Water-soluble unit dose articles

Abstract

In a water-soluble unit-dose product containing dicrosan, both cleaning properties and the solubility of the water-soluble resin substrate are achieved. [Solution] In the water-soluble unit-dose article, granular material is held within a water-soluble resin substrate. The water-soluble unit-dose article contains dicrosan and a surfactant. The dicrosan is contained within the granular material.

Description

Technical Field

[0001] The present invention relates to water-soluble unit-dose articles.

Background Art

[0002] A technique of configuring a laundry detergent as a water-soluble unit-dose article is known (for example, see Patent Document 1). In such a water-soluble unit-dose article, since a water-soluble unit-dose article containing a certain amount of laundry detergent can be directly put into a washing machine without the consumer having to measure it themselves when using the laundry detergent, high convenience can be obtained in daily laundry.

[0003] In the water-soluble unit-dose article described in Patent Document 1, a water-soluble fiber structure formed of a water-soluble resin such as polyvinyl alcohol (PVA) is used as a substrate for holding particles of cleaning components such as surfactants.

[0004] In recent years, with the diversification of lifestyles, the demand for being able to comfortably perform indoor drying or drying at night of laundry has been increasing. In order to meet such a demand, it is effective to incorporate an antibacterial component into the laundry detergent. Since the antibacterial component has the effect of suppressing the growth of bacteria, it is possible to prevent the generation of odors in the laundry even when it takes a long time to dry the laundry.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Diphenyl ether compounds are known as antibacterial components with high antibacterial properties, and among them, dicrosan is often used in laundry detergents. In contrast, the inventors of this application have found that when liquid raw materials such as dicrosan are incorporated into water-soluble unit-dose articles, the original solubility in water of the water-soluble fiber structure constituting the base is easily impaired.

[0007] This invention relates to a technology for achieving both cleanability and water solubility of a water-soluble resin substrate in a water-soluble unit-dose article containing dicrosan. [Means for solving the problem]

[0008] In a water-soluble unit-dose article according to one embodiment of the present invention, granular material is held within a water-soluble resin substrate. The aforementioned water-soluble unit-dose article contains diclosan and a surfactant. The dichrosan is contained in the granular material. [Effects of the Invention]

[0009] According to the present invention, it is possible to achieve both cleaning properties and water solubility of the water-soluble resin substrate in a water-soluble unit-dose article containing dicrosan. [Brief explanation of the drawing]

[0010] [Figure 1] This figure schematically shows an example of the structure of a water-soluble unit-dose article according to one embodiment of the present invention. [Figure 2] This figure schematically shows other examples of the above-mentioned water-soluble unit-dose articles. [Modes for carrying out the invention]

[0011] The embodiments of the present invention will be described below. The present invention is not limited to the embodiments shown below, and various modifications can be made without departing from the spirit of the invention.

[0012] [Overall composition of water-soluble unit dose article W] A water-soluble unit-dose article W according to one embodiment of the present invention may be a unit-dose article of a laundry detergent used for washing clothes and the like. The water-soluble unit-dose article W comprises a water-soluble resin substrate X and granular material Y. In the water-soluble unit-dose article W, the granular material Y is held by the water-soluble resin substrate X. The water-soluble unit-dose article W also contains dicrosan and a surfactant. The dicrosan is contained in the granular material Y. The specific configuration of the water-soluble unit-dose article W will be described below.

[0013] [Water-soluble resin base X and granular material Y] The water-soluble resin substrate X is mainly composed of a water-soluble resin and, from the viewpoint of ease of manufacture, is preferably configured as a sheet extending in an in-plane direction perpendicular to the thickness direction. In the water-soluble resin substrate X, the content of the water-soluble resin is preferably 10% by mass or more from the viewpoint of shapeability. The water-soluble resin is defined as the resin in which no insoluble matter is visible after adding 1 g of the resin to a 1 liter glass beaker containing 500 g of ion-exchanged water at 30°C, placing a Teflon® stirring bar with a diameter of 10 mm (maximum diameter) and a total length of 8 cm, and stirring at 100 rpm for 30 minutes.

[0014] Examples of water-soluble resins usable for the water-soluble resin substrate X include polyvinyl alcohol (PVA), vinyl alcohol copolymers, polyvinylpyrrolidone, polyalkylene oxides, (modified) cellulose, (modified) cellulose ethers or esters or amides, polycarboxylic acids and their salts such as polyacrylate, maleic acid / acrylic acid copolymers, polyamino acids i.e., peptides, polyamides such as polyacrylamide, polysaccharides such as starch and gelatin, and natural rubbers such as xanthan gum and carragum. Vinyl alcohol copolymers include copolymers of vinyl alcohol with other monomers, such as ethylene and acrylic acid. For example, from the viewpoint of use as a water-soluble film forming a unit dose, the water-soluble resin is preferably selected from the group consisting of polyacrylate and water-soluble acrylate, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, maltodextrin, polymethacrylate, polyvinyl alcohol, vinyl alcohol copolymer, hydroxypropyl methylcellulose (HPMC), and combinations thereof. From a similar viewpoint, the water-soluble resin is more preferably selected from polyvinyl alcohol, vinyl alcohol copolymer, and hydroxypropyl methylcellulose. From a similar viewpoint, even more preferably, the water-soluble resin is polyvinyl alcohol, for example, Solbron, available from Aicello Corporation. Water-soluble resins that can be used for the water-soluble resin substrate X are described, for example, in U.S. Patent No. 6,995,126.

[0015] Figure 1 is a schematic diagram showing an example of the structure of a water-soluble unit-dose article W. In the water-soluble unit-dose article W shown in Figure 1, the water-soluble resin substrate X is a water-soluble fiber structure composed of an aggregate of multiple water-soluble fibers. In the water-soluble unit-dose article W shown in Figure 1, the granular material Y is held between the water-soluble fibers that make up the water-soluble resin substrate X. As a result, in the water-soluble unit-dose article W, the water-soluble resin substrate X and the granular material Y are maintained as an integrated unit.

[0016] The water-soluble fiber structure used as the water-soluble resin substrate X can be composed of one or more water-soluble fabric materials selected from, for example, nonwoven and woven water-soluble fibers. The water-soluble resin substrate X may be configured as a laminate of multiple water-soluble fabric materials or as a folded water-soluble fabric material. Furthermore, in the water-soluble unit-dose article W, the granular material Y does not necessarily have to be held between the water-soluble fibers of the water-soluble resin substrate X; for example, some or all of the granular material Y may be held by adhering to the surface of the water-soluble resin substrate X. Also, as shown in Figure 2, in the water-soluble unit-dose article W, the granular material Y may be held by being contained in a bag-shaped water-soluble resin substrate X. In the water-soluble unit-dose article W shown in Figure 2, the water-soluble resin substrate X is configured as a flat bag, and the granular material Y is contained within the water-soluble resin substrate X. Note that Figure 2 shows the granular material Y inside the water-soluble resin substrate X by viewing it through the water-soluble resin substrate X.

[0017] In the water-soluble unit-dose article W, the water-soluble resin substrate X only needs to be composed mainly of a water-soluble resin and capable of holding granular material Y, and does not have to be a water-soluble fiber structure. For example, the water-soluble resin substrate X may be composed of one or more water-soluble films. In this case, the water-soluble unit-dose article W can be configured such that the granular material Y is attached to and held on the surface of the water-soluble resin substrate X, or that the granular material Y is contained and held in a bag-shaped water-soluble resin substrate X. Furthermore, the water-soluble resin substrate X can be a combination of a water-soluble fiber structure and a water-soluble film. In addition, the shape of the water-soluble resin substrate X is not limited to a sheet shape, but may be any three-dimensional shape.

[0018] A water-soluble film bag-shaped water-soluble resin substrate X can be manufactured by any suitable process known in the art, such as a known detergent pouch manufacturing process. Examples of pouch manufacturing processes are described in U.S. Patents 6,995,126, 7,127,874, 8,156,713, 7,386,971, 7,439,215, and U.S. Patent Application Publication 2009 / 199877.

[0019] In the water-soluble unit-dose article W, the granular material Y is composed of components other than those contained in the water-soluble resin base X. Each granular material Y may be composed of a single component, or it may be composed of a mixture or aggregation of multiple components. In the water-soluble unit-dose article W, the amount of granular material Y is preferably 5 g or more, more preferably 8 g or more, and even more preferably 10 g or more, from the viewpoint of obtaining the effect of the granular material Y more effectively (for example, from the viewpoint of improving washability if the granular material Y has washability), and preferably 48 g or less, more preferably 38 g or less, and even more preferably 28 g or less, from the viewpoint of economy and lightness. In addition, in the water-soluble unit-dose article W, the average particle diameter of the granular material Y is preferably 100 μm or more, more preferably 150 μm or more, even more preferably 200 μm or more, and from the viewpoint of improving solubility, preferably 800 μm or less, more preferably 750 μm or less, and even more preferably 700 μm or less. The average particle size of granular material Y is determined from the mass fraction based on the sieve mesh size after vibrating it for 5 minutes using a standard sieve specified in JIS Z 8801.

[0020] The preferred shape and size of each water-soluble unit-dose article W is not particularly limited, but for example, from the viewpoint of efficient packaging and ease of use, it is a quadrilateral shape, with the length of one side preferably being 1 cm to 10 cm, more preferably 2 cm to 9 cm, and even more preferably 3 cm to 8 cm. From the viewpoint of robustness and ease of handling, the thickness is preferably 0.2 cm to 4 cm, more preferably 0.4 cm to 3 cm, and even more preferably 0.6 cm to 2 cm. The mass of each water-soluble unit-dose article W is preferably 5 g or more, more preferably 8 g or more, even more preferably 10 g or more, and preferably 50 g or less, more preferably 40 g or less, and even more preferably 30 g or less.

[0021] [Dichrosan] Diclosan, also known as 4,4'-dichloro-2-hydroxydiphenyl ether, is incorporated into the water-soluble unit-dose article W as an antibacterial component. In the water-soluble unit-dose article W, the action of diclosan suppresses the growth of bacteria during the drying process of laundry, thus preventing, for example, the occurrence of a musty odor in laundry when drying indoors, and preventing unpleasant odors from remaining on laundry after drying. In order to obtain sufficient antibacterial performance from diclosan, the water-soluble unit-dose article W is preferably neutral or acidic. Specifically, the pH at 25°C when dissolved in 30L of water is preferably 8.5 or less, more preferably 8.0 or less, and preferably 3.0 or higher.

[0022] Dicrosan is generally handled in a liquid state dispersed in propylene glycol. In a water-soluble unit-dose article W, granular material Y containing pre-mixed dicrosan is held on a water-soluble resin substrate X. This prevents a decrease in the solubility of the water-soluble resin substrate X due to contact with propylene glycol, which is the dispersion medium for dicrosan, in the water-soluble unit-dose article W. In particular, when a water-soluble fiber structure with very high water solubility is used as the water-soluble resin substrate X, the benefits of mixing dicrosan with granular material Y are more effectively obtained.

[0023] In the water-soluble unit-dose article W, dichrosan may be retained on the surface of granular material Y composed of other components such as surfactants, or dichrosan itself may constitute granular material Y. As a commercially available dichrosan, for example, "Tinosan® HP 100" manufactured by BASF Japan (effective content concentration 30% by mass, propylene glycol 70% by mass) can be used.

[0024] In the water-soluble unit-dose article W, from the viewpoint of more effectively obtaining the effects of dicrosan, the dicrosan content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more. Also, in the water-soluble unit-dose article W, from the same viewpoint, the dicrosan content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0025] [Surfactants] In water-soluble unit-dose article W, the cleaning performance can be improved by incorporating an alkaline agent, but in order to obtain sufficient antibacterial performance from diclosan, it is preferable to include as little alkaline agent as possible. On the other hand, in water-soluble unit-dose article W, by incorporating a surfactant, high cleaning performance can be easily obtained even in neutral or acidic compositions where no alkaline agent is included or the amount of alkaline agent is small.

[0026] In the water-soluble unit-dose article W, when a surfactant is included, from the viewpoint of improving cleaning performance, the surfactant content is preferably 45% by mass or more, more preferably 48% by mass or more, even more preferably 50% by mass or more, and preferably 60% by mass or less, more preferably 57% by mass or less, and even more preferably 55% by mass or less.

[0027] In the water-soluble unit-dose article W, the surfactant may be contained in either the water-soluble resin substrate X or the granular material Y, or in both, but from the viewpoint of improving solubility, it is preferably contained in the granular material Y.

[0028] (Anionic surfactant) The surfactant preferably contains an anionic surfactant to broaden the cleaning spectrum to remove mud particles and the like. In the water-soluble unit-dose article W, the surfactant is more preferably a sulfate ester type surfactant, and even more preferably an alkyl ether sulfate and / or a salt thereof, in order to improve cleaning performance.

[0029] When the surfactant contains an anionic surfactant, the content of the anionic surfactant in the water-soluble unit dose article W is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of improving cleaning performance, and preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less, from the viewpoint of economic efficiency.

[0030] When the surfactant contains a sulfate ester type surfactant, the content of the sulfate ester type surfactant in the water-soluble unit dose article W is preferably 6.5% by mass or more, more preferably 13% by mass or more, and even more preferably 20% by mass or more, from the viewpoint of improving cleaning performance, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of economic efficiency.

[0031] When the surfactant contains alkyl ether sulfate and / or a salt thereof, the content of alkyl ether sulfate and / or a salt thereof in the water-soluble unit dose article W is preferably 5% by mass or more, more preferably 6.5% by mass or more, from the viewpoint of improving cleaning performance, and preferably 20% by mass or less, more preferably 15% by mass or less, from the viewpoint of economic efficiency.

[0032] Furthermore, the surfactant may contain alkyl sulfate esters and / or salts thereof. In this case, in the water-soluble unit dose article W, the content of alkyl sulfate ester or salt thereof is preferably 5% by mass or more, more preferably 6.5% by mass or more, from the viewpoint of improving cleaning performance, and preferably 20% by mass or less, more preferably 15% by mass or less, from the viewpoint of economic efficiency. The content of alkyl sulfate ester or salt thereof is preferably 5% by mass or more and 20% by mass or less, more preferably 6.5% by mass or more and 15% by mass or less, from the viewpoint of improving cleaning performance and economic efficiency.

[0033] When the sulfate ester type surfactant is a salt, examples of the salt of the sulfate ester type surfactant include inorganic salts such as sodium salt, potassium salt, ammonium salt, and magnesium salt, and organic salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, and morpholine salt. The salt of the anionic surfactant is preferably an inorganic salt selected from alkali metal salts such as sodium salt and potassium salt, and alkaline earth metal salts such as magnesium salt, from the viewpoint of availability. From the viewpoint of improving solubility, alkali metal salts are more preferable, and from the viewpoint of economic efficiency, sodium salts are even more preferable.

[0034] The sulfate ester type surfactant is preferably a compound represented by the following general formula (1-1). R 1a -O-(AO) n -SO3M (1-1) (In the formula, R 1a (where A is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, A is one or more alkylene groups selected from ethylene and propylene groups, n is a number between 0 and 20 representing the average number of moles of alkylene oxy groups AO, and M is a cation.)

[0035] In formula (1-1), R 1a The aliphatic hydrocarbon group is preferably 10 or more, more preferably 11 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less. 1a is a linear or branched aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group, and more preferably a linear alkyl group.

[0036] In formula (1-1), AO is one or more alkylene oxy groups selected from ethylene oxy groups and propylene oxy groups. When AO contains both ethylene oxy and propylene oxy groups, the ethylene oxy and propylene oxy groups may be in the form of block bonds or random bonds. From the viewpoint of improving washability, it is preferable that AO is a group containing an ethylene oxy group.

[0037] In formula (1-1), n ​​is 0 or greater, preferably 20 or less, more preferably 16 or less, even more preferably 12 or less, even more preferably 8 or less, and even more preferably 4 or less, from the viewpoint of improving cleanability.

[0038] In formula (1-1), when AO contains a propyleneoxy group, the average number of moles of propyleneoxy groups is preferably 4 or less, more preferably 3 or less, and preferably 0 or more.

[0039] In formula (1-1), the average number of moles of propyleneoxy groups may be 0.

[0040] In formula (1-1), when AO contains ethyleneoxy groups, the average number of moles of ethyleneoxy groups is preferably 0 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.

[0041] In formula (1-1), M is preferably an alkali metal ion such as a hydrogen ion, sodium ion, or potassium ion, an alkaline earth metal (1 / 2 atom) ion such as a magnesium ion or calcium ion, or an organic ammonium ion. The organic ammonium salt may be a salt of an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal ion such as a sodium ion or potassium ion, or an alkanol ammonium ion such as a monoethanolammonium ion or a diethanolammonium ion, and more preferably a sodium ion.

[0042] The surfactant is represented by formula (1-1), where n represents the (non-average) number of moles n1 (integer value) of alkylene oxy group AO, and n1 is 1 or greater, R 1a When M contains compound ES as described above, the content of compound ES in the water-soluble unit dose article W is preferably 5% by mass or more, more preferably 6.5% by mass or more, from the viewpoint of improving cleaning performance, and preferably 20% by mass or less, more preferably 15% by mass or less, from the viewpoint of economic efficiency.

[0043] The surfactant is represented by formula (1-1), where n is 0 and R 1a When M contains the same compound AS as described above, the preferred embodiment of the content of compound AS in the water-soluble unit dose article W is the same as the content of the alkyl sulfate ester or its salt described above.

[0044] As anionic surfactants other than sulfate ester type surfactants, one or more selected from alkylaryl sulfonic acid type surfactants, alkane sulfonic acid type surfactants, olefin sulfonic acid type surfactants, alkyl sulfosuccinate type surfactants, sulfo fatty acid ester type surfactants, and fatty acids and their salts are preferred, one or more selected from alkylaryl sulfonic acid type surfactants, alkyl sulfosuccinate type surfactants, and fatty acids and their salts are more preferred, and one or more selected from alkylaryl sulfonic acid type surfactants, and fatty acids and their salts are even more preferred.

[0045] Furthermore, if an anionic surfactant other than a sulfate ester type surfactant is a salt, the salt of the anionic surfactant is the same as the salt of a sulfate ester type surfactant as described above.

[0046] Examples of anionic surfactants other than sulfate ester-type surfactants include one or more compounds selected from the compounds represented by the following general formulas (1-2), (1-3), and (1-4).

[0047] For anionic surfactants other than sulfate ester-type surfactants, from the viewpoint of improving cleaning performance, one or more selected from compounds represented by general formulas (1-2), (1-3), and (1-4) are preferred, and one or more selected from compounds represented by general formulas (1-2) and (1-3) are more preferred.

[0048] When the surfactant contains a compound represented by the general formula (1-2), in the water-soluble unit-dose article W, the content of the compound represented by the general formula (1-2) is preferably 5% by mass or more, more preferably 6.5% by mass or more, still more preferably 10% by mass or more, from the viewpoint of improving detergency, and preferably 25% by mass or less, more preferably 20% by mass or less, from the viewpoint of economy.

[0049] R 2a -Φ-SO3M …(1-2) (In the formula (1-2), R 2a represents an alkyl group having 9 to 14 carbon atoms, Φ represents a phenylene group, and the carbon atom of R 2a bonded to the carbon atom of Φ is a secondary carbon atom, and M represents a cation. The sulfonic acid group is bonded to the ortho, meta or para position with respect to R 2a bonded to Φ.)

[0050] R 3a -COOM …(1-3) (In the formula (1-3), R 3a represents an alkyl group or an alkenyl group having 9 to 17 carbon atoms, and M represents a cation.)

[0051] R 4a -CH(SO3M)COOR 5a (1-4)<00002​​​​​​​​​​​​​​In general formula (1-2), M is preferably an alkali metal ion such as a hydrogen ion, sodium ion, or potassium ion, an alkaline earth metal (1 / 2 atom) ion such as a magnesium ion or calcium ion, or an organic ammonium ion. The organic ammonium salt may be a salt of an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal ion such as a sodium ion or potassium ion, or an alkanolammonium ion such as a monoethanolammonium ion or a diethanolammonium ion, and more preferably a sodium ion.

[0054] As compounds represented by general formula (1-2), p-alkylbenzenesulfonates with an alkyl group having 10 to 14 carbon atoms are preferred, and p-alkylbenzenesulfonate sodium salts with an alkyl group having 10 to 14 carbon atoms are more preferred. That is, compounds represented by general formula (1-1) are those in general formula (1-2), where R 2a Compounds in which C1 is an alkyl group having 10 to 14 carbon atoms and M is a sodium ion are preferred.

[0055] In general formula (1-3), R 3a The alkyl or alkenyl group has preferably 9 or more carbon atoms, more preferably 10 or more, even more preferably 11 or more, and preferably 17 or fewer carbon atoms, more preferably 15 or fewer, and even more preferably 13 or fewer carbon atoms. 3a The group can be one or more groups selected from a linear alkyl group, a branched alkyl group, a linear alkenyl group, and a branched alkenyl group, with a linear alkyl group being preferred.

[0056] In general formula (1-3), M is preferably an alkali metal ion such as a hydrogen ion, sodium ion, or potassium ion, an alkaline earth metal (1 / 2 atom) ion such as a magnesium ion or calcium ion, or an organic ammonium ion. The organic ammonium salt may be a salt of an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal ion such as a sodium ion or potassium ion, or an alkanolammonium ion such as a monoethanolammonium ion or a diethanolammonium ion, and more preferably a sodium ion.

[0057] The compound represented by general formula (1-3) is preferably one or more selected from lauric acid, myristic acid, isostearic acid, palmitic acid, isopalmitic acid, oleic acid and their salts, more preferably one or more selected from lauric acid, myristic acid, palmitic acid and their salts, and even more preferably one or more selected from lauric acid, myristic acid and their salts.

[0058] Compounds represented by general formula (1-3) are those in general formula (1-3) where R 3a Compounds in which C1 is an alkyl group having 11 to 15 carbon atoms and M is a cation are preferred, and compounds in which M is a hydrogen ion or a sodium ion are more preferred.

[0059] In general formula (1-4), R 4a is preferably an alkyl group having 8 or more carbon atoms, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or fewer, more preferably 16 or fewer. In general formula (1-4), R 5a The alkyl group is preferably one or more carbon atoms, preferably five or fewer, more preferably four or fewer, and even more preferably three or fewer.

[0060] In general formula (1-4), M is preferably an alkali metal ion such as a hydrogen ion, sodium ion, or potassium ion, an alkaline earth metal (1 / 2 atom) ion such as a magnesium ion or calcium ion, or an organic ammonium ion. The organic ammonium salt may be a salt of an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal ion such as a sodium ion or potassium ion, or an alkanolammonium ion such as a monoethanolammonium ion or a diethanolammonium ion, and more preferably a sodium ion.

[0061] Compounds represented by general formula (1-4) include, in general formula (1-4), R 4a is an alkyl group having 11 or more carbon atoms and 14 or fewer carbon atoms, R 5a A sodium methyl ester salt of α-sulfo fatty acid is preferred, in which is a methyl group and M is a sodium ion.

[0062] (Nonionic surfactant) The surfactant may include a nonionic surfactant. From the viewpoint of improving cleaning performance, examples of nonionic surfactants include one or more selected from polyoxyalkylene alkyl or alkenyl ethers, alkyl (poly)glycosides (glycoside-type nonionic surfactants), sorbitan-based nonionic surfactants, compounds in which alkylene oxide is added between the ester bonds of long-chain fatty acid alkyl esters, fatty acid monoglycerides, and sucrose fatty acid esters.

[0063] As a nonionic surfactant, a nonionic surfactant containing an alkylene oxy group is preferred, and from the viewpoint of improving cleaning performance, a nonionic surfactant having an average number of added alkylene oxy groups of 1 to 30 is preferred. The alkylene oxy group is preferably one or more groups selected from alkylene oxy groups having 2 to 4 carbon atoms, and more preferably one or more groups selected from ethylene oxy groups and propylene oxy groups. From the viewpoint of improving cleaning performance against sebum stains, the average number of added alkylene oxy groups is preferably 1 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, and even more preferably 15 or less.

[0064] When the surfactant includes a nonionic surfactant, the content of the nonionic surfactant in the water-soluble unit-dose article W is preferably 5% by mass or more, more preferably 6.5% by mass or more, from the viewpoint of improving cleaning performance, and preferably 20% by mass or less, more preferably 15% by mass or less, from the viewpoint of economic efficiency. The content of alkyl ether sulfate or its salt is preferably 5% by mass or more and 20% by mass or less, more preferably 6.5% by mass or more and 15% by mass or less, from the viewpoint of improving cleaning performance and economic efficiency.

[0065] Nonionic surfactants containing alkylene oxy groups, wherein the average number of added alkylene oxy groups is 1 or more and 30 or less, are preferably nonionic surfactants represented by the following general formula (2-1).

[0066] R 6a (CO) m O-(A 1a O) n -R 7a …(2-1) (In formula (2-1), R 6a R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, 7a is a hydrogen atom or a methyl group. CO is a carbonyl group, and m is a number, either 0 or 1. 1a O is one or more alkylene groups with 2 to 4 carbon atoms. n is an alkylene oxy group A 1a(This is the average number of moles of oxygen, and is between 1 and 30.)

[0067] In general formula (2-1), R 6a The number of carbon atoms is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less, from the viewpoint of improving cleansing performance against sebum. 6a This is an aliphatic hydrocarbon group, preferably one or more groups selected from alkyl groups and alkenyl groups.

[0068] In general formula (2-1), A 1a O is one or more alkylene oxy groups having 2 to 4 carbon atoms, preferably one or more alkylene oxy groups having 2 to 3 carbon atoms, more preferably an ethylene oxy group. 1a If oxygen contains multiple different alkylene oxy groups, these different alkylene oxy groups may be either block-type or random-type bonds.

[0069] In general formula (2-1), n ​​is 1 or more, preferably 6 or more, more preferably 8 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less, from the viewpoint of improving cleanability against sebum stains.

[0070] In general formula (2-1), m is preferably 0 from the viewpoint of improving cleaning performance.

[0071] In general formula (2-1), R 7a From the viewpoint of improving cleaning performance, hydrogen atoms are preferred.

[0072] Specific examples of nonionic surfactants that do not have an alkylene oxy group include one or more selected from sucrose fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, alkyl glycosides, and glyceryl monoethers.

[0073] (cationic surfactant) Furthermore, the surfactant may also include a cationic surfactant. Examples of cationic surfactants include quaternary ammonium salt type surfactants. The cationic surfactant may have one or more effects selected from bactericidal action, antibacterial action, and disinfectant action. As the quaternary ammonium salt type surfactant of the cationic surfactant, one or more compounds selected from the compounds represented by the following general formula (3-1) and the compounds represented by the following general formula (3-2) are preferred.

[0074] [ka]

[0075] (In the formula, R 8a R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, 9a R is a group selected from aliphatic hydrocarbon groups having 8 to 18 carbon atoms, alkyl groups having 1 to 3 carbon atoms, and hydroxyalkyl groups having 1 to 3 carbon atoms. 10a and R 11a Each of these is independently selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, X - It is an anion.

[0076] [ka]

[0077] (In the formula, R 12a R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, 13a and R 14a Each of these is independently selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, X - It is an anion.

[0078] In general formula (3-1), R 8a The number of carbon atoms is preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 16 or less, from the viewpoint of improving cleanability.8a R is preferably an alkyl group or an alkenyl group, with alkyl groups being preferred. In general formula (3-1), 9a R is a group selected from aliphatic hydrocarbon groups having 8 to 18 carbon atoms, alkyl groups having 1 to 3 carbon atoms, and hydroxyalkyl groups having 1 to 3 carbon atoms. 9a However, if it is an aliphatic hydrocarbon group with 8 to 18 carbon atoms, R 9a From the viewpoint of improving cleaning performance, alkyl or alkenyl groups are preferably 8 or more, preferably 14 or less, and more preferably 12 or less, with alkyl groups being more preferred.

[0079] In general formula (3-1), R 10a and R 11a Each of these groups is independently selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms. 10a and R 11a Preferably, each of these groups is independently selected from alkyl groups having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include methyl, ethyl, and propyl groups. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include hydroxymethyl, hydroxyethyl, and hydroxypropyl groups.

[0080] In general formula (3-1), X - It is an anion. Examples of anions include halogen ions and one or more anions selected from alkyl sulfate ions having 1 to 3 carbon atoms. Examples of halogen ions include chloride ions, bromide ions, and iodide ions. Examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

[0081] In general formula (3-2), R 12a R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms. 12aThe number of carbon atoms is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, and more preferably 16 or less, from the viewpoint of improving antibacterial properties. 12a The group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.

[0082] In general formula (3-2), R 13a and R 14a Each of these groups is independently selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms. 13a and R 14a Preferably, each of these groups is independently selected from alkyl groups having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include methyl, ethyl, and propyl groups. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include hydroxymethyl, hydroxyethyl, and hydroxypropyl groups.

[0083] In general formula (3-2), X - It is an anion. Examples of anions include halogen ions and one or more anions selected from alkyl sulfate ions having 1 to 3 carbon atoms. Examples of halogen ions include chloride ions, bromide ions, and iodide ions. Examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

[0084] Specific examples of compounds of general formula (3-2) include N-dodecyl-N,N-dimethyl-N-benzylammonium salt, N-tridecyl-N,N-dimethyl-N-benzylammonium salt, N-tetradecyl-N,N-dimethyl-N-benzylammonium salt, N-pentadecyl-N,N-dimethyl-N-benzylammonium salt, N-hexadecyl-N,N-dimethyl-N-benzylammonium salt, N-dodecyl-N,N-diethyl-N-benzylammonium salt, N-tridecyl-N,N-diethyl-N-benzylammonium salt, and N-tetradecyl-N,N-diethyl-N-benzylammonium salt. Examples include one or more compounds selected from ammonium salt, N-pentadecyl-N,N-diethyl-N-benzylammonium salt, N-hexadecyl-N,N-diethyl-N-benzylammonium salt, N-dodecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tridecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tetradecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-pentadecyl-N-methyl-N-ethyl-N-benzylammonium salt, and N-hexadecyl-N-methyl-N-ethyl-N-benzylammonium salt.

[0085] The cationic surfactant is preferably one or more selected from benzalkonium chloride, dialkyldimethylammonium chloride, and alkyltrimethylammonium chloride. Benzalkonium chloride is preferably a compound represented by general formula (3-2). Dialkyldimethylammonium chloride, such as dioctyldimethylammonium chloride, and alkyltrimethylammonium chloride, such as dodecyltrimethylammonium chloride, are preferably compounds represented by general formula (3-1).

[0086] When the surfactant contains a cationic surfactant, the content of the cationic surfactant in the water-soluble unit-dose article W is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and may be greater than 0% by mass, from the viewpoint of economy and stability. From a similar viewpoint, the content of the cationic surfactant in the water-soluble unit-dose article W may be 0% by mass.

[0087] (Amphoteric surfactant) Furthermore, the surfactant may include an amphoteric surfactant. Examples of amphoteric surfactants include one or more selected from N-alkanoylaminopropyl-N,N-dimethylamine oxide, N-alkyl-N,N-dimethylamine oxide, N-alkanoylaminopropyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine. In these, the alkanoyl group is, for example, lauroyl or myristyl. In these, the alkyl group is, for example, a lauryl group or a myristyl group.

[0088] In the water-soluble unit-dose article W, when an amphoteric surfactant is included, from the viewpoint of improving cleaning performance and foaming, the content of the amphoteric surfactant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.2% by mass or less.

[0089] In the water-soluble unit-dose article W, the surfactant may be contained in either the water-soluble resin substrate X or the granular material Y, or in both, but from the viewpoint of improving solubility, it is preferably contained in the granular material Y.

[0090] [Other ingredients] In the water-soluble unit-dose article W, components other than surfactants may be added as needed. For example, the water-soluble unit-dose article W may contain one or more selected from rheological modifiers, chelating agents, water-insoluble inorganic components, anionic polymers, and water.

[0091] (Rheological modifier) In the water-soluble unit-dose article W, for example, a rheological modifier is added to prevent the generation of undissolved material due to gelation when the water-soluble unit-dose article W is dissolved in water. The water-soluble unit-dose article W preferably contains an alkoxylated amine as the rheological modifier, more preferably an alkoxylated polyamine, even more preferably an alkoxylated polyethyleneimine, and even more preferably an ethoxylated polyethyleneimine.

[0092] In the water-soluble unit-dose article W, if a rheological modifier is included, the content of the rheological modifier is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and from the viewpoint of ease of formulation, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0093] In addition, in the water-soluble unit dose article W, the rheology modifier may be contained in either the water-soluble resin substrate X or the granular material Y, or it may be contained in both.

[0094] (Chelating agent) In water-soluble unit-dose article W, a chelating agent is added to enhance the action of the surfactant and improve cleaning performance. Specific examples of chelating agents include, for example, aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, or their salts; organic acids such as citric acid, lactic acid, tartaric acid, and malic acid, or their salts; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and alkali metal or lower amine salts thereof; one or more of these can be used. Examples of chelating agent salts include alkali metal salts such as sodium salts and potassium salts; and lower amine salts such as monoethanolamine, diethanolamine, and triethanolamine.

[0095] In the water-soluble unit-dose article W, if a chelating agent is included, from the viewpoint of improving washability, the chelating agent content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more. From the viewpoint of ease of formulation, it is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.

[0096] (Water-insoluble inorganic components) The water-insoluble inorganic component may be a water-insoluble carrier. "Water-insoluble" in the context of the water-insoluble inorganic component means that 1 g or more of it does not dissolve in 100 g of water at 20°C. The water-insoluble inorganic component may be one or more selected from amorphous silica, calcium silicate, clay minerals, crystalline aluminosilicate, and amorphous aluminosilicate, preferably one or more selected from clay minerals and crystalline aluminosilicate. The water-insoluble inorganic component has the effect of suppressing undissolved residue after washing the object to be washed using a water-soluble unit-dose article W, and reducing the turbidity of the rinse water.

[0097] The average primary particle size of the water-insoluble inorganic component is preferably 0.1 μm or more, more preferably 1 μm or more, and preferably 10 μm or less, and more preferably 5 μm or less. The average primary particle size of the water-insoluble inorganic component was measured using a laser diffraction / scattering particle size distribution analyzer (e.g., HORIBA LA-950). This average primary particle size is the D50 (median diameter) of the cumulative particle size distribution based on volume.

[0098] Examples of water-insoluble inorganic components include amorphous aluminosilicates (oil absorption capacity: 285 mL / 100 g) as described in Japanese Patent Publication No. 9-132794, Japanese Patent Publication No. 7-10526, Japanese Patent Publication No. 6-227811, and Japanese Patent Publication No. 8-119622.

[0099] More specifically, as the water-insoluble inorganic component calcium silicate, Fluorite R (manufactured by Tokuyama Corporation, oil absorption capacity: 400-500 mL / 100 g) can be used; as the water-insoluble inorganic component amorphous silica, Toxil NR (manufactured by Tokuyama Corporation, oil absorption capacity: 210-270 mL / 100 g) and Silopure (manufactured by Fuji Silicia Chemical Co., Ltd., oil absorption capacity: 240-280 mL / 100 g) can be used; and as the water-insoluble inorganic component amorphous aluminosilicate, TIXOREX25 (manufactured by Hanfutsu Chemical Co., Ltd., 220-270 mL / 100 g) can be used.

[0100] Furthermore, crystalline aluminosilicates include zeolites. Specific examples of zeolites include crystalline aluminosilicates such as type A, type X, and type P zeolites. Among crystalline aluminosilicates, type A zeolite (e.g., trade name "Toyobuilder": manufactured by Tosoh Corporation, oil absorption capacity according to JIS K 5101: 40 mL / 100 g or more) is preferred. Other preferred types include type P (e.g., trade names "Doucil A24", "ZSEO64", etc.; both manufactured by Crosfield; oil absorption capacity 60-150 mL / 100 g), type X (e.g., trade name "WessalithXD"; manufactured by Degussa; oil absorption capacity 80-100 mL / 100 g), and hybrid zeolites described in International Publication No. 98 / 42622.

[0101] Examples of water-insoluble inorganic clay minerals include bentonite. Bentonite with an ion exchange capacity of 50 to 100 meq / 100g is preferred. Bentonite can be one or more selected from the group consisting of alkali metal or alkaline earth metal montmorillonite, saponite, or hectorite (smectitic clay), illite, attapulgite, and kaolinite. Bentonite can be used in powdered or granular form. For example, refer to Japanese Patent Publication No. 2008-189719 for granulated clay minerals.

[0102] In the water-soluble unit-dose article W, the water-insoluble inorganic component may be contained in either the water-soluble resin substrate X or the granular material Y, or in both, but from the viewpoint of ease of manufacture, it is preferably contained in the granular material Y.

[0103] (Anionic polymer) Examples of anionic polymers include polymers having a carboxylic acid group or a salt thereof and having a weight-average molecular weight of 3,000 or more. Examples of anionic polymers include one or more polymers selected from polyacrylic acid and its salts, copolymers of acrylic acid and maleic acid and their salts, and polymaleic acid and its salts.

[0104] Examples of polyacrylic acid and its salts include one or more selected from polyacrylic acid, sodium polyacrylate, and potassium polyacrylate, and preferably one or more selected from sodium polyacrylate and potassium polyacrylate.

[0105] Examples of acrylic acid-maleic acid copolymers and their salts include one or more selected from acrylic acid-maleic acid copolymers, sodium salts of acrylic acid-maleic acid copolymers, and potassium salts of acrylic acid-maleic acid copolymers, and preferably one or more selected from sodium salts of acrylic acid-maleic acid copolymers and potassium salts of acrylic acid-maleic acid copolymers. The molar ratio of the acrylic acid-maleic acid copolymer is preferably 1 / 99 or more, more preferably 10 / 90 or more, and preferably 99 / 1 or less, and more preferably 90 / 10 or less, as the number of moles of acrylic acid / the number of moles of maleic acid.

[0106] Examples of polymaleic acid and its salts include one or more selected from polymaleic acid, sodium polymaleate, and potassium polymaleate, and preferably one or more selected from sodium polymaleate and potassium polymaleate.

[0107] The anionic polymer may be a copolymer containing monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and / or maleic acid, as long as this does not hinder the expression of the effects of the present invention. Examples of monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and / or maleic acid include one or more selected from vinyl monomers, acrylic monomers, and styrene monomers, and more specifically, one or more selected from methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene. The molar ratio of monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and / or maleic acid in the anionic polymer is preferably 0 mol% or more, preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 0 mol% in the anionic polymer. Accordingly, the polyacrylic acid and its salts, the copolymer of acrylic acid and maleic acid and its salts, and the polymaleic acid and its salts of the present invention may be polymers or copolymers that, in the total constituent monomers, contain monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and / or maleic acid in an amount of 0 mol% to 5 mol%.

[0108] The weight-average molecular weight of the anionic polymer is preferably 3,000 or more, more preferably 3,500 or more, even more preferably 4,000 or more, even more preferably 5,000 or more, even more preferably 6,000 or more, even more preferably 7,000 or more, even more preferably 8,000 or more, even more preferably 9,000 or more, even more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, even more preferably 25,000 or less, and even more preferably 15,000 or less. This weight-average molecular weight can be measured according to the weight-average molecular weight measurement method described below.

[0109] The weight-average molecular weight of anionic polymers can be measured by GPC (gel permeation chromatography), and the weight-average molecular weight (Mw) can be determined using a conversion standard. The GPC measurement conditions are shown below. ·column: Manufactured by Tosoh Corporation, Product name: TSK-GEL guard PWXL Manufactured by Tosoh Corporation, Product name: TSK-GEL G4000 PWXL Manufactured by Tosoh Corporation, Product name: TSK-GEL G2500 PWXL Mobile phase: 0.1 mol / L potassium dihydrogen phosphate and 0.1 mol / L sodium dihydrogen phosphate aqueous solutions / acetonitrile = 90 / 10 (volume ratio) • Detector: Differential refractive index detector Column temperature: 40°C ·Flow rate: 1.0mL / min • Conversion reference material: Polyacrylic acid (manufactured by American Standard Corporation) • Sample: An aqueous polymer solution containing 0.8 g of solids is mixed with deionized water to prepare a total volume of 200 mL. 10 μL of this prepared solution is then taken and injected into the column.

[0110] In addition, in the water-soluble unit-dose article W, the anionic polymer may be contained in either the water-soluble resin substrate X or the granular material Y, or it may be contained in both.

[0111] (water) Water may be added to the water-soluble unit-dose article W. Examples of water include ion-exchanged water, purified water, and distilled water. The water also includes water used to add the components of the water-soluble unit-dose article W. In the water-soluble unit-dose article W, water may be contained in either the water-soluble resin substrate X or the granular material Y, or in both.

[0112] [Examples and Comparative Examples] Examples and comparative examples of the present invention will be described below, but the present invention is not intended to be limited to these examples.

[0113] In the examples and comparative examples, samples of water-soluble unit-dose articles were first prepared. For the water-soluble unit-dose article W sample, a nonwoven fabric made of polyvinyl alcohol (PVA) (manufactured by WBLLGG Co., Ltd.) was used as the water-soluble resin substrate. In addition, the following materials were used as granular material for the water-soluble unit-dose article W sample. • LAS: Sodium laurylbenzenesulfonate "Neoperex G-65" (manufactured by Kao Corporation) AES: Sodium polyoxyethylene (2) lauryl ether sulfate (average number of moles of oxyethylene groups is 2, containing 30% by mass of sodium lauryl sulfate) • AS: Sodium lauryl sulfate "Emal 10G" (manufactured by Kao Corporation) AEO(10): Polyoxyethylene(10) lauryl ether (average number of moles of oxyethylene groups: 10) • Sodium carbonate: Light ash (bulk density 600 g / L, average particle size 100 μm, manufactured by Central Glass Co., Ltd.) • Sodium bicarbonate: Sodium bicarbonate (manufactured by AGC Inc.) • Sodium citrate: Trisodium citrate (crystalline, manufactured by Showa Chemical Co., Ltd.) • Ethoxylated polyethyleneimine (PEI-EO): "Sokalan HP 20" (manufactured by BASF) • Silica: "Toxeal NR" (manufactured by Oriental Silicas Corporation) • Zeolite: "Zeobuilder" (Type 4A, average particle size 3.5 μm, manufactured by ZEOBUILDER) • Dichrosan: 4,4'-Dichloro-2-hydroxydiphenyl ether "Tinosan® HP 100" (effective content 30% by mass, propylene glycol (PG) 70% by mass, manufactured by BASF)

[0114] In the examples and comparative examples, water-soluble unit-dose articles were prepared by holding granular material in a water-soluble resin substrate. Specifically, in both the examples and comparative examples, 12 g of granular material was placed in a 7.5 cm x 7.5 cm rectangular flat bag (0.6 g) of the water-soluble resin substrate to prepare a sample of approximately 13 g of water-soluble unit-dose article (40 mL). Table 1 shows the content of each component (amount of effective portion of each material) (mass %) in the water-soluble resin substrate and granular material as a whole for the water-soluble unit-dose article samples prepared in the examples and comparative examples.

[0115] [Table 1]

[0116] In the samples of Examples 1 to 5, only PVA constitutes the water-soluble resin substrate, and each component other than PVA constitutes granular material. The samples of Examples 1 to 5 have the configuration of the water-soluble unit-dose articles according to the above embodiment. On the other hand, the sample of Comparative Example 1 was prepared by spraying dicrosan to hold dicrosan and then containing granular material in a water-soluble resin substrate. In other words, in the sample of Comparative Example 1, PVA, dicrosan, and PG constitute the water-soluble resin substrate, and each component other than PVA, dicrosan, and PG constitutes granular material. The sample of Comparative Example 1 differs from the configuration of the water-soluble unit-dose articles according to the above embodiment in that dicrosan is included in the water-soluble resin substrate.

[0117] The samples for Examples 1-5 and Comparative Example 1 were subjected to tactile evaluation. In the tactile evaluation, evaluators touched each sample by hand and evaluated it according to the following criteria. For tactile evaluation, samples with an evaluation of A were considered acceptable, and samples with an evaluation of B were considered unacceptable. A: Not sticky B: Sticky

[0118] Furthermore, the cleaning performance of the samples related to Examples 1 to 5 was also evaluated. The cleaning performance was evaluated according to the following procedure.

[0119] • Creation of artificially soiled cloth with sebum stains The artificial soiled cloth used was a 6cm x 6cm cotton / polyester broadcloth blend dyed cloth (cotton / polyester ratio = 35 / 65, purchased from Tanigashira Shoten) to which 100mg of artificial soiling consisting of the following composition was gravure coated.

[0120] ·Artificial dirt A composition containing the following components a, b, c, d, and e was used as artificial sludge. The mass percentages for each component represent the proportion of artificial sludge in the final composition, and the amount of B was adjusted so that the total mass percentage was 100%. a: Model sebum stain (used in an amount that results in the following mass percentages of artificial dirt: lauric acid 0.44% by mass, myristic acid 3.15% by mass, pentadecanoic acid 2.35% by mass, palmitic acid 6.31% by mass, heptadecanoic acid 0.44% by mass, stearic acid 1.60% by mass, oleic acid 7.91% by mass, n-hexadecyl palmitate 2.22% by mass, squalene 6.66% by mass) b: Hard water obtained by weighing 105 mg of calcium chloride dihydrate, dissolving it in distilled water to make 1,000 mL. c: 1.98% by mass of egg white lecithin liquid crystal (prepared by dissolving 11.37 g of arginine hydrochloride, 4.20 g of histidine, and 2.44 g of serine in 80 mL of distilled water, adjusting the pH to 5.0 with concentrated hydrochloric acid, and then thoroughly mixing this solution with egg white lecithin in a mixer to obtain egg white lecithin liquid crystal) d: Kanuma red soil 8.11% by mass e: Carbon Black 0.025% by mass

[0121] • Evaluation of cleaning performance The cleaning performance of four artificially soiled cloths with sebum stains was evaluated by cleaning them using the following method. Four artificially soiled cloths were cleaned at 100 rpm for 10 minutes using a turgotometer (Ueshima, MS-8212). Specifically, the cleaning conditions were as follows: four artificially soiled cloths and 0.43 g of each cleaning agent composition listed in Table 1 were placed in the turgotometer, 600 mL of water was added, and the cleaning solution was prepared while dissolving the cleaning agent composition in water, while the artificially soiled cloths were cleaned at 100 rpm for 10 minutes. The water temperature for each cleaning solution was 20°C. After cleaning, the cloths were rinsed with tap water (20°C) for 1 minute. After that, the soiled cloths were dewatered for 3 minutes using a twin-tub washing machine, and then left to dry for 5 hours under conditions of 20°C and 50% RH. The cleaning rate (%) was calculated based on the following formula, and the average value for the four cloths was obtained. Cleaning rate (%) = 100 × [(Reflectance of the artificially soiled fabric after cleaning - Reflectance of the artificially soiled fabric before cleaning) / (Reflectance of the original fabric - Reflectance of the artificially soiled fabric before cleaning)] The reflectance at a wavelength of 550 nm of the original fabric of the artificially soiled cloth, and the artificially soiled cloth before and after washing, was measured using a spectrocolorimeter (SE2000, manufactured by Nippon Denshoku Co., Ltd.). A higher washing rate indicates better washing performance. Regarding washing performance, samples with a washing rate of 20 or higher were considered acceptable, while samples with a washing rate of less than 20 were considered unacceptable.

[0122] Table 2 shows the evaluation results for the feel of samples from Examples 1-5 and Comparative Example 1, as well as the evaluation results for the cleaning performance of samples from Examples 1-5. All samples from Examples 1-5, in which dichrosan was not included in the water-soluble resin substrate, passed the feel evaluation. However, the sample from Comparative Example 1, in which dichrosan was included in the water-soluble resin substrate, failed the feel evaluation. Furthermore, all samples from Examples 1-5 passed the cleaning performance evaluation.

[0123] [Table 2] [Explanation of symbols]

[0124] W...Water-soluble unit dosage items X…water-soluble resin matrix Y…granular body

Claims

1. A water-soluble unit-dose article in which granular material is held in a water-soluble resin substrate, It contains dichrosan and a surfactant, The dicrosan contained in the granular material Water-soluble unit dose product.

2. The surfactant includes a sulfate ester type surfactant. The water-soluble unit dose article according to claim 1.

3. The content of the aforementioned sulfate ester-type surfactant is 6.5% by mass or more. The water-soluble unit dose article according to claim 2.

4. The sulfate ester type surfactant is contained in the granular material. The water-soluble unit dose article according to claim 2.

5. The pH at 25°C when dissolved in 30L of water is 8.5 or less. The water-soluble unit dose article according to claim 1.

6. The water-soluble resin substrate is composed of a water-soluble fiber structure. The water-soluble unit dose article according to claim 1.

7. This is a unit-dose product of laundry detergent. A water-soluble unit-dose article according to any one of claims 1 to 6.

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