Unit dose product packaging

Abstract

To reduce stickiness in water-soluble unit-dose products. [Solution] The unit-dose article packaging 10 contains a water-soluble unit-dose article W. The unit-dose article packaging comprises a packaging material 20 and a water-soluble unit-dose article. The packaging material has a storage section 23 and a dispensing opening 11, and in a closed state with the dispensing opening closed, the ratio of the total area of ​​the openings that connect the storage section to the external space to the volume of the storage section is 40 mm 2 It is less than or equal to / L. The water-soluble unit dose article is contained in the container.

Description

Technical Field

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

Background Art

[0002] Techniques for configuring laundry detergents as water-soluble unit-dose articles are known (see, for example, Patent Document 1). In such water-soluble unit-dose articles, since the consumer can directly put a water-soluble unit-dose article containing a certain amount of laundry detergent into the washing machine without 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, particles of cleaning components such as surfactants are held by a water-soluble fiber structure formed of a water-soluble resin such as polyvinyl alcohol (PVA).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in water-soluble unit-dose articles using a water-soluble fiber structure, stickiness is likely to occur in the water-soluble fiber structure due to moisture absorption during storage. As a result, in such water-soluble unit-dose articles, deterioration of the touch during input into the washing machine and adhesion of water-soluble components to the hands are likely to occur.

[0006] ]]The present invention relates to a technique for making it difficult for stickiness to occur in water-soluble unit-dose articles.

Means for Solving the Problems

[0007] In one embodiment of the present invention, a unit-dose article package contains a water-soluble unit-dose article. The aforementioned unit-dose article packaging comprises a packaging material and a water-soluble unit-dose article. The packaging material has a storage compartment and an opening, and in the closed state with the opening closed, the ratio of the total area of ​​the openings connecting the storage compartment and the external space to the volume of the storage compartment is 40 mm². 2 It is less than or equal to / L. The aforementioned water-soluble unit dose article is contained in the aforementioned storage section. [Effects of the Invention]

[0008] According to the present invention, it is possible to make water-soluble unit-dose articles less likely to become sticky. [Brief explanation of the drawing]

[0009] [Figure 1] This is a perspective view showing the closed state of a unit-dose article package according to one embodiment of the present invention. [Figure 2] A perspective view showing the opened state of the above-mentioned unit-dose article packaging. [Figure 3] This figure schematically shows an example of the structure of a water-soluble unit-dose article in the above-mentioned unit-dose article packaging. [Figure 4] This figure schematically shows other examples of the above-mentioned water-soluble unit-dose articles. [Figure 5] This graph shows the results of the storage tests in the examples and comparative examples. [Modes for carrying out the invention]

[0010] 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.

[0011] [Overall composition of unit-dose article packaging 10] Figures 1 and 2 are perspective views of a unit-dose article packaging 10 according to one embodiment of the present invention. Figure 1 shows the unit-dose article packaging 10 in a closed state, and Figure 2 shows the unit-dose article packaging 10 in an open state. The unit-dose article packaging 10 comprises a packaging material 20 and a plurality of water-soluble unit-dose articles W. The unit-dose article packaging 10 is a packaging of a plurality of water-soluble unit-dose articles W that are packaged together with the packaging material 20 for storage.

[0012] The packaging material 20 has a main body 21, a lid 22, and a storage section 23. The storage section 23 is a space separated from the outside by the main body 21 and the lid 22 in the closed state shown in Figure 1. The packaging material 20 is rectangular parallelepiped, with the five sides other than the top surface 10a being composed of the main body 21, and the top surface 10a being composed of the lid 22. In the packaging material 20, a hinge 24 is provided on one of the four sides that make up the top surface 10a, connecting the main body 21 and the lid 22.

[0013] In the packaging material 20, the lid portion 22 has an extended portion 22a that extends downward from the three sides other than the one side on the top surface 10a where the hinge portion 24 is provided, to the vicinity of the center in the height direction on the outer surface of the main body portion 21 when the lid portion 22 is closed as shown in Figure 1. In the packaging material 20, by providing the extended portion 22a on the lid portion 22 that wraps around to the outer surface of the main body portion 21, a gap is less likely to occur between the main body portion 21 and the lid portion 22 when the lid portion 22 is closed as shown in Figure 1.

[0014] In the packaging material 20, from the closed state shown in Figure 1, the lid portion 22 is rotated upward relative to the main body portion 21 using the hinge portion 24 as a pivot, thereby opening the upper end of the main body portion 21, which serves as the dispensing opening 11, and creating an open state where the contents of the storage portion 23 can be accessed from the dispensing opening 11. Conversely, in the packaging material 20, from the open state shown in Figure 2, the lid portion 22 is rotated downward relative to the main body portion 21 using the hinge portion 24 as a pivot, creating a closed state where the dispensing opening 11 is closed.

[0015] In a unit-dose article packaging 10, it is preferable that the packaging material 20 is made of paper from the viewpoint of reducing environmental impact, aesthetics, and lightness. It is preferable that the paper forming the packaging material 20 is non-permeable or has low moisture permeability. The moisture permeability of the paper forming the packaging material 20 can be evaluated by the moisture permeability value measured according to JIS Z 0208, for example, and is preferably 500 g / m². 2 • 24 hours or less, more preferably 200 g / m² 2 • 24 hours or less, more preferably 100 g / m² 2 • Less than 24 hours. Examples of paper with no or low moisture permeability include coated paper. The packaging material 20 may be made of a material other than paper, for example, resin.

[0016] Multiple water-soluble unit-dose articles W are housed within the storage section 23 of the packaging material 20. Each of the multiple water-soluble unit-dose articles W is a rectangular sheet in planar shape and is arranged in three rows upright on the bottom surface of the storage section 23 of the packaging material 20. The multiple water-soluble unit-dose articles W are stored in the closed state shown in Figure 1 and can be opened in the open state shown in Figure 2 when in use, allowing them to be removed from the dispensing opening 11.

[0017] The water-soluble unit-dose article W may be a unit-dose article of 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. Furthermore, it is preferable that the water-soluble unit-dose article W contains a surfactant and a water-soluble inorganic salt. Each component such as the surfactant and water-soluble inorganic salt in the water-soluble unit-dose article W is contained in at least one of the water-soluble resin substrate X and the granular material Y.

[0018] In the case of the water-soluble unit-dose article W, stickiness is likely to occur on the water-soluble resin substrate X due to moisture absorption during storage. In particular, in the case of the water-soluble resin substrate X containing polyvinyl alcohol (PVA), stickiness is more likely to occur. On the other hand, in the unit-dose article package 10, the packaging material 20 is configured such that stickiness of the water-soluble resin substrate X due to moisture absorption is suppressed, and in each water-soluble unit-dose article W, it is possible to suppress the unpleasant feeling caused by the sticky touch with moisture and the adhesion of the water-soluble component of the water-soluble resin substrate X to the hand.

[0019] Specifically, in the closed state shown in FIG. 1, when the volume of the accommodating portion 23 is V (L) and the total area of the openings such as gaps and through-holes that communicate the accommodating portion 23 and the external space in the packaging material 20 is T, the ratio T / V of the total area T of the openings in the packaging material 20 to the volume V of the accommodating portion 23 is 40 mm 2 / L or less, the inventors of the present application have found that moisture absorption of the water-soluble resin substrate X of each water-soluble unit-dose article W accommodated in the accommodating portion 23 can be effectively suppressed. In particular, in the case of the packaging material 20 made of paper, gaps are inevitably generated and it is difficult to completely seal the accommodating portion 23. However, by reducing the total area of the openings in the packaging material 20 so that the ratio T / V of the total area T of the openings in the packaging material 20 to the volume V of the accommodating portion 23 is 40 mm 2 / L or less, stickiness of the water-soluble resin substrate X of the water-soluble unit-dose article W can be effectively suppressed. From this viewpoint, the ratio T / V of the total area T of the openings in the packaging material 20 to the volume V of the accommodating portion 23 is preferably 37 mm 2 / L or less, more preferably 35 mm 2 / L or less, still more preferably 32 mm 2 / L or less.

[0020] Further, for example, when the water-soluble unit-dose article W has a fragrance, by charging the same fragrance component as the fragrance into the unit-dose article package 10, from the viewpoint of being able to confirm the fragrance tone of the water-soluble unit-dose article W, the ratio T / V of the total area T of the openings in the packaging material 20 to the volume V of the accommodating portion 23 is preferably more than 0 mm 2 / L, more preferably 0.1 mm2 / L or more, more preferably 1 mm 2 It is / L or higher.

[0021] The total area T of the openings in the packaging material 20 of the unit-dose article packaging 10 can be calculated as follows.

[0022] The packaging material 20, with its adjusted total opening area T, contains 10% by volume of calcium chloride (average particle size 300 μm, density 0.8 g / cm³) of the volume V of the containment section 23. 3 The container is filled with calcium chloride and stored for 24 hours at a temperature of 40°C and a humidity of 90%. After that, the amount of calcium chloride absorbed (g) is measured against the total surface area (m²) of the packaging material 20. 2 The value obtained by dividing by ) is called moisture permeability P (g / m 2 (24hr). By measuring the water vapor permeability P for multiple packaging materials 20 having mutually different ratios T / V of the total area T of the openings to the volume V of the storage section 23, a calibration curve showing the relationship between the ratio T / V and the water vapor permeability P in the packaging material 20 can be obtained. As the packaging material 20 for obtaining the calibration curve showing the relationship between the ratio T / V and the water vapor permeability P, for example, a 100 mL vial can be used, and in this case, the total area T of the openings can be adjusted by the number of through holes with a diameter of 2 mm formed in the lid of the vial.

[0023] The total area T of the openings in the packaging material 20 can be determined using this calibration curve as follows. The storage section 23 of the packaging material 20 for which the total area T of the openings is to be determined contains calcium chloride equivalent to 10% of the volume V of the storage section 23, and in a closed state, the moisture permeability P (g / m³) of the packaging material 20 is determined in the same manner as above. 2 Measure the moisture content (24hr). For the packaging material 20, use the calibration curve described above to determine the ratio T / V of the total area of ​​the openings to the volume V of the containment section 23 from the moisture permeability P. For the packaging material 20, calculate the total area T of the openings by multiplying the obtained ratio T / V by the volume V of the containment section 23.

[0024] The configuration of the unit-dose article packaging 10 is not limited to the above. For example, in the unit-dose article packaging 10, the size and shape of the packaging material 20 can be arbitrarily determined, and the arrangement of the multiple water-soluble unit-dose articles W in the storage section 23 of the packaging material 20 can also be arbitrarily determined. Furthermore, in the unit-dose article packaging 10, the number of water-soluble unit-dose articles W to be stored in the storage section 23 of the packaging material 20 can be arbitrarily determined, and there may be only one.

[0025] 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.

[0026] Furthermore, in the unit-dose product packaging 10, the planar shape of the water-soluble unit-dose product W is not limited to a rectangle, but may be, for example, circular, elliptical, or a polygon other than a rectangle. Moreover, in the unit-dose product packaging 10, the water-soluble unit-dose product W does not have to be in sheet form, but may be in any three-dimensional shape. In addition, the unit-dose product packaging 10 does not have to be configured to close the dispensing opening 11 with a lid portion 22, but may be closed with, for example, adhesive tape.

[0027] [Overall composition of water-soluble unit dose article W] 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.

[0028] Examples of water-soluble resins usable for the water-soluble resin substrate X include polyvinyl alcohol, vinyl alcohol copolymer, polyvinylpyrrolidone, polyalkylene oxide, (modified) cellulose, (modified) cellulose ether or ester or amide, polycarboxylic acids and their salts such as polyacrylate, maleic acid / acrylic acid copolymer, 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.

[0029] Figure 3 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 3, the water-soluble resin substrate X is a water-soluble fiber structure composed of aggregates of multiple water-soluble fibers. In the water-soluble unit-dose article W shown in Figure 3, 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.

[0030] 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 4, 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 4, 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 4 shows the granular material Y inside the water-soluble resin substrate X by viewing it through the water-soluble resin substrate X.

[0031] 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.

[0032] 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.

[0033] 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 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.

[0034] [Surfactants] The water-soluble unit-dose article W preferably contains a surfactant to enhance its cleaning properties. Examples of surfactants include one or more selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and it is even more preferable that one or more selected from anionic surfactants and nonionic surfactants are present from the viewpoint of improving cleaning properties and foaming.

[0035] In the water-soluble unit-dose article W, when a surfactant is added, from the viewpoint of improving cleaning performance, the surfactant content 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 economic efficiency, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

[0036] 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.

[0037] (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, alkyl sulfosuccinate ester type surfactants, and fatty acids and their salts are more preferred, and sulfate ester type surfactants and alkylaryl sulfonic acid type surfactants 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 even more preferably one or more selected from alkyl sulfate salts and alkyl ether sulfate salts.

[0038] 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 one or more inorganic salts selected from alkali metal salts such as sodium salts and potassium salts, and alkaline earth metal salts such as magnesium salts, more preferably alkali metal salts, and even more preferably sodium salts.

[0039] 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.

[0040] Examples of anionic surfactants include one or more compounds selected from the compounds represented by the following general formulas (1-1), (1-2), (1-3), and (1-4). From the viewpoint of cleaning performance, the anionic surfactant is preferably one or more compounds selected from the compounds represented by general formulas (1-1), (1-2), or (1-3), more preferably one or more compounds selected from the compounds represented by general formulas (1-1) or (1-2), and even more preferably one or more compounds selected from the compounds represented by general formula (1-1).

[0041] R 1a -O-(AO) n -SO3M (1-1) (In formula (1-1), R 1a (wherein is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is one or more alkylene oxy groups selected from ethylene oxy groups and propylene oxy groups, n is a number between 0 and 20, and M is a cation.)

[0042] R 2a -Φ-SO3M …(1-2) (In formula (1-2), R 2a Φ represents an alkyl group having 9 to 14 carbon atoms, Φ represents a phenylene group, and R is bonded to the carbon atom of Φ. 2a The carbon atoms are secondary carbon atoms, and M indicates a cation. R is bonded to Φ. 2a In contrast, the sulfonic acid group is bonded to the ortho, meta, or para position.

[0043] R 3a -COOM …(1-3) (In formula (1-3), R3a (wherein represents an alkyl or alkenyl group with 9 to 17 carbon atoms, and M represents a cation.)

[0044] R 4a -CH(SO3M)COOR 5a (1-4) (In formula (1-4), R 4a R represents an alkyl group with 8 to 18 carbon atoms. 5a (wherein represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M represents a cation.)

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In formula (1-1), the average number of moles of propyleneoxy groups may be 0.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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 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.

[0054] In general formula (1-2), R 2aThe alkyl group has a carbon number of carbon atoms, preferably 9 or more, more preferably 10 or more, and preferably 14 or less, more preferably 13 or less. In general 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 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 the surfactant 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, from the viewpoint of improving cleaning performance, and preferably 25% by mass or less, more preferably 20% by mass or less, from the viewpoint of economic efficiency.

[0057] In general formula (1-3), R 3a This is an alkyl or alkenyl group having 9 or more carbon atoms, more preferably 10 or more, even more preferably 11 or more, and more preferably 17 or less, more preferably 15 or less, and even more preferably 13 or less. 3aThe 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 M is an alkyl group having 10 to 16 carbon atoms are preferred, and compounds in which M is a cation are more preferred, with M being a hydrogen ion or a sodium ion being 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 carbon atoms, more preferably 16 or fewer carbon atoms. 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 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.

[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. A 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 cleansing properties 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 cleanability.

[0073] In general formula (2-1), R 7a From the viewpoint of cleanability, 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. 12aFrom the viewpoint of antibacterial performance, 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. 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] 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.

[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 salts] In the water-soluble unit-dose article W, it is preferable that a water-soluble inorganic salt is included as an alkaline agent to obtain high cleansing properties against sebum and the like by improving the penetration action of the surfactant. Examples of water-soluble inorganic salts include one or more selected from carbonates, bicarbonates, silicates, and tripolyphosphates, and from the viewpoint of improving cleansing properties, one or more selected from carbonates and bicarbonates 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 to obtain high cleaning performance by improving the penetration action of the surfactant, and it is preferable not to have too much water-soluble inorganic salt to suppress the generation of undissolved residue. From these viewpoints, in the water-soluble unit-dose article W, when it contains water-soluble inorganic salt, the content of water-soluble inorganic salt 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 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 surfactants and water-soluble inorganic salts 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 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.

[0100] In the water-soluble unit-dose article W, if a chelating agent is included, from the viewpoint of cleaning performance, 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 a water-soluble inorganic salt, it 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.

[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 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), International Publication No. 98 / 4262 The hybrid zeolite described in item 2 is also a suitable option.

[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] [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.

[0118] 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.) • PEI-EO: Ethoxylated polyethyleneimine "Sokalan HP 20" (manufactured by BASF) • Silica: "Toxeal NR" (average particle size 181 μm, manufactured by Oriental Silicas Corporation) • Zeolite: "Zeobuilder" (Type 4A, average particle size 3.5 μm, manufactured by ZEOBUILDER)

[0119] In the examples and comparative examples, samples of water-soluble unit-dose articles with a common composition were prepared by holding granular material in a water-soluble resin substrate. Specifically, in both the examples and comparative examples, a sample of approximately 13 g of water-soluble unit-dose article (40 mL) was prepared by containing 12 g of granular material in a 7.5 cm x 7.5 cm rectangular flat bag (0.6 g) of the water-soluble resin substrate. 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.

[0120] [Table 1]

[0121] Next, a sample of the unit-dose product packaging was prepared by placing a sample of the water-soluble unit-dose product into a 100 mL vial. In other words, in the examples and comparative examples, vials were used as the packaging material for the unit-dose product packaging. In the examples and comparative examples, the opening of the packaging material was reproduced by forming a through-hole with a diameter of 2 mm in the lid of the vial.

[0122] In the vial according to Example 1, no through-holes are formed, and the ratio of the total area of ​​the openings to the volume is 0 mm². 2 The volume is / L. In the vial according to Example 2, one through hole is formed, and the ratio of the total area of ​​the opening to the volume is 31 mm². 2 The volume is / L. In the vial according to Comparative Example 1, two through holes are formed, and the ratio of the total area of ​​the openings to the volume is 63 mm². 2 The volume is / L. In the vial according to Comparative Example 2, three through holes are formed, and the ratio of the total area of ​​the openings to the volume is 94 mm². 2 The volume is / L. In the vial according to Comparative Example 3, four through holes are formed, and the ratio of the total area of ​​the openings to the volume is 126 mm². 2 / is

[0123] Samples of the unit-dose article packages according to Example 1, Example 2, and Comparative Examples 1 to 3 were subjected to a storage test. In the storage test, each sample was held in a thermostatic chamber at 30°C and 70% RH, and the mass increase rate and the tactile evaluation of the sample were performed at each time point after 1 to 14 days had elapsed since the start of the holding. The mass increase rate was determined as the ratio of the increase in mass at each time point to the mass at the start of the test for each sample.

[0124] Regarding the tactile feeling, the evaluator touched the sample of the water-soluble unit-dose article taken out from the vial by hand and evaluated it according to the following criteria. A: Without unpleasant moisture B: With slightly unpleasant moisture C: With unpleasant moisture D: With very unpleasant moisture

[0125] Table 2 shows, for the samples of the unit-dose article packages according to Example 1, Example 2, and Comparative Examples 1 to 3, the ratio of the total area of the openings to the volume of the vial, and the evaluation results of the mass increase rate and the tactile feeling at the time points when 1 day, 2 days, 7 days, and 14 days had elapsed since the start of the storage test.

[0126]

Table 2

[0127] Regarding the tactile feeling at the time point when 1 day had elapsed since the start of the holding, good evaluation results were obtained for any of the samples according to Example 1, Example 2, and Comparative Examples 1 to 3. However, regarding the tactile feeling at the time point when 2 days or more had elapsed since the start of the holding, no change was observed in the samples according to Example 1 and Example 2 in which the ratio of the total area of the openings to the volume of the vial was 40 mm 2 / L or less. On the other hand, in the samples according to Comparative Examples 1 to 3 in which the ratio of the total area of the openings to the volume of the vial exceeded 40 cm 2 / L, a tendency to deteriorate with the passage of days was observed.

[0128] Figure 5 is a graph showing the change in the rate of mass increase over time for each sample. Referring to Figure 5, the ratio of the total area of ​​the opening to the volume of the vial is 40 mm 2 In Examples 1 and 2, where the ratio of the total area of ​​the opening to the volume of the vial is 40 mm², the ratio of the total area of ​​the opening to the volume of the vial is 40 mm². 2 It can be seen that a significantly lower mass increase rate is obtained compared to Comparative Examples 1-3, which exceeded / L. This means that the ratio of the total area of ​​the openings to the volume of the packaging material is 40 cm². 2 It was confirmed that by setting the amount to less than / L, a unit-dose product packaging can be obtained that effectively suppresses the occurrence of stickiness in water-soluble unit-dose products. [Explanation of Symbols]

[0129] 10... Unit dose product packaging 11…Dispensing opening 20...Packaging material 21...Main body 22...Lid part 23...Detention Unit W...Water-soluble unit dose article X…Water-soluble resin base Y...granular

Claims

1. A unit-dose article package containing a water-soluble unit-dose article, It has a storage compartment and an outlet, and in the closed state with the outlet closed, the ratio of the total area of ​​the openings connecting the storage compartment and the external space to the volume of the storage compartment is 40 mm ２ Packaging materials that are / L or less, The water-soluble unit dose article contained in the aforementioned storage section, A unit-dose article packaging comprising the following:

2. The water-soluble unit-dose article comprises a water-soluble resin substrate and granular material held within the water-soluble resin substrate. A unit-dose article packaging according to claim 1.

3. The aforementioned water-soluble unit dose article contains a surfactant. The unit dose article packaging according to claim 2.

4. The surfactant is one or more selected from anionic surfactants and nonionic surfactants. The unit dose article packaging according to claim 3.

5. The aforementioned water-soluble unit dose article further contains a water-soluble inorganic salt. The unit dose article packaging according to claim 3.

6. The aforementioned water-soluble inorganic salt is one or more selected from carbonates and bicarbonates. The unit dose article packaging according to claim 5.

7. The water-soluble resin substrate is composed of one or more selected from water-soluble fiber structures and water-soluble films. The unit dose article packaging according to claim 3.

8. The packaging material is made of paper and has the opening A unit-dose article packaging according to claim 1.

9. The aforementioned water-soluble unit-dose article is a unit-dose article of laundry detergent. A unit-dose article packaging according to any one of claims 1 to 8.

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