Water-soluble unit dose articles

Abstract

In water-soluble unit-dose articles containing percarbonate powder, the degradation of the water-soluble resin substrate is suppressed. [Solution] In the water-soluble unit dose article, granular material is held in a water-soluble resin substrate. The water-soluble unit dose article contains percarbonate powder a and a coating agent b that coats the percarbonate powder a.

Description

Technical Field

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

Background Art

[0002] Techniques for configuring a laundry detergent as a water-soluble unit-dose article are known (see, for example, Patent Document 1). In such water-soluble unit-dose articles, since a water-soluble unit-dose article containing a fixed amount of laundry detergent can be directly put into a washing machine without the consumer measuring 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] Patent Document 2 discloses a powdery or granular bleaching agent composition containing sodium percarbonate, a bleach activator satisfying specific conditions, and a surfactant.

Prior Art Documents

Patent Documents

[0005] <00000,98>

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] Even though water-soluble unit-dose articles are used for convenient laundry, using a plurality of agents such as detergents and bleaches together increases the labor. Therefore, in order to achieve more convenient laundry, a detergent containing a bleach is considered to be effective.

[0007] Percarbonates are known as bleaching agents with high bleaching performance. However, the inventors of this invention have found that when percarbonates are incorporated into a water-soluble unit-dose article, particularly in high-humidity environments, the hydrogen peroxide generated by the percarbonates as they absorb moisture causes deterioration of the substrate formed from the water-soluble resin, leading to a decrease in the particle-holding function of the substrate and deterioration of its appearance.

[0008] This invention relates to a technique for suppressing the degradation of a water-soluble resin substrate in a water-soluble unit-dose article containing percarbonate powder. [Means for solving the problem]

[0009] 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 percarbonate powder a and a coating agent b that coats the percarbonate powder a. [Effects of the Invention]

[0010] According to the present invention, the deterioration of the water-soluble resin substrate can be suppressed in a water-soluble unit-dose article containing percarbonate powder. [Brief explanation of the drawing]

[0011] [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]

[0012] 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.

[0013] [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 a percarbonate powder a and a coating agent b that coats the percarbonate powder a. Furthermore, it is preferable that the water-soluble unit-dose article W further contains one or more selected from surfactant c and water-soluble inorganic salt d.

[0014] 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.

[0015] The specific composition of the water-soluble unit dose product W will be described below.

[0016] [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.

[0017] 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, for example, described in U.S. Patent No. 6,995,126. From the viewpoint of effectively obtaining the effects of the present invention, it is preferable that the water-soluble resin substrate X contains polyvinyl alcohol.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] The water-soluble film constituting the water-soluble resin substrate X can be obtained by methods known in the art, such as polymer casting, blow molding, extrusion molding, and injection molding. The thickness of the water-soluble film constituting the water-soluble resin substrate X is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 30 μm or more, from the viewpoint of preventing accidental ingestion, and preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less, from the viewpoint of improving solubility.

[0022] 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.

[0023] 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.

[0024] 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 0.4 cm to 3 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.

[0025] [Percarbonate powder a] Percarbonate powder a is a powder formed from percarbonate and is blended into a water-soluble unit-dose article W as a bleaching component. Percarbonate powder a constitutes granular material Y. From the viewpoint of storage stability, the average particle size of percarbonate powder a is preferably 150 μm to 2000 μm, more preferably 200 μm to 1000 μm, and even more preferably 250 μm to 500 μm. The average particle size of percarbonate powder a is measured using a rotap-type sieve shaker. Specifically, the average particle size of percarbonate powder a is determined by sieving using standard sieves specified in JIS Z 8801, measuring the mass of the sample remaining on each sieve, and calculating the mass fraction according to the sieve size.

[0026] The percarbonate forming the percarbonate powder a preferably contains an alkali metal percarbonate, and more preferably an alkali percarbonate, from the viewpoint of improving bleaching performance. The alkali percarbonate is preferably one or more selected from sodium percarbonate and potassium percarbonate, and more preferably sodium percarbonate, from the viewpoint of improving bleaching performance. Percarbonate is a common name for the hydrogen peroxide of carbonates; for example, the chemical formula for sodium percarbonate is 2Na2CO3·3H2O2.

[0027] In the water-soluble unit-dose article W, from the viewpoint of more effectively obtaining the effect of percarbonate powder a, the content of percarbonate powder a is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. Furthermore, in the water-soluble unit-dose article W, from the viewpoint of economy, the content of percarbonate powder a is preferably 100% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less.

[0028] [Coating agent b] In the water-soluble unit-dose article W, coating the percarbonate powder a with coating agent b makes it difficult for moisture in the air to come into contact with the percarbonate powder a, thereby suppressing moisture absorption by the percarbonate powder a. As a result, the water-soluble resin substrate X can suppress the generation of hydrogen peroxide associated with moisture absorption in the percarbonate powder a.

[0029] Therefore, in the water-soluble unit-dose article W, degradation of the water-soluble resin substrate X due to hydrogen peroxide generated by the percarbonate powder a can be prevented. Consequently, in the water-soluble unit-dose article W, a decrease in the retention function of the granular material Y and deterioration of appearance due to changes in the surface condition, which accompany the degradation of the water-soluble resin substrate X, can be prevented. This effect of coating agent b is more effective in configurations using a water-soluble resin substrate X containing polyvinyl alcohol, which is prone to degradation by hydrogen peroxide.

[0030] From the viewpoint of more effectively suppressing the moisture absorption of percarbonate powder a, coating agent b preferably contains a borate, and more preferably is a borate. From the viewpoint of more effectively suppressing the moisture absorption of percarbonate powder a, the borate is preferably sodium borate, and more preferably sodium metaborate. Examples of sodium borate include sodium tetraborate decahydrate (borax, Na2O·2B2O3·10H2O), sodium tetraborate pentahydrate (Na2O·2B2O3·5H2O), sodium tetraborate tetrahydrate (Na2O·2B2O3·4H2O), (anhydrous) sodium tetraborate (Na2O·2B2O3), sodium octaborate tetrahydrate (Na2O·4B2O3·4H2O), and sodium pentaborate. Examples include sodium phosphate pentahydrate (Na2O·5B2O3·10H2O), sodium perborate tetrahydrate (NaBO3·4H2O), sodium perborate monohydrate (NaBO3·1H2O), sodium metaborate tetrahydrate (NaBO2·4H2O), and sodium metaborate dihydrate (NaBO2·2H2O). Among these, sodium metaborate dihydrate and sodium metaborate tetrahydrate are preferred.

[0031] Coating agent b may contain other compounds in addition to or instead of borate. For example, coating agent b may contain inorganic compounds such as sodium carbonate, Glauber's salt, magnesium sulfate, magnesium silicate, magnesium chloride, magnesium oxide, and sodium silicate, or metal ion sequestering agents such as ethylenediaminetetraacetate, nitrilotriacetate, and phosphate.

[0032] In the water-soluble unit-dose article W, from the viewpoint of more effectively suppressing moisture absorption of percarbonate powder a, the mass ratio of coating agent b to percarbonate powder a is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more. Furthermore, in the water-soluble unit-dose article W, from the viewpoint of improving bleaching properties, the mass ratio of coating agent b to percarbonate powder a is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0033] [Surfactant c] The water-soluble unit-dose article W preferably contains a surfactant c to improve cleaning performance. Examples of surfactant c include one or more selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and from the viewpoint of improving cleaning performance, it is even more preferable that it contains one or more selected from anionic surfactants and nonionic surfactants.

[0034] In the water-soluble unit-dose article W, when surfactant c is included, from the viewpoint of improving cleaning performance, the content of surfactant c 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.

[0035] In the water-soluble unit-dose article W, the surfactant c 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.

[0036] (Anionic surfactant) As anionic surfactants, from the viewpoint of improving the cleaning performance of particulate dirt, one or more selected from sulfate ester type surfactants, alkylaryl sulfonic acid type surfactants, alkane sulfonic acid type surfactants, olefin sulfonic acid type surfactants, alkyl sulfosuccinate ester type surfactants, sulfo fatty acid ester type surfactants, and fatty acids and their salts are preferred, one or more selected from sulfate ester type surfactants, alkylaryl sulfonic acid type surfactants, sulfate ester type surfactants, alkyl sulfosuccinate ester type surfactants, and fatty acids and their salts are more preferred, and one or more selected from sulfate ester type surfactants, alkylaryl sulfonic acid type surfactants, and fatty acids and their salts are even more preferred. Furthermore, the anionic surfactant is more preferably one or more selected from alkyl sulfate salts, alkyl ether sulfate salts, and alkylbenzene sulfonates, and more preferably one or more selected from alkyl sulfate salts and alkyl ether sulfate salts.

[0037] When the anionic surfactant is a salt, examples of salts of the anionic surfactant include inorganic salts such as sodium salts, potassium salts, ammonium salts, and magnesium salts, and organic salts such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and morpholine salts. Preferably, the salt of the anionic surfactant is an inorganic salt selected from alkali metal salts such as sodium salts and potassium salts, and alkaline earth metal salts such as magnesium salts, more preferably an alkali metal salt, and even more preferably a sodium salt.

[0038] When surfactant c 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.

[0039] Examples of the anionic surfactant include one or more compounds selected from the compounds represented by the following general formula (1-1), the compound represented by general formula (1-2), the compound represented by general formula (1-3), and the compound represented by general formula (1-4). From the viewpoint of improving detergency, one or more compounds selected from the compounds represented by general formula (1-1), (1-2), or (1-3) are preferable, one or more compounds selected from the compounds represented by general formula (1-1) or (1-2) are more preferable, and one or more compounds selected from the compounds represented by general formula (1-1) are still more preferable.

[0040] R -O-(AO) n -SO3M (1-1) (In formula (1-1), R 1a is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, A is one or more alkylene groups selected from an ethylene group and a propylene group, n is a number from 0 to 20 representing the average molar number of the alkyleneoxy group AO, and M is a cation.)

[0041] <​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​5a (wherein represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M represents a cation.)

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] In formula (1-1), the average number of moles of propyleneoxy groups may be 0.

[0049] 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.

[0050] 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.

[0051] The surfactant c 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.

[0052] The surfactant c is represented by formula (1-1), n ​​is 0, and R 1a When M contains the same compound AS as described above, the content of compound AS in the water-soluble unit dose article W is preferably 6.5% by mass or more, more preferably 13% by mass or more, 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, even more preferably 30% by mass or less, from the viewpoint of economic efficiency.

[0053] In general formula (1-2), R 2a This is an alkyl group having 9 or more carbon atoms, more preferably 10 or more, and more preferably 14 or fewer carbon atoms, and more preferably 13 or fewer carbon atoms.

[0054] 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.

[0055] 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.

[0056] When surfactant c contains a compound represented by general formula (1-2), the content of the compound represented by general formula (1-2) in the water-soluble unit dose article W is preferably 5% by mass or more, more preferably 6.5% by mass or more, even more preferably 10% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, from the viewpoint of improving cleaning performance.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] (Nonionic surfactant) Examples of nonionic surfactants that improve cleaning performance 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 oxides are added between the ester bonds of long-chain fatty acid alkyl esters, fatty acid monoglycerides, and sucrose fatty acid esters.

[0065] As a nonionic surfactant, a nonionic surfactant containing an alkylene oxy group, wherein the average number of added alkylene oxy groups is 1 or more and 30 or less, 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 the 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.

[0066] When surfactant c contains 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.

[0067] 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).

[0068] 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 n is one or more alkylene groups with 2 to 4 carbon atoms. 1a (This is the average number of moles of oxygen, and is between 1 and 30.)

[0069] 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.

[0070] 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.

[0071] 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.

[0072] In general formula (2-1), m is preferably 0 from the viewpoint of improving cleaning performance.

[0073] In general formula (2-1), R 7a From the viewpoint of improving cleaning performance, hydrogen atoms are preferred.

[0074] 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.

[0075] (cationic surfactant) Examples of cationic surfactants include quaternary ammonium salt type surfactants. Cationic surfactants may have one or more effects selected from bactericidal action, antibacterial action, and disinfectant action. As cationic surfactants, quaternary ammonium salt type surfactants, one or more selected from compounds represented by the following general formula (3-1) and compounds represented by the following general formula (3-2) are preferred.

[0076] [ka]

[0077] (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.

[0078] [ka]

[0079] (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.

[0080] 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. 8aR 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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).

[0088] If surfactant c 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.

[0089] (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.

[0090] 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.

[0091] [Water-soluble inorganic salt d] The water-soluble inorganic salt d is a water-soluble inorganic salt other than percarbonate powder a that is not coated with percarbonate powder a. In other words, if coating agent b contains a water-soluble inorganic salt such as borate, then water-soluble inorganic salt d is a water-soluble inorganic salt other than percarbonate powder a and coating agent b. In the water-soluble unit dose article W, it is preferable that water-soluble inorganic salt d is blended as an alkaline agent to obtain high cleaning performance by improving the penetration action of surfactant c. Examples of water-soluble inorganic salt d include one or more selected from carbonate, bicarbonate, silicate, and tripolyphosphate, and from the viewpoint of improving cleaning performance, one or more selected from carbonate and bicarbonate are preferred.

[0092] Examples of carbonates include one or more selected from sodium carbonate and potassium carbonate, with sodium carbonate being preferred. Examples of bicarbonates include one or more selected from sodium bicarbonate and potassium bicarbonate. Examples of silicates include one or more selected from sodium silicate and potassium silicate. Examples of tripolyphosphates include alkali metal salts of tripolyphosphate.

[0093] In the water-soluble unit-dose article W, it is preferable to have a large amount of water-soluble inorganic salt d in order to obtain high cleansing properties against sebum and the like by improving the penetration action of surfactant c, and it is preferable that the amount of water-soluble inorganic salt d is not too large in order to suppress the occurrence of undissolved residue. From these viewpoints, in the water-soluble unit-dose article W, when water-soluble inorganic salt d is contained, the content of water-soluble inorganic salt d is preferably 15% by mass or more, more preferably 17% by mass or more, even more preferably 18% by mass or more, and preferably 25% by mass or less, more preferably 24% by mass or less, and even more preferably 22% by mass or less.

[0094] In addition, in the water-soluble unit dose article W, the water-soluble inorganic salt d may be contained in either the water-soluble resin substrate X or the granular material Y, or it may be contained in both.

[0095] [Other ingredients] In the water-soluble unit-dose article W, components other than surfactant c and water-soluble inorganic salt d 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.

[0096] (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.

[0097] 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.

[0098] 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.

[0099] (Chelating agent) In the water-soluble unit-dose article W, a chelating agent is added to enhance the action of surfactant c 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.

[0100] 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.

[0101] (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. By using the water-insoluble inorganic component in a specific ratio with the water-soluble inorganic salt d, it has the effect of suppressing undissolved residue after washing the object with the water-soluble unit-dose article W and reducing the turbidity of the rinse water.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] (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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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%.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] (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.

[0117] (bleach activator) The water-soluble unit-dose article W may contain a bleaching activator. Examples of bleaching activators include tetraacetylethylenediamine, alkanoyloxybenzene sulfonate, and alkanoyloxybenzene carboxylic acid (salt). The bleaching activator is preferably one or more compounds selected from those represented by the following general formula (I) or (II), and more preferably a compound represented by general formula (I), and even more preferably a compound represented by general formula (I) with an s value of 10 or more and 13 or less. C s H 2s+1 -COO-Φ-SO3M (I) C t H 2t+1 -COO-Φ-COOH (II) (In the formula, s and t are integers between 5 and 17, respectively; Φ represents a phenylene group; and M represents a hydrogen ion or alkali metal ion.)

[0118] The bleach activator can be incorporated into a water-soluble unit-dose article W as bleach activator particles containing the bleach activator.

[0119] Bleaching activator particles can be manufactured, for example, by extrusion granulation using the above-mentioned bleaching activator, a surfactant, a binder substance, an acid, etc. Here, as the surfactant, from the viewpoint of improving the solubility of the bleach activator in the laundry bath, it is preferable to use one or more selected from alkyl sulfates and alkyl ether sulfates (average number of oxyethylene groups is preferably 1 to 10, more preferably 1 to 5) which have a number of carbon atoms preferably between 10 and 18, more preferably between 12 and 14. As the binder substance, from the viewpoint of improving the fluidity of the bleach activator particles, it is preferable to use one or more selected from fatty acids (which may be in soap form) and polyoxyalkylenes (average molecular weight preferably between 2000 and 20000, more preferably between 4000 and 10000) which have a number of carbon atoms preferably between 8 and 20, more preferably between 10 and 18. As the acidifying agent, from the viewpoint of the stability of the bleach activator, it is preferable to use one or more selected from succinic acid, maleic acid, fumaric acid, citric acid, glycolic acid, and p-hydroxybenzoic acid.

[0120] The bleaching activator particles preferably contain 1% to 90% by mass of bleaching activator, more preferably 10% to 90% by mass, and even more preferably 30% to 70% by mass; preferably 0% to 50% by mass of surfactant, more preferably 1% to 45% by mass, and even more preferably 5% to 40% by mass; preferably 0.5% to 30% by mass of binder substance, more preferably 1% to 20% by mass, and even more preferably 5% to 20% by mass; and preferably 0% to 20% by mass of acidifying agent, more preferably 1% to 15% by mass, and even more preferably 1% to 10% by mass.

[0121] The average particle size of the bleach activator particles is preferably 600 μm or more, more preferably 800 μm or more, and preferably 1400 μm or less, and more preferably 1200 μm or less. Furthermore, from the viewpoint of storage stability, the proportion of particles with a particle size of 350 μm or less is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less of the total bleach activator particles. Furthermore, the bulk density of the bleach activator particles is preferably 500 kg / m³. 3 More than 800kg / m 3 More preferably 600 kg / m 3 More than 700kg / m 3 The following applies:

[0122] [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.

[0123] In Examples 1-3 and Comparative Examples 1-3, samples of water-soluble unit-dose articles were first prepared. In Examples 1-3 and Comparative Examples 1-3, a common sodium percarbonate powder was prepared as percarbonate powder a. In Examples 1-3, sodium metaborate tetrahydrate was further prepared as coating agent b, and percarbonate powder a coated with 5% by mass of coating agent b was used to prepare percarbonate powder a coated with coating agent b. Large particles were removed using a 500 μm mesh sieve, and small particles were removed using a 150 μm mesh sieve. In Comparative Examples 1-3, percarbonate powder a that was not coated with coating agent b was used as is.

[0124] In Examples 1 and 2 and Comparative Examples 1 and 2, the following materials were used as granular materials constituting the cleaning components other than percarbonate powder a. In Example 3 and Comparative Example 3, no granular materials other than percarbonate powder a were used. • 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.) • PEI-EO: Ethoxylated polyethyleneimine "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)

[0125] Examples 1 and 2 and Comparative Examples 1 and 2 share the same composition of granular material other than percarbonate powder a. Table 1 shows the content (amount of each material) (mass%) of each component of the granular material other than percarbonate powder a in Examples 1 and 2 and Comparative Examples 1 and 2.

[0126] [Table 1]

[0127] In Example 1 and Comparative Example 1, a water-soluble resin substrate was prepared using PVA nonwoven fabric. The PVA nonwoven fabric was made from PVA fibers obtained by electrospinning PVA "Gosenol® EG-05C" manufactured by Mitsubishi Chemical Corporation. The water-soluble resin substrates in Example 1 and Comparative Example 1 were prepared by stacking two 7.5cm x 7.5cm rectangular pieces of PVA nonwoven fabric, using a heat sealer (manufactured by Fuji Impulse Co., Ltd.), setting the heat sealer's sealing condition to 4, and fusing three sides from the edge of each side with a width of 2mm using the heat sealer, resulting in a flat bag with one side open.

[0128] In Examples 2 and 3 and Comparative Examples 2 and 3, a water-soluble resin substrate was prepared using PVA film (Monosol "M8685"). The water-soluble resin substrates in Examples 2 and 3 and Comparative Examples 2 and 3 were prepared by stacking two 7.5cm x 7.5cm rectangular PVA films, using a heat sealer (Fuji Impulse Co., Ltd.), setting the heat sealer's sealing condition to 6, and fusing three sides with the heat sealer from the edges of each side by a width of 2mm, resulting in a flat bag with one side open.

[0129] In Examples 1-3 and Comparative Examples 1-3, a sample of a water-soluble unit-dose article was obtained by containing 13.3 g of granular material in 0.7 g of the water-soluble resin substrate prepared as described above. In all samples related to Examples 1-3 and Comparative Examples 1-3, the PVA content constituting the water-soluble resin substrate X in the entire sample was 5% by mass. In the samples related to Example 1 and Comparative Example 1, the amount of percarbonate powder a blended per 100 parts by mass of granular material was 50 parts by mass. In the samples related to Example 2 and Comparative Example 2, the amount of percarbonate powder a blended per 100 parts by mass of granular material was 80 parts by mass. In the samples related to Example 3 and Comparative Example 3, the amount of percarbonate powder a blended per 100 parts by mass of granular material was 100 parts by mass. Note that the amount of percarbonate powder a blended in the samples related to Examples 1-3 also includes the amount of coating agent b that coats the percarbonate powder a.

[0130] Storage tests were conducted on the samples related to Examples 1-3 and Comparative Examples 1-3. In the storage tests, each sample was kept in a constant temperature bath at 30°C and 70%RH, and the samples were visually observed at various points in time from 1 to 4 weeks from the start of storage. The appearance of the water-soluble resin substrate was evaluated according to the following criteria. A: No cosmetic defects. B: The surface is partially deformed. C: The entire surface is deformed or has tears.

[0131] Table 2 shows the results of the appearance evaluation of the samples from Examples 1-3 and Comparative Examples 1-3 at 1 week, 2 weeks, and 4 weeks after the start of the storage test. Table 2 also shows the type and content of the water-soluble resin substrate, the proportions of percarbonate powder a and other materials per 100 parts by mass of granular material, and the presence or absence of coating agent b for the samples from Examples 1-3 and Comparative Examples 1-3.

[0132] [Table 2]

[0133] In all samples from Examples 1 to 3, which used coating agent b, no appearance defects were observed at any point in time. In contrast, in all samples from Comparative Examples 1 to 3, which did not use coating agent b, appearance defects were observed at least four weeks after the start of holding. In particular, in Comparative Example 1, which used a water-soluble resin substrate formed from PVA nonwoven fabric, tears had already occurred in the water-soluble resin substrate after one week from the start of holding. In the samples from Comparative Examples 2 and 3, which used water-soluble resin substrates formed from PVA film, the sample from Comparative Example 3, which contained 100 parts by mass of percarbonate powder a, showed an uneven surface shape across the entire surface of the water-soluble resin substrate after two weeks from the start of holding, and the sample from Comparative Example 2, which contained 80 parts by mass of percarbonate powder a, showed a partial uneven surface shape on the surface of the water-soluble resin substrate after four weeks from the start of holding. [Explanation of symbols]

[0134] W...Water-soluble unit dose article X…Water-soluble resin base Y...granular

Claims

1. A water-soluble unit-dose article in which granular material is held in a water-soluble resin substrate, Percarbonate powder a, A coating agent b that coats the percarbonate powder a, A water-soluble unit-dose article containing the following.

2. The percarbonate powder a contains an alkali metal percarbonate. The water-soluble unit dose article according to claim 1.

3. The coating agent b contains a borate. The water-soluble unit dose article according to claim 1.

4. The water-soluble resin substrate contains polyvinyl alcohol. The water-soluble unit dose article according to claim 1.

5. It further contains one or more selected from surfactant c and water-soluble inorganic salt d. The water-soluble unit dose article according to claim 1.

6. The water-soluble resin substrate is composed of one or more selected from water-soluble fiber structures and water-soluble films. 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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