE Corporation). Then, add an appropriate amount of the pH regulator to adjust the pH at 25 °C to 6.5 - 7.5, and then add the coated alkali agent and stir. It should be noted that the addition amount of the coated alkali agent is adjusted so that the content of component (A) relative to the total mass of the liquid detergent is the value shown in Table 2. Add the remaining glycerol to make the total amount 100% by mass to obtain the liquid detergent.

[0382] In the obtained liquid detergent, a part of component (A) exists in a solid state.

[0383] For the obtained liquid detergent, evaluate the dispersion stability, appearance stability, and sebum detergency. The results are shown in Table 2.

[0384] "Examples 20 - 21"

[0385] <Coating of component (A): Fluidized bed granulation>

[0386] Add 600 g of component (A) of the type shown in Table 3 to a fluidized bed granulator (manufactured by Powrex Corporation, product name "FD-MP-01D / SPC"). Then, send air at 80 °C into the fluidized bed. After confirming that the powder has been fluidized, spray a 12% by mass aqueous solution of HPMC from the upper part into the fluidized powder layer according to the formulation amounts recorded in Table 3 (two-fluid nozzle).

[0387] Adjust the wind speed in the fluidized bed to maintain the fluidized state while performing the granulation / coating operation. It should be noted that the formulation amount of the coating agent shown in Table 3 is the amount (mass%) relative to the total mass of the liquid detergent.

[0388] After the granulation / coating operation is completed, send air at 80 °C into the fluidized bed for about 30 minutes to dry until the water content of the coated alkali agent is about 7% by mass. Take out the granulated product from the fluidized bed granulator and cool it to room temperature (25 °C) to obtain the granulated product.

[0389] Sieve the obtained granulated product using a sieve with a mesh size of 1000 μm, and use the particles passing through the 1000 μm sieve as the coated alkali agent with the surface of component (A) coated with the coating agent.

[0390] Measure the particle size (median particle size) of the obtained coated alkali agent. The results are shown in Table 3.

[0391] <Preparation of liquid detergent>

[0392] In a 500 mL beaker, according to the components in Table 3, add component (B), component (C), water, a part of glycerol, and any components other than the pH regulator, and stir well with a Three-One Motor stirrer (manufactured by AS ONE Corporation). Then, add an appropriate amount of the pH regulator to make the pH at 25°C be 6.5 - 7.5, and then add the coated alkali agent and stir. It should be noted that the addition amount of the coated alkali agent is adjusted so that the content of component (A) is the value shown in Table 3 relative to the total mass of the liquid detergent. Add the remaining glycerol to make the total amount 100% by mass to obtain the liquid detergent.

[0393] In the obtained liquid detergent, a part of component (A) exists in a solid state.

[0394] For the obtained liquid detergent, evaluate the dispersion stability, appearance stability, and sebum detergency. The results are shown in Table 3.

[0395] "Example 22"

[0396] <Coating of component (A): Fluidized bed granulation>

[0397] Add 600 g of component (A) of the type shown in Table 3 to a fluidized bed granulator (manufactured by Powrex Corporation, product name "FD-MP-01D / SPC"). Then, send air at 80°C into the fluidized bed. After confirming that the powder has been fluidized, a 20% by mass aqueous solution of sodium sulfate is sprayed onto the fluidized powder layer from the upper part according to the addition amount recorded in Table 3 (two-fluid nozzle). Then, a 12% by mass aqueous solution of HPMC is sprayed onto the fluidized powder layer from the upper part according to the addition amount recorded in Table 3 (two-fluid nozzle). Adjust the wind speed in the fluidized bed to maintain the fluidized state while performing the granulation / coating operation. It should be noted that the addition amount of the coating agent shown in Table 3 is the amount (mass%) relative to the total mass of the liquid detergent.

[0398] After the granulation / coating operation is completed, send air at 80°C into the fluidized bed for about 30 minutes to dry until the water content of the coated alkali agent is about 7%. Take out the granulated product from the fluidized bed granulator and cool it to room temperature (25°C) to obtain the granulated product.

[0399] Sieve the obtained granulated product using a sieve with a mesh of 1000 μm, and use the particles passing through the 1000 μm sieve as the coated alkali agent with the surface of component (A) coated with the coating agent.

[0400] Measure the particle size (median particle size) of the obtained coated alkali agent. The results are shown in Table 3.

[0401] <Preparation of liquid detergent>

[0402] In a 500 mL beaker, according to the formulation composition in Table 3, add component (B), component (C), water, a part of glycerol, and any components other than the pH regulator, and stir well with a Three-One Motor stirrer (manufactured by AS ONE Corporation). Then, add an appropriate amount of the pH regulator to adjust the pH at 25°C to 6.5 - 7.5, and then add the coated base agent and stir. It should be noted that the addition amount of the coated base agent is adjusted so that the content of component (A) relative to the total mass of the liquid detergent is the value shown in Table 3. Add the remaining glycerol to make the total amount 100% by mass to obtain the liquid detergent.

[0403] In the obtained liquid detergent, a part of component (A) exists in a solid state.

[0404] For the obtained liquid detergent, evaluate the dispersion stability, appearance stability, and sebum detergency. The results are shown in Table 3.

[0405] "Examples 23 - 24"

[0406] <Preparation of Liquid Detergent>

[0407] In a 500 mL beaker, according to the formulation composition in Table 3, add component (B), component (C), water, a part of glycerol, and any components other than the pH regulator, and stir well with a Three-One Motor stirrer (manufactured by AS ONE Corporation). Then, add an appropriate amount of the pH regulator to adjust the pH at 25°C to 6.5 - 7.5, and then add component (A) of the type shown in Table 3 and stir. Add the remaining glycerol to make the total amount 100% by mass to obtain the liquid detergent.

[0408] In the obtained liquid detergent, a part of component (A) exists in a solid state.

[0409] For the obtained liquid detergent, evaluate the dispersion stability, appearance stability, and sebum detergency. The results are shown in Table 3. In addition, measure the particle size (median particle size) of component (A) (inorganic base agent) used in Examples 23 - 24. The results are shown in Table 3.

[0410] "Comparative Example 1"

[0411] <Preparation of Liquid Detergent>

[0412] In a 500 mL beaker, according to the composition shown in Table 4, add component (B), component (C), water, a part of glycerol, and any components other than the pH regulator, and stir well with a Three-One Motor stirrer (manufactured by AS ONE Corporation). Then, add an appropriate amount of the pH regulator to adjust the pH at 25 °C to 6.5 - 7.5, and then add the remaining glycerol to make the total amount 100% by mass, obtaining a liquid detergent.

[0413] For the obtained liquid detergent, evaluate the dispersion stability, appearance stability, and sebum detergency. The results are shown in Table 4.

[0414] "Examples 26 - 29"

[0415] <Coating of component (A): Spray-dried granulation>

[0416] · Manufacturing method of coated alkali agent 1 by spray drying

[0417] Within the components shown in Table 5, by stirring all the components to be incorporated except calcium nitrate in component (A) and the coating agent for component (A) at an adjusted temperature of 80 °C for 15 minutes, an aqueous slurry with 60% by mass of solid components is obtained.

[0418] Then, spray-dry the above aqueous slurry to prepare spray-dried particles (coated alkali agent 1) with a moisture content of 10.47% by mass.

[0419] Then, put it into a horizontal cylindrical rolling mixer.

[0420] Next, according to the composition shown in Table 5, spray and add calcium nitrate (solution) using a pressure nozzle while mixing for 3 minutes to obtain granulated products. At this time, control the Froude number at 0.08. Screen the obtained granulated products using a sieve with a mesh size of 1000 μm, and use the particles passing through the 1000 μm mesh sieve as A-4.

[0421] · Manufacturing method of coated alkali agent 2 by spray drying

[0422] Except for changing the incorporated composition as shown in Table 5, prepare spray-dried particles (coated alkali agent 2) with a moisture content of 8.62% by mass in the same manner as the above coated alkali agent 1.

[0423] Next, screen the obtained coated alkali agent 2 in the same manner as the above coated alkali agent 1, and use the particles passing through the 1000 μm mesh sieve as A-5.

[0424] It should be noted that LAS-Na in Table 5 is incorporated as LAS-H when manufacturing coated alkali agents (A-4) and (A-5), but exists in the form of LAS-Na in the obtained coated alkali agents (A-4) and (A-5).

[0425] <Preparation of Liquid Detergent>

[0426] In a 500 mL beaker, according to the composition ratio in Table 6, add component (C), water, a part of glycerol, and any component other than the pH regulator, and stir well with a Three-One Motor stirrer (manufactured by AS ONE Corporation). Then, add component (A-1) and stir well until dissolved. Next, add component (B) and confirm thoroughly. Finally, add the coated alkali agent (A-4) or (A-5) and stir. Add the remaining glycerol to make the total amount 100% by mass to obtain the liquid detergent.

[0427] In the obtained liquid detergent, a part of component (A) exists in a solid state.

[0428] For the obtained liquid detergent, evaluate the dispersion stability, appearance stability, and sebum detergency. The results are shown in Table 6.

[0429] [Table 1]

[0430]

[0431] [Table 2]

[0432]

[0433] [Table 3]

[0434]

[0435] [Table 4]

[0436]

[0437] [Table 5]

[0438] [Mass %] A-4 A-5 Sodium carbonate 71.1 74.3 LAS-H 0.83 0.88 Acrylic acid maleic acid copolymer 7.7 8.1 Zeolite 4.5 4.7 Calcium nitrate 5.4 3.4 Water content 10.47 8.62 Total 100 100

[0439] [Table 6]

[0440]

[0441] In Tables 1 to 4 and 6, the incorporation amounts (mass %) of each component other than B-1 are all ratios relative to the total mass of the liquid detergent, and represent values converted to pure components except in cases where otherwise specified. The incorporation amount (mass %) of B-1 is the current state. "Appropriate amount" means incorporating a pH regulator so that the pH of the liquid detergent at 25°C is the value shown in Tables 1 to 4 and 6. "Balance" means incorporating glycerin so that the total incorporation amount (mass %) of all incorporated components contained in the liquid detergent in each example reaches 100 mass %. That is, the incorporation amount of glycerin is the remainder obtained by subtracting the total incorporation amount (converted to pure components) of the incorporated components other than glycerin from the total mass of the liquid detergent. In addition, a blank column for the incorporation amount means that the component is not incorporated (the incorporation amount is 0 mass %).

[0442] In addition, the "washing liquid pH" in Tables 1 to 4 and 6 is the pH of a dilution obtained by diluting 10 g of the liquid detergent in 30 L of tap water at 25°C.

[0443] As can be seen from Tables 1 to 3 and 6, in the liquid detergents obtained in each example, the dispersion stability and appearance stability of the inorganic base agent present in a solid state are excellent, and the sebum detergency is strong.

[0444] On the other hand, as can be seen from Table 4, the sebum detergency of the liquid detergent of Comparative Example 1 that does not contain component (A) is poor.

[0445] In the liquid detergent of Comparative Example 2 that does not contain component (B), the dispersion stability of the inorganic base agent present in a solid state is poor.

[0446] In the liquid detergent of Comparative Example 3 in which the water content is 35 mass %, the appearance stability of the inorganic base agent present in a solid state is poor.

[0447] Industrial availability

[0448] According to the present invention, it is possible to provide a liquid detergent having excellent dispersion stability, particle appearance stability and aesthetics, and strong detergency of an inorganic base agent present in a solid state.

Claims

1. A liquid detergent, comprising: (A) component: an inorganic base agent; and (B) component: one or more structurants selected from the group consisting of bacterial cellulose, non-bacterial cellulose, and compounds represented by the following general formula (1), In the liquid detergent, at least a part of the (A) component exists in a solid state, and the proportion of the (A) component existing in a solid state is 20 to 95% by mass based on the total mass of the (A) component, The water content is 5 to 25% by mass based on the total mass of the liquid detergent, In the liquid detergent, the surface of the (A) component existing in a solid state is coated with a coating agent to form a coating layer, The coating agent is 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, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate, aluminosilicate, calcium chloride, and calcium nitrate, When the coating agent is polyacrylic acid, salts of polyacrylic acid, acrylic acid-maleic acid copolymer, salts of acrylic acid-maleic acid copolymer, the coating layer further contains one or more selected from the group consisting of calcium chloride, magnesium chloride, and aluminum chloride, In formula (1), Z 1 ~Z 3 are each independently a hydrogen atom, a hydroxyl group, or a carboxyl group, 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 in the liquid detergent, the particle size of the (A) component existing in a solid state is 10 to 2000 μm.

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