Sheet for application to body

Abstract

To provide a sheet for application to a body that demonstrates high motion adaptability and effectively enhances blood circulation by carbonic acid gas, while maintaining adhesion (tack strength) to the body.SOLUTION: Provided is a sheet for application to a body, which comprises a gel layer. The gel layer comprises (A) 100 ppm or more and 20000 ppm or less of carbonic acid gas, (B) polyacrylic acid and / or a salt thereof, (C) aluminum atoms, and (D) 60 mass% or more and 90 mass% or less of water. A ball number of the gel layer is 15 or more to 30 or less in a ball tack test performed in accordance with JIS Z0237:2009 at an inclined board angle of 30°, a temperature of 23°C, and humidity of 50%R.H. A loss tangent in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz is 0.20 or more and 0.50 or less. A loss tangent in dynamic viscoelasticity measurement at a frequency of 10 Hz is 0.25 or more and 0.50 or less. Weight is 800 g / m2 or more and 2500 g / m2 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a sheet for application to the body. [Background technology]

[0002] Conventionally, sheets for application to the body (hydrous gel sheets) that utilize the blood circulation promoting effect of carbon dioxide gas have been developed for the purpose of preventing and treating skin diseases, providing beauty benefits, and recovering from fatigue. For example, Patent Document 1 describes a method for producing a hydrogel article containing carbon dioxide gas, which comprises preparing a hydrogel article containing a water-soluble polymer, a crosslinking agent and water and having a specific loss tangent, for the purpose of producing a hydrogel article having high carbon dioxide gas retention in the hydrogel with good productivity, and causing the hydrogel to absorb carbon dioxide gas while evaluating the degree of crosslinking of the water-soluble polymer using the loss tangent of the hydrogel as a measure. The method describes a sheet-like article as the hydrogel article. Patent Document 2 describes a containerized sheet for application to the body, which is made by sealing a laminated sheet of a foamed gel layer or foamed liquid layer containing bubbles with a specific bubble ratio and a resin film in a gas-impermeable container, and contains a gas that is physiologically active in the body, such as oxygen or carbon dioxide, in the void space in the container during storage, with the aim of providing a preparation that can be easily and inexpensively produced and can continuously supply a sufficient amount of gas that is physiologically active in the body to the skin. Patent Document 3 describes a sheet material for application to the body, which is made by sealing a sheet-type patch together with carbon dioxide in a packaging pillow that is poorly permeable to carbon dioxide, with the aim of providing a means for supplying carbon dioxide to the skin that is not irritating to the skin, can supply carbon dioxide to the skin continuously, and is easy to use, in which the sheet-type patch contains a liquid or gel with a pH of 3.5 to 6.5 in which a specific amount of carbon dioxide is dissolved, and the filling ratio of the liquid or gel to the volume calculated from the internal surface area of ​​the packaging pillow is specified. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-165252 [Patent Document 2] JP 2010-202609 A [Patent Document 3] JP 2005-170937 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the hydrogel sheets described in these patent documents, if the amount of carbon dioxide gas is to be increased, the moisture content and basis weight of the gel layer must be increased, and the sheet becomes thicker. As a result, the hydrogel sheet does not have sufficient movement tracking ability, and it is difficult to maintain the state of attachment to the body, particularly when the sheet is attached to a part of the body that moves a lot, such as the neck, shoulders, calves, or knees, and the hydrogel sheet may float or peel off. It has been found that such a hydrogel sheet requires adhesion to the body (adhesiveness) and the ability to follow the movement of the body (skin) after attachment (motion tracking ability) in order to be used by attaching it to the body. [Means for solving the problem]

[0005] The present invention relates to the following [1]. [1] A sheet for application to the body having a gel layer, The gel layer comprises the following components (A) to (D): (A) Carbon dioxide: 100 ppm or more and 20,000 ppm or less (B) Polyacrylic acid and / or its salt (C) Aluminum atom (D) Water: 60% by mass or more and 90% by mass or less Contains the gel layer has a ball number of 15 or more and 30 or less in a ball tack test performed in accordance with JIS Z0237:2009 under conditions of an inclined plate angle of 30°, a temperature of 23° C. and a relative humidity of 50%; the gel layer has a loss tangent of 0.20 or more and 0.50 or less in dynamic viscoelasticity measurement at a temperature of 25° C. and a frequency of 0.1 Hz; the gel layer has a loss tangent of 0.25 or more and 0.50 or less in dynamic viscoelasticity measurement at a temperature of 25° C. and a frequency of 10 Hz; The basis weight of the gel layer is 800 g / m 2 More than 2500g / m 2 Below is the Sheet for application to the body. Effect of the Invention

[0006] According to the present invention, it is possible to provide a sheet for application to the body that has excellent adhesion (tackiness) to the body, excellent movement-following properties, and a high blood circulation promoting effect due to carbon dioxide gas. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] [Body application sheet] The sheet for application to the body of the present invention (hereinafter also simply referred to as the "sheet of the present invention") is a sheet for application to the body having a gel layer, and the gel layer comprises the following components (A) to (D): (A) Carbon dioxide: 100 ppm or more and 20,000 ppm or less (B) Polyacrylic acid and / or its salt (C) Aluminum atom (D) Water: 60% by mass or more and 90% by mass or less Contains the gel layer has a ball number of 15 or more and 30 or less in a ball tack test performed in accordance with JIS Z0237:2009 under conditions of an inclined plate angle of 30°, a temperature of 23° C. and a relative humidity of 50%; the gel layer has a loss tangent of 0.20 or more and 0.50 or less in dynamic viscoelasticity measurement at a temperature of 25° C. and a frequency of 0.1 Hz; the gel layer has a loss tangent of 0.25 or more and 0.50 or less in dynamic viscoelasticity measurement at a temperature of 25° C. and a frequency of 10 Hz; The basis weight of the gel layer is 800 g / m 2 More than 2500g / m 2 The following is the result. The body application sheet of the present invention has the above-mentioned specific composition, a ball number in a ball tack test that is within a prescribed range, a loss tangent in dynamic viscoelasticity measurement at a specific frequency that is within a specific range, and a basis weight of the gel layer that is within a specific range, thereby achieving both adhesion to the body and movement-following ability while enhancing the blood circulation promoting effect of carbon dioxide.

[0008] <Gel layer> The body application sheet of the present invention comprises the following components (A) to (D): (A) Carbon dioxide: 100 ppm or more and 20,000 ppm or less (B) Polyacrylic acid and / or its salt (C) Aluminum atom (D) Water: 60% by mass or more and 90% by mass or less Contains The ball number in the ball tack test conducted according to JIS Z0237:2009 under the conditions of an inclined plate angle of 30°, a temperature of 23°C, and 50% RH is 15 or more and 30 or less. The loss tangent in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz is 0.20 or more and 0.50 or less, The loss tangent in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 10 Hz is 0.25 to 0.50, Basis weight 800g / m 2 More than 2500g / m 2 The gel layer is: In the gel layer, component (B) has a crosslinked structure crosslinked by component (C). The sheet of the present invention having the gel layer can enhance the blood circulation promoting effect by carbon dioxide while achieving both adhesion to the body and movement-following ability.

[0009] Each component contained in the gel layer will be described below. The contents of components other than component (A) are based on the total amount of the gel layer excluding component (A), unless otherwise specified. (Component (A): Carbon dioxide gas) The gel layer constituting the sheet of the present invention contains carbon dioxide gas in an amount of 100 ppm or more and 20,000 ppm or less, thereby enhancing the blood circulation promoting effect when the sheet of the present invention is applied to the body. The content of component (A) in the total amount of the gel layer is 100 ppm or more, preferably 200 ppm or more, more preferably 500 ppm or more, even more preferably 800 ppm or more, and even more preferably 900 ppm or more from the viewpoint of improving the blood circulation promoting effect, and is 20000 ppm or less, preferably 10000 ppm or less, more preferably 5000 ppm or less, even more preferably 3000 ppm or less, and even more preferably 2000 ppm or less from the viewpoint of ease of production. The carbon dioxide content in the gel layer can be measured by the method described in the Examples.

[0010] (Component (B): Polyacrylic acid and / or its salt) The gel layer constituting the sheet of the present invention contains polyacrylic acid and / or a salt thereof as component (B). Component (B) is a carboxy group (-COOH) or a carboxylate group (-COO - ) which can form a crosslinked structure through ionic interactions with component (C). Examples of the salt of polyacrylic acid include alkali metal salts such as sodium salt and potassium salt, ammonium salt, etc. From the viewpoints of availability and improving operational tracking, the salt of polyacrylic acid is preferably an alkali metal salt of polyacrylic acid, and more preferably a sodium salt of polyacrylic acid (sodium polyacrylate). Examples of commercially available polyacrylic acids used as component (B) include the Accusol series manufactured by Dow Chemical Japan Co., Ltd. Examples of commercially available sodium polyacrylates include the Aronvis series and Julimer series manufactured by Toagosei Co., Ltd., and the Aqualic series manufactured by Nippon Shokubai Co., Ltd.

[0011] One or more kinds of component (B) can be used. Among them, from the viewpoints of availability and improving operational followability, it is preferable that component (B) is one or more kinds selected from the group consisting of polyacrylic acid and sodium polyacrylate.

[0012] The content of component (B) in the total amount of the gel layer (excluding component (A)) is preferably 3% by mass or more, more preferably 4% by mass or more, even more preferably 4.5% by mass or more, and even more preferably 5% by mass or more from the viewpoint of improving the shape retention and adhesiveness (tackiness) of the gel layer. And, from the viewpoint of suppressing an excessive increase in viscosity and improving the handling properties such as ease of application, the content is preferably 10% by mass or less, more preferably 9% by mass or less, even more preferably 8% by mass or less, and even more preferably 7% by mass or less. In addition to the above, from the viewpoint of improving the movement-following ability and blood circulation-promoting effect when the sheet of the present invention is applied to the body, the content of component (B) in the total amount of the gel layer (excluding component (A)) is preferably 5.5 mass% or more and preferably 6.5 mass% or less.

[0013] As the polyacrylic acid and / or a salt thereof, it is preferable to use at least a polyacrylic acid salt, and the polyacrylic acid salt may be a fully neutralized polyacrylic acid in which all of the carboxy groups of the polyacrylic acid are neutralized, or a partially neutralized polyacrylic acid in which some of the carboxy groups are neutralized. As component (B), from the viewpoint of facilitating the adjustment of the balance between adhesion, water retention, and shape retention, it is preferable to use a combination of polyacrylic acid or a fully neutralized polyacrylic acid and a partially neutralized polyacrylic acid, and it is even more preferable to use a combination of a fully neutralized polyacrylic acid and a partially neutralized polyacrylic acid.

[0014] Such a neutralized polyacrylic acid may be obtained, for example, by polymerizing acrylic acid to form polyacrylic acid and then neutralizing the polyacrylic acid, or by polymerizing an acrylate salt obtained by neutralizing acrylic acid. In addition, the ratio of unneutralized carboxy groups to neutralized carboxy groups contained in the total amount of component (B), i.e., the molar ratio of acrylic acid units to acrylate units (acrylic acid units / acrylate units) contained in the total amount of component (B), is, from the viewpoint of forming a gel layer exhibiting viscous properties over a wide frequency range (including 0.1 Hz and 10 Hz; the same applies below) and improving motion tracking, preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, still more preferably 0.4 or more, and is preferably 3.0 or less, more preferably 2.0 or less, even more preferably 1.6 or less, still more preferably 1.0 or less, and still more preferably 0.7 or less. It is believed that by changing the molar ratio of acrylic acid units to acrylate units in this way (for example, the amount of sodium ions present when the acrylate is sodium acrylate), the crosslinked structure between aluminum ions, which are ionized aluminum atoms, and carboxy groups of polyacrylic acid changes, resulting in the above-mentioned effects.

[0015] (Component (C): Aluminum atom) The gel layer constituting the sheet of the present invention contains aluminum atoms as component (C). The trivalent aluminum ions that are the ionized product of component (C) can act as a crosslinking agent for component (B), and it is believed that a crosslinked structure is formed in the gel layer by ionic interaction with component (B). The source of aluminum atoms, which is component (C), is not particularly limited as long as it is an aluminum-containing compound (hereinafter also referred to as "component (C1)"), but from the viewpoint of ease of supply as aluminum ions capable of crosslinking component (B), it is preferably an inorganic aluminum-containing compound that contains aluminum.

[0016] Examples of the aluminum-containing compound (C1) which can act as a crosslinking agent for component (B) and which serves as a supply source of component (C) include aluminum hydroxide, aluminum magnesium hydroxide, sodium aluminate, aluminum sulfate, aluminum potassium sulfate, aluminum ammonium sulfate, aluminum carbonate, aluminum nitrate, aluminum chloride, magnesium aluminium (meta)silicate, aluminum acetate, aluminum lactate, aluminum stearate, aluminum myristate, aluminum glycinate, aluminum benzoate, and aluminum allantoin chlorohydroxylate, and one or more of these can be used. Among the above, from the viewpoint of ease of supplying aluminum ions, it is preferable that component (C1) be one or more selected from the group consisting of aluminum hydroxide and magnesium aluminosilicate (meta)silicate. From the viewpoints of easy availability and improving motion tracking, and from the viewpoint of forming a gel layer that exhibits viscous properties over a wide frequency range (including 0.1 Hz and 10 Hz) and improving motion tracking, aluminum hydroxide is particularly preferable.

[0017] The content of component (C) in the total amount of the gel layer (excluding component (A)) is preferably 0.0015% by mass or more, more preferably 0.0035% by mass or more, even more preferably 0.007% by mass or more, still more preferably 0.0085% by mass or more, and even more preferably 0.012% by mass or more, from the viewpoints of suppressing the exudation of the gel layer into the substrate (nonwoven fabric) when the gel layer is laminated thereon and suppressing excessive stickiness of the gel layer. From the viewpoints of forming a gel layer exhibiting viscous properties in a wide frequency range (including 0.1 Hz and 10 Hz; the same applies below) to improve movement tracking, improve the blood circulation promoting effect, and facilitate the incorporation of carbon dioxide gas into the gel layer, the content is preferably 0.035% by mass or less, more preferably 0.020% by mass or less, and even more preferably 0.016% by mass or less. The content of component (C) in the gel layer can be measured according to the 18th Edition of the Japanese Pharmacopoeia, General Test Methods, Inductively Coupled Plasma Atomic Emission Spectroscopy and Inductively Coupled Plasma Mass Spectroscopy. Either the plasma atomic emission spectroscopic analysis or the inductively coupled plasma mass spectrometry can be used.

[0018] The mass ratio [(B) / (C)] in the gel layer is preferably 250 or more, more preferably 300 or more, even more preferably 375 or more, still more preferably 400 or more, and even more preferably 520 or more, from the viewpoints of forming a gel layer that exhibits viscous properties in a wide frequency range (including 0.1 Hz and 10 Hz) to improve motion tracking, improve the blood circulation promoting effect, and make it easier to incorporate carbon dioxide gas into the gel layer. In addition, the mass ratio is preferably 900 or less, more preferably 850 or less, even more preferably 700 or less, and even more preferably 600 or less, from the viewpoints of suppressing seepage into the base material when the gel layer is laminated on the base material (nonwoven fabric) and suppressing excessive stickiness of the gel layer. In addition, in the composition of the gel layer of the sheet of the present invention, when the content of component (C) is reduced, the loss tangent tends to increase over a wide frequency range (including 0.1 Hz and 10 Hz), and when the content of component (C) is increased, the loss tangent tends to decrease. Therefore, by adjusting the content of component (C), it is possible to adjust the loss tangent over a wide frequency range.

[0019] (Component (D): water) The gel layer constituting the sheet of the present invention contains 60% by mass or more and 90% by mass or less of water, which allows a sufficient amount of carbon dioxide gas to be retained within the gel layer, and the carbon dioxide gas retained within the gel layer can be applied to the skin to achieve the effect of promoting blood circulation. As the component (D), for example, purified water such as deionized water, distilled water, highly pure water, and ultrapure water can be used. The content of component (D) in the entire gel layer (excluding component (A)) is 60% by mass or more, preferably 65% ​​by mass or more, more preferably 70% by mass or more, from the viewpoint of facilitating incorporation of carbon dioxide gas into the gel layer, and from the viewpoint of effectively penetrating carbon dioxide gas into the skin and improving the blood circulation promoting effect. From the viewpoint of improving shape retention, increasing viscosity, and improving movement tracking, the content is 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less. The content of component (D) in the entire gel layer (excluding component (A)) is 60% by mass or more and 90% by mass or less, preferably 65% ​​by mass or more and 85% by mass or less, more preferably 70% by mass or more and 80% by mass or less.

[0020] From the viewpoint of more effectively obtaining the effects of the present invention, the total content of the components (B) to (D) in the gel layer excluding the component (A) is preferably 60 mass % or more, more preferably 70 mass % or more, and even more preferably 75 mass % or more, and is 100 mass % or less.

[0021] The gel layer constituting the sheet of the present invention preferably further contains at least one member selected from the group consisting of (E) carboxymethyl cellulose and / or a salt thereof, and (F) polyvinyl alcohol. By including such a component, the shape retention of the gel layer can be improved and exudation into the nonwoven fabric support can be suppressed. Among these, from the viewpoint of improving the adhesion (tackiness), movement tracking, and blood circulation promoting effect of the gel layer, it is preferable to contain at least component (F). That is, the gel layer preferably contains only component (F) (not containing component (E)), or contains both components (E) and (F), and more preferably contains only component (F) (not containing component (E)). Components (E) and (F) will be described below.

[0022] (Component (E): Carboxymethylcellulose and / or its salt) By including component (E), the gel layer can improve the shape retention of the gel layer and inhibit the gel layer from bleeding into the nonwoven fabric support. Examples of the salt of carboxymethylcellulose include alkali metal salts such as sodium salt and potassium salt, ammonium salt, etc. From the viewpoints of availability and improving operational followability, the salt of carboxymethylcellulose is preferably an alkali metal salt of carboxymethylcellulose, and more preferably a sodium salt of carboxymethylcellulose (sodium carboxymethylcellulose).

[0023] From the viewpoint of obtaining appropriate shape retention of the gel layer and improving the stability of the gel layer, component (E) preferably has a viscosity at 25°C when made into a 1% by mass aqueous solution, as measured with a Brookfield viscometer, of at least 1,000 mPa·s, more preferably at least 1,200 mPa·s, even more preferably at least 1,500 mPa·s, and preferably at most 7,000 mPa·s, more preferably at most 6,000 mPa·s, even more preferably at most 5,000 mPa·s.

[0024] One or more kinds of component (E) can be used. Among them, from the viewpoints of availability and improving the movement tracking property, the component (E) is preferably one or more kinds selected from the group consisting of carboxymethylcellulose and sodium carboxymethylcellulose, and more preferably sodium carboxymethylcellulose. Examples of commercially available sodium carboxymethylcellulose used as component (E) include CMC Daicel series manufactured by Daicel Corporation and Sunrose series manufactured by Nippon Paper Industries Co., Ltd.

[0025] When the gel layer contains component (E), the content of component (E) in the total amount of the gel layer (excluding component (A)) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, still more preferably 2% by mass or more, and even more preferably 3% by mass or more from the viewpoint of obtaining a suitable shape retention of the gel layer. And, from the viewpoint of improving the adhesiveness (tackiness), the movement followability, and the blood circulation promoting effect, it is preferably 5.0% by mass or less, more preferably 4.8% by mass or less, even more preferably 4.4% by mass or less, and even more preferably 4% by mass or less. When component (E) is a salt of carboxymethyl cellulose, the content of component (E) in the gel layer means the content as the salt.

[0026] In addition, from the viewpoint of obtaining appropriate shape retention of the gel layer, the mass ratio of component (E) to component (B) in the gel layer (mass ratio [(E) / (B)]) is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.4 or more. And from the viewpoints of improving adhesiveness (tack force), motion followability, and blood circulation promoting effect, it is preferably 1.0 or less, more preferably 0.9 or less, still more preferably 0.8 or less.

[0027] (Component (F): Polyvinyl alcohol) By including component (F), the gel layer can improve its shape retention, and the tack force and viscous properties in a wide frequency range (including 0.1 Hz and 10 Hz) are improved, so that the adhesion to the skin (motion followability) and blood circulation promoting effect can be improved. The weight average molecular weight of component (F) is not particularly limited, but from the viewpoint of obtaining appropriate shape retention of the gel layer, it is preferably 30,000 or more, more preferably 50,000 or more, still more preferably 70,000 or more. And from the viewpoints of improving the tack force of the gel layer and the adhesion of the sheet to the skin, it is preferably 150,000 or less, more preferably 130,000 or less, still more preferably 120,000 or less. The weight average molecular weight of the powder raw material of component (F) is obtained by measuring an aqueous solution in which the powder raw material is dissolved in water by size exclusion chromatography (SEC) under the following conditions. Note that the "powder raw material of component (F)" means component (F) in a powder state before being contained in the gel layer or the gel-forming composition described later. Also, the weight average molecular weight of component (F) in the gel layer is obtained by measuring the extract of the gel layer by SEC under the following conditions. <SEC measurement conditions> Measuring device: "SEC-8320" manufactured by Tosoh Corporation Eluent: 0.2 mol / L phosphate buffer / acetonitrile = 9 / 1 (V / V%) Guard column: Tosoh Corporation's "PWXL (6mm x 4cm)" Analytical column: Tosoh Corporation "G4000PWxL + G2500PWxL (7.8 mm x 30 cm) Flow rate: 1mL / min Column temperature: 40℃ Injection volume: 100μL Sample size: 1mg / mL Molecular weight conversion standard: PEO manufactured by Tosoh Corporation (SE-150 (977,000), SE-70 (580,000), SE-30 (394,000), SE-15 (143,000), SE-8 (101,000), SE-2 (21,000)) Detector: RI

[0028] The saponification degree of component (F) is preferably 75 mol% or more, more preferably 82 mol% or more, and even more preferably 85 mol% or more from the viewpoint of improving the tackiness of the gel layer and thereby improving the adhesion of the sheet to the skin. The saponification degree of component (F) may be 100 mol% or less, and from the viewpoint of increasing the water solubility of component (F) and improving its handling, it is preferably 98 mol% or less, more preferably 96 mol% or less. The saponification degree of component (F) is preferably 75 mol% or more and 98 mol% or less, more preferably 82 mol% or more and 98 mol% or less, and even more preferably 85 mol% or more and 96 mol% or less. The degree of saponification of component (F) can be measured in accordance with JIS K6726:1994.

[0029] Component (F) is preferably unmodified polyvinyl alcohol, but may be modified polyvinyl alcohol into which ionic groups or the like have been introduced as necessary. However, it is preferable that component (F) contains a small amount of functional groups capable of forming a crosslinked structure through ionic interactions with aluminum ions, in order not to inhibit the formation of a crosslinked structure in component (B). For example, the content of carboxyl groups in component (F) is preferably 0.1 mol% or less, more preferably 0.01 mol% or less, and even more preferably 0 mol%. Examples of commercially available polyvinyl alcohols that can be used as component (F) include the Gohsenol series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., the Kuraray Poval series manufactured by Kuraray Co., Ltd., and the J Poval series manufactured by Nippon Vinyl Acetate Poval Co., Ltd.

[0030] When the gel layer contains component (F), the content of component (F) in the total amount of the gel layer (excluding component (A)) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of improving adhesiveness (tackiness) and movement followability, and from the viewpoint of improving the blood circulation promoting effect. And, from the viewpoint of suppressing excessive stickiness of the gel layer, it is preferably 6% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, and even more preferably 3% by mass or less. The content of component (F) in the gel layer was measured by extracting the gel layer under the following conditions. 1 This can be obtained by measuring with H-NMR. < 1 H-NMR measurement conditions> Measuring device: JEOL "MR-400" Observation kernel: 1 H Frequency: 300MHz or higher Pulse delay time: 25 seconds Number of times: 32 Mode:Presaturation Solvent: DO Internal standard: 0.1% sodium trimethylpropionate Sample size: 10mg / mL

[0031] The mass ratio of component (F) to component (B) in the gel layer (mass ratio [(F) / (B)]) is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more, from the viewpoint of improving the movement tracking ability and the blood circulation promoting effect. And, from the viewpoint of suppressing excessive stickiness of the gel layer, it is preferably 1.0 or less, more preferably 0.8 or less, and even more preferably 0.6 or less.

[0032] From the viewpoint of more effectively obtaining the effects of the present invention, the total content of the components (B) to (F) in the gel layer is preferably 70% by mass or more, more preferably 76% by mass or more, and even more preferably 80% by mass or more, and is 100% by mass or less.

[0033] (Other Ingredients) The gel layer may contain other components than the components (A) to (F) as appropriate, provided that the object of the present invention is not impaired. Examples of other components include components commonly used in cosmetics, perfumes, cosmetics, medicines, quasi-drugs, etc. The gel layer may contain a moisturizing agent. Examples of moisturizing agents include polyhydric alcohols such as glycerin, diglycerin, polyglycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene glyceryl ether, methyl glucoside, polyoxyethylene methyl glucoside, erythritol, xylitol, sorbitol, mannitol, maltitol, and trehalose, sugar alcohols, sugars, amino acids and their derivatives, and proteins and their derivatives, and may contain one or more of these in combination. The content of the moisturizing agent is preferably 1% by mass or more and 25% by mass or less in the total amount of the gel layer (excluding component (A)). Among these, glycerin is preferably used since it has little effect on the efficacy of the components (B) to (F) in the gel layer and can also be used as a bulking agent to adjust the composition ratio of the components within a suitable range. The gel layer may contain a pH adjuster, such as tartaric acid, succinic acid, citric acid, lactic acid, malic acid, acetic acid, glycolic acid, hydrochloric acid, oxalic acid, phosphoric acid, sodium hydroxide, potassium hydroxide, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, citrate, phosphate, or carbonate.

[0034] In addition, since carbon dioxide gas turns into carbonate under alkaline conditions, the pH of the gel layer of the sheet of the present invention at 25°C is preferably pH 7 or less, more preferably pH 3.5 to 6.5, and even more preferably pH 4.0 to 6.5, from the viewpoint of suppressing the formation of carbonate. In addition to the above, other ingredients that are generally used in these products include, for example, water-soluble polymers other than components (B), (E), and (F), whitening agents, blood circulation promoters, anti-inflammatory agents, bactericides, UV absorbers, colorants, preservatives, antioxidants, fragrances, oils, cooling agents, chelating agents, water retention agents, medicines, cooling sensation agents, warming sensation agents, and alcohols.

[0035] The basis weight of the gel layer is set at 800g / m2 in order to increase the carbon dioxide content, improve the blood circulation promoting effect, and improve strength. 2 More than 1100g / m 2 More preferably, 1150 g / m 2 More preferably, it is 1200 g / m 2 In addition, from the viewpoint of improving adhesion to the skin, 2500 g / m 2 Less than 2000g / m 2 Less than 1500g / m 2 More preferably, 1400 g / m or less 2 More preferably, 1300 g / m or less 2 The following is the result. The thickness of the gel layer is preferably 0.8 mm or more, more preferably 1.0 mm or more, and even more preferably 1.2 mm or more, from the viewpoint of increasing the carbon dioxide content and improving the blood circulation promoting effect and improving strength, and is preferably 3.0 mm or less, more preferably 2.5 mm or less, and even more preferably 2.0 mm or less, from the viewpoint of improving adhesion to the skin. The motion followability of a body application sheet can be improved by reducing the thickness of the sheet as in the past, but in order to increase the amount of carbon dioxide gas in order to obtain a blood circulation promoting effect, it is necessary to increase the moisture content of the gel layer and increase the basis weight of the gel layer of the body application sheet, which are contradictory properties, and it has been difficult to achieve both motion followability and the blood circulation promoting effect of carbon dioxide gas. According to the sheet of the present invention, it has the above-mentioned specific configuration, the ball number in the ball tack test is within a specific range, and the loss tangent in the dynamic viscoelasticity measurement at a specific frequency is within a specific range, so that it is possible to obtain a body application sheet that has excellent motion followability and excellent blood circulation promoting effect even if the basis weight of the gel layer is large.

[0036] (Physical properties of gel layer) The gel layer constituting the sheet of the present invention has a ball number of 15 or more and 30 or less in a ball tack test carried out according to JIS Z0237:2009 under conditions of an inclined plate angle of 30°, a temperature of 23° C. and 50% RH. Tackiness is an index of adhesive strength that can be exerted in a short time with light pressure. In other words, a sheet with high tackiness indicates high adhesion immediately after application to the skin. In addition, in the configuration of the present invention, this adhesive strength is thought to be maintained while the sheet is applied, which is also thought to contribute to improved movement tracking. The ball number of the gel layer in the ball tack test performed according to JIS Z0237:2009 under conditions of an inclined plate angle of 30°, a temperature of 23°C, and 50% RH is preferably 17 or more, more preferably 20 or more, even more preferably 22 or more, even more preferably 24 or more, and even more preferably 25 or more, from the viewpoint of improving the adhesion immediately after application to the skin. In addition, from the viewpoint of improving the handling property such as suppressing excessive stickiness, the ball number is preferably 29 or less, more preferably 28 or less, and even more preferably 27 or less. As a means for controlling the ball number to a desired value, adjustment of the mass ratio [(B) / (C)] in the gel layer and the content of component (F) can be mentioned. When the mass ratio [(B) / (C)] in the gel layer is increased, the ball number increases, and when it is decreased, the ball number decreases. In addition, when the content of component (F) is increased, the ball number increases, and when the content is decreased or not contained, the ball number decreases. Specifically, the ball tack test can be carried out by the method described in the Examples.

[0037] The gel layer constituting the sheet of the present invention has a loss tangent of 0.20 or more and 0.50 or less in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz, and a loss tangent of 0.25 or more and 0.50 or less in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 10 Hz. In the present invention, the viscous and elastic properties of the gel layer can be evaluated using the loss tangent (tan δ) as an index. A gel layer with a larger loss tangent value has a higher viscous property.

[0038] Furthermore, the loss tangent of the gel layer constituting the sheet of the present invention, as measured by dynamic viscoelasticity at a temperature of 25°C and a frequency of 0.1 Hz, is preferably 0.45 or less, more preferably 0.40 or less, and even more preferably 0.35 or less, and the loss tangent of the gel layer, as measured by dynamic viscoelasticity at a temperature of 25°C and a frequency of 10 Hz, is preferably 0.30 or more, and preferably 0.48 or less, and more preferably 0.45 or less. When the loss tangent of the gel layer is 0.20 or more in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz, the gel layer has good movement tracking ability in areas of the body where movement is relatively small (e.g., the calves), and when it is 0.50 or less, the gel layer tends to have excellent handleability, such as being less sticky when the sheet is applied. Furthermore, when the loss tangent of the gel layer is 0.25 or more in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 10 Hz, the gel layer exhibits good movement-following ability in areas of the body that experience large movements, such as joints (e.g., elbows and knees), whereas when the loss tangent is 0.50 or less, the gel layer tends to have excellent handleability, such as reduced stickiness when the sheet is applied. The loss tangent can be controlled to a desired value by adjusting the mass ratio [(B) / (C)] in the gel layer and the content of component (E). Increasing the mass ratio [(B) / (C)] in the gel layer increases the loss tangent at 0.1 Hz and 10 Hz, while decreasing the mass ratio [(B) / (C)] decreases the loss tangent. Increasing the content of component (E) decreases the loss tangent at 0.1 Hz and 10 Hz, while decreasing the content of component (E) or not including it increases the loss tangent. It is believed that the loss tangent at 0.1 Hz is related to the adhesion when no major movements are being made and the ability to follow parts of the body where movement is relatively small, while the loss tangent at 10 Hz is related to the ability to follow large movements when moving joints, etc., and it is believed that the excellent movement following ability of the present invention can be obtained by satisfying the above specified range not only in the low frequency range such as 0.1 Hz, but particularly in the high frequency range such as 10 Hz. Specifically, the loss tangent of the gel layer can be measured by the method described in the Examples. According to the present invention, by setting the ball number within the above-mentioned specific range and the loss tangent in dynamic viscoelasticity measurement at two specific frequencies within the above-mentioned specific range, a body application sheet is obtained which has good adhesion to the body and excellent movement tracking properties, and as a result has a high blood circulation promoting effect.

[0039] From the viewpoint of improving motion tracking, the gel layer has a (loss tangent in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz) / (loss tangent in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 10 Hz) ratio of preferably less than 1.3, more preferably 1.25 or less, and preferably 0.4 or more, more preferably 0.45 or more. As described above, the gel layer constituting the sheet of the present invention preferably further contains at least one selected from the group consisting of (E) carboxymethylcellulose and / or a salt thereof, and (F) polyvinyl alcohol. Here, from the viewpoint of controlling the loss tangent at 10 Hz, it is preferable that the gel layer does not contain (E) carboxymethylcellulose and / or a salt thereof, but contains polyvinyl alcohol. By doing so, the value of the loss tangent can be increased, and the value of (loss tangent in dynamic viscoelasticity measurement at temperature 25 ° C. and frequency 0.1 Hz) / (loss tangent in dynamic viscoelasticity measurement at temperature 25 ° C. and frequency 10 Hz) decreases. On the other hand, when carboxymethylcellulose and / or a salt thereof is contained, the loss tangent at 10 Hz decreases, and the value of (loss tangent in dynamic viscoelasticity measurement at temperature 25 ° C. and frequency 0.1 Hz) / (loss tangent in dynamic viscoelasticity measurement at temperature 25 ° C. and frequency 10 Hz) increases. In this way, the loss tangent for each frequency can be controlled by the contained components.

[0040] <Gel-forming composition> The gel layer constituting the sheet of the present invention comprises the following components (B) to (D): (B) Polyacrylic acid and / or its salt (C) Aluminum atom (D) Water: 60% by mass or more and 90% by mass or less The gel forming composition can be formed from a gel forming composition containing the above. Moreover, it is preferable that the gel-forming composition further contains at least one member selected from the group consisting of (E) carboxymethyl cellulose and / or a salt thereof, and (F) polyvinyl alcohol. In the present invention, the content of each component in the gel layer can be considered to be the same as the content of each component in the gel-forming composition used to form the gel layer.

[0041] The gel layer constituting the sheet of the present invention comprises the following components (B), (C1) and (D): (B) Polyacrylic acid and / or its salt (C1) Aluminum-containing compounds (D) Water: 60% by mass or more and 90% by mass or less The gel forming composition can be formed from a gel forming composition containing the above. Moreover, the gel-forming composition preferably further contains at least one selected from the group consisting of (E) carboxymethyl cellulose and / or a salt thereof, and (F) polyvinyl alcohol. The components (B) and (D) contained in the gel-forming composition, the optional components (E) and (F), and other components, as well as preferred embodiments thereof, are the same as those described above for the gel layer, unless otherwise specified.

[0042] In the gel-forming composition, the content of component (B) relative to the content of component (C1) (mass ratio [(B) / (C1)]) is preferably 50 or more, more preferably 80 or more, even more preferably 110 or more, still more preferably 130 or more, and even more preferably 140 or more, from the viewpoints of forming a gel layer that exhibits viscous properties over a wide frequency range to improve motion tracking, improve the blood circulation promoting effect, and make it easier to incorporate carbon dioxide gas into the gel layer. In addition, from the viewpoints of suppressing seepage into the base material when the gel layer is laminated on the base material (nonwoven fabric) and suppressing excessive stickiness of the gel layer, the content is preferably 400 or less, more preferably 350 or less, even more preferably 240 or less, and even more preferably 175 or less.

[0043] The amount of component (C1) contained in the gel-forming composition may be an amount such that the mass ratio [(B) / (C1)] falls within the above range. The amount of component (C1) contained in the gel-forming composition is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, even more preferably 0.025% by mass or more, and even more preferably 0.035% by mass or more in the gel-forming composition, from the viewpoint of suppressing the gel layer from seeping out into the substrate (nonwoven fabric) when the gel layer is laminated on the substrate, and suppressing excessive stickiness of the gel layer. And, from the viewpoint of forming a gel layer exhibiting viscous properties in a wide frequency range, improving motion tracking, improving the blood circulation promoting effect, and facilitating the incorporation of carbon dioxide gas into the gel layer, the amount is preferably 0.1% by mass or less, more preferably 0.055% by mass or less, even more preferably 0.045% by mass or less, and even more preferably 0.042% by mass or less. The amount of component (C1) contained in the gel forming composition is preferably 0.005% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.055% by mass or less, and even more preferably 0.02% by mass or more and 0.045% by mass or less.

[0044] In order to more effectively obtain the effects of the present invention, the total content of the components (B), (C1) and (D) in the gel layer is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more, and is 100% by mass or less. The total content of the components (B), (C1), (D), and optionally (E) and (F) in the gel-forming composition is, from the viewpoint of more effectively obtaining the effects of the present invention, preferably 70% by mass or more, more preferably 76% by mass or more, and even more preferably 80% by mass or more, and 100% by mass or less.

[0045] The method for preparing the gel-forming composition is not particularly limited, and all of the components may be charged into a kneader and mixed, or some of the components may be mixed or dispersed in advance, and then the remaining components may be charged into the kneader and mixed.

[0046] <Composition of the body application sheet> The structure of the sheet for application to the body of the present invention is not particularly limited as long as it has the gel layer, but from the viewpoint of improving the handling property and strength of the sheet, it is preferable to have the gel layer and a substrate. That is, the sheet for application to the body of the present invention can have a two-layer structure in which the gel layer and the substrate are laminated. In addition, a release film may be laminated on the surface of the gel layer on which the substrate is not laminated. From the viewpoint of improving the handleability of the sheet, the sheet for application to the body of the present invention preferably has a three-layer structure having a substrate, a gel layer, and a release film in this order. (Release film) The release film is used to protect the gel layer, and is a film that is peeled off from the gel layer when the sheet is applied, and can be, for example, a non-axially oriented polypropylene film, a biaxially oriented polypropylene film, a polyethylene terephthalate film, etc. Among these, from the viewpoint of imparting excellent peelability, those that have been embossed are preferred, and an embossed non-axially oriented polypropylene film is more preferred.

[0047] (base material) The substrate constituting the sheet of the present invention may be a sheet-like substrate such as a woven fabric, a nonwoven fabric, a biased cloth, a synthetic resin film, or a waterproof paper. A laminated substrate formed by laminating a plurality of such sheet-like substrates may also be used. Specific examples of the substrate include woven or nonwoven synthetic fibers such as nylon, polypropylene, polyester, polyethylene, polystyrene, polyurethane, polyolefin, etc.; woven or nonwoven natural fibers such as silk, cotton, hemp, rayon, collagen, etc.; films made of synthetic resins such as nylon, polypropylene, polyester, polyethylene, polyurethane, etc.; sheet-like substrates made of pullulan, starch, etc.; and laminated substrates formed by laminating a plurality of these. Among the above, from the viewpoints of improving the handleability of the sheet, ease of laminating the gel layer, and movement followability, the substrate is preferably a nonwoven fabric, and more preferably a nonwoven fabric made of nylon, polypropylene, polyester, or polyethylene.

[0048] The thickness of the substrate is not particularly limited, but from the viewpoint of improving the handleability of the sheet and the ease of laminating the gel layer, it is preferably 0.5 mm or more, and from the viewpoint of improving the movement tracking, it is preferably 1.8 mm or less, more preferably 1.5 mm or less, and even more preferably 1.0 mm or less. The basis weight of the substrate is not particularly limited, but from the viewpoint of improving the handling of the sheet and the ease of laminating the gel layer, it is preferably 80 g / m 2 From the viewpoint of improving the movement tracking, it is preferably 140 g / m 2 Less than 120 g / m 2 Less than 110 g / m 2 The following is the result. In addition, when the substrate is laminated on the gel layer, the basis weight of the laminate of the gel layer and the substrate (also referred to as the "basis weight of the gel layer and the substrate") is preferably 890 g / m from the viewpoint of providing an appropriate thickness for the gel layer to contain carbon dioxide gas and improving the handling properties of the sheet. 2 More preferably, 1190 g / m 2 More preferably, 1240 g / m 2 More preferably, 1290 g / m 2 From the viewpoint of improving the movement tracking, it is preferable that the thickness is 2590 g / m 2 Less than 2090g / m 2 More preferably, 1590 g / m 2 or less, even more preferably 1490 g / m 2 or less, even more preferably 1390 g / m 2 The following is the result. The basis weight of the gel layer of the finished body patch sheet can be calculated by subtracting the basis weight of the release film and the substrate from the basis weight of the entire product. In this case, the basis weight of the substrate can be measured, for example, by removing the release film and then immersing the gel layer in a solution containing a chelating agent to destroy the gel structure. The gel layer with the destroyed gel structure is then washed with water and dried.

[0049] [Manufacturing method of body application sheet] The method for producing the body patch sheet of the present invention is not particularly limited, but it can be produced, for example, by the following procedure. (I) First, a gel-forming composition is prepared. The gel-forming composition, the preparation method thereof, and the preferred embodiments thereof are as described above. (II) Next, a laminate sheet is prepared in which the gel-forming composition is sandwiched between a substrate and a release film. Specifically, the gel-forming composition is sandwiched between a substrate and a release film, and then spread to a desired thickness using a Baker-type applicator or the like; the gel-forming composition is applied to a release film to a desired thickness, and then a substrate is laminated thereon; and the like. Alternatively, the substrate and the release film are made to face each other and run on a conveying roll, and the gel-forming composition is filled between the substrate and the release film, and the substrate is sent out while being pressed by the roll to form a laminated sheet. In this case, the thickness of the gel-forming composition layer can be adjusted to a desired thickness by adjusting the distance between the two rolls.

[0050] (III) Next, the gel-forming composition layer of the obtained laminate sheet is crosslinked (crosslinking step), and carbon dioxide gas is introduced under a carbon dioxide gas atmosphere (carbon dioxide gas introduction step), thereby obtaining the body application sheet of the present invention. The order of the crosslinking step and the carbon dioxide gas-containing step does not matter, and the crosslinking step and the carbon dioxide gas-containing step may be carried out simultaneously, for example, in a carbon dioxide gas atmosphere, or the crosslinking may be allowed to proceed to a certain extent, and then the sheet may be placed in a carbon dioxide gas atmosphere and absorbed. Also, the carbon dioxide gas-containing step may be carried out after the crosslinking step is completed.

[0051] Hereinafter, a specific description will be given of an example of a method in which a carbon dioxide gas-containing step is carried out after the crosslinking step is completed. The crosslinking step begins when the polyacrylic acid and / or sodium polyacrylate (B) in the gel-forming composition layer comes into contact with the component (C) that acts as a crosslinking agent. The crosslinking conditions for the gel-forming composition layer are not particularly limited, but from the viewpoint of improving the productivity of the gel-forming composition and the body patch sheet having a gel layer made of the composition, the crosslinking temperature is preferably 15 to 60°C, more preferably 15 to 30°C, and the crosslinking time (aging time) is preferably 1 to 21 days, more preferably 1 to 14 days. After the crosslinking step is completed, the laminated sheet may be cut to a desired size, if necessary. Next, the laminated sheet having undergone the crosslinking step is subjected to a carbon dioxide gas-containing step. The carbon dioxide gas-incorporating step is a step of incorporating carbon dioxide gas into the laminated sheet in a carbon dioxide gas atmosphere, and is carried out, for example, in a sealable container filled with carbon dioxide gas. Here, the term "carbon dioxide atmosphere" refers to a gas atmosphere containing carbon dioxide, such as a mixed gas of air and carbon dioxide, or a mixed gas of nitrogen and carbon dioxide, and may be 100% by volume. From the viewpoint of efficiently incorporating carbon dioxide into the gel layer, the concentration of carbon dioxide in the container is preferably 10% by volume or more, more preferably 30% by volume or more, even more preferably 60% by volume or more, still more preferably 80% by volume or more, and even more preferably 90% by volume or more. The concentration of carbon dioxide in the container can be measured specifically by the method described in the Examples.

[0052] The carbon dioxide gas-containing step can be carried out by placing the laminated sheet in a container and then replacing the atmosphere in the container with carbon dioxide gas at a desired concentration. The timing for filling the container with carbon dioxide gas may be before or at the same time as inserting the laminated sheet.

[0053] As the sealable container, for example, a packaging container (packaging body) can be used, and when a packaging body is used, it is preferable because the sheet can be stored and provided as it is. The packaging material must be impermeable to carbon dioxide. Here, impermeable means that the permeability of carbon dioxide is less than 50cc / m 21·day·atm (ASTM D-1434) or less, but it is preferably non-permeable. Preferred materials are those having heat sealability, specifically, laminate films with aluminum foil laminated thereon, laminate films with aluminum vapor deposition layers, polyvinylidene chloride films, laminate films containing polyvinylidene chloride layers, etc. The packaging body is preferably in the form of a flat bag, gusset, etc.

[0054] The sheet for application to the body obtained by carrying out steps (I) to (III) can be made into a product in a sealed state in a package. When using the sheet for application to the body, it is taken out of the package, the release film is peeled off, and the gel layer surface is applied to the body.

[0055] The body patch sheet of the present invention is applied to the outer skin (excluding the scalp). There are no particular limitations on the part of the body, and even when applied to parts of the body that move a lot, such as the elbows and knees, it follows the movement and is not easily peeled off, and has a good blood circulation promoting effect for a long time. EXAMPLES

[0056] The present invention will be described below with reference to examples, but the present invention is not limited to the scope of the examples. Various measurements in the examples were carried out by the following methods.

[0057] <How to calculate the carbon dioxide concentration in the gap inside the aluminum pillow when sealed> After filling the aluminum pillow with carbon dioxide gas, the oxygen concentration inside the aluminum pillow was measured, and the carbon dioxide gas concentration inside the aluminum pillow was calculated from the obtained value. Specifically, the oxygen concentration F (%) inside the pillow was measured using a zirconia oxygen concentration meter (LC-450F, manufactured by Toray Industries, Inc.). Since the oxygen concentration in the atmosphere is 20.6% by volume, the proportion of air inside the pillow G (%) can be calculated as G = (F / 20.6) x 100. Assuming that the gas other than the atmosphere is carbon dioxide gas, the carbon dioxide gas concentration H (%) inside the pillow is defined as H = 100-G.

[0058] <Method for measuring carbon dioxide concentration in the gel layer of a sheet for application to the body> The sheet for application to the body was immersed in an alkaline solution bottle with a lid, and the gel of the sheet was dissolved while converting the carbon dioxide gas into carbonate. The sheet was then returned to an acidic state with an acidic buffer solution (pH 4.5), and the concentration of the generated carbon dioxide gas was measured using a carbon dioxide electrode (CE-2041, manufactured by DKK-TOA Corporation). The carbon dioxide gas concentration of the sheet for application to the body was calculated from the obtained carbon dioxide gas concentration.

[0059] [Examples 1 to 8, 10 to 11, Comparative Examples 1 to 5, 9] (Preparation of gel-forming composition) The gel-forming composition in the uncrosslinked state was prepared according to the recipe shown in Tables 1 to 3. Specifically, tartaric acid was first dissolved in purified water to prepare an aqueous tartaric acid solution. Next, this aqueous tartaric acid solution was mixed with partially neutralized polyacrylic acid (a copolymer of 67 mol% acrylic acid and 33 mol% sodium acrylate, neutralization degree 33 mol%), sodium polyacrylate (neutralization degree 100 mol%, completely neutralized product), sodium carboxymethylcellulose (viscosity of 1 mass% aqueous solution: 3400 mPa / s), polyvinyl alcohol (weight average molecular weight: 117000, saponification degree: 88 mol%), dried aluminum hydroxide gel, glycerin, methyl paraoxybenzoate, and tri(caprylic acid / capric acid)glycerin, and then charged into a kneader. Then, propylene glycol in which menthol had been dissolved by heating was added and mixed to prepare an uncrosslinked gel-forming composition. The content shown in the table is the amount of active ingredient (mass%) of each component. The calculated molar ratio of acrylic acid units to acrylate units (acrylic acid units / acrylate units) in the gel-forming compositions of the Examples and Comparative Examples (except Example 5) was 0.57, and in Example 5 it was 0.58.

[0060] (Manufacture of body adhesive sheets) The obtained uncrosslinked gel-forming composition was applied to a polyethylene release film and a nonwoven fabric (made of polyester, thickness 0.8 mm, basis weight 90 g / m) as a substrate. 2 ) and the gel-forming composition layer was sandwiched between the sheet and the sheet using a Baker-type applicator until the basis weight of the gel-forming composition layer was 1250 g / m 2(thickness 1.5 mm), a sheet in which a nonwoven fabric, a gel-forming composition layer, and a release film were laminated in this order was obtained. The sheet was then aged at 23°C for 10 days to promote the ionic crosslinking reaction of the gel-forming composition layer, and a crosslinked gel sheet was obtained. The crosslinked gel sheet obtained was cut into a rectangle (12.5 x 8.5 cm) and placed in an aluminum pillow. The air in the aluminum pillow was replaced with carbon dioxide gas by 90% or more by volume, and the aluminum pillow was sealed and kept for 5 days to obtain a sheet for application to the body. The carbon dioxide gas concentration in the gel layer of the sheet for application to the body obtained in the example and comparative example was 1200 ppm. However, the carbon dioxide gas concentration was 1000 ppm in Example 10 and Comparative Examples 4 to 5, and 850 ppm in Comparative Example 9. The pH of the obtained body application sheet was 4.5 to 5.5. The pH of the sheet was measured with a pH meter at 25° C. after diluting the gel 10-fold with purified water. The obtained body application sheet was used as a gel sheet for evaluation. When evaluating the sheet, the aluminum pillow was opened, the release film was quickly peeled off, and the gel layer side of the body patch sheet was applied to the skin, and the blood flow increasing effect (blood circulation promoting effect) on the inside of the forearm, and the sensation (movement tracking) when applied to the calf and knee were evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 3.

[0061] Example 9 After preparing a body application sheet in the same manner as in Example 1, the aluminum pillow was opened and the sheet was left to stand in the air for about 15 minutes to adjust the carbon dioxide concentration to 250 ppm. The sheet with a carbon dioxide concentration of 250 ppm obtained was used as an evaluation gel sheet and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2. In order to facilitate the preparation of the gel sheets for evaluation, the carbon dioxide concentration in the gel layer was adjusted by leaving the completed body application sheet in the atmosphere to release carbon dioxide, but it is also possible to adjust the concentration of carbon dioxide contained in the body application sheet by changing the proportion of carbon dioxide that replaces the air in the aluminum pillow, and the results will be the same regardless of the preparation method.

[0062] Comparative Example 6 In the manufacturing process of the body patch sheet, the basis weight of the gel-forming composition layer is 750 g / m 2 A body patch sheet was produced in the same manner as in Comparative Example 5, except that the gel sheet was spread so that the gel sheet had a thickness of 1000 mm. The body patch sheet thus obtained was used as an evaluation gel sheet and evaluated in the same manner as in Comparative Example 5. The carbon dioxide gas concentration was 1000 ppm. The evaluation results are shown in Table 3.

[0063] Comparative Example 7 In the manufacturing process of the body patch sheet, the basis weight of the gel-forming composition layer is 750 g / m 2 A body patch sheet was produced in the same manner as in Example 1, except that the gel sheet was spread so that the gel sheet had a thickness of 100 mm. The body patch sheet thus obtained was used as an evaluation gel sheet and evaluated in the same manner as in Example 1. The carbon dioxide gas concentration was 1200 ppm. The evaluation results are shown in Table 3.

[0064] Comparative Example 8 A gel sheet for application to the body was produced in the same manner as in Example 1, except that the atmosphere in the aluminum pillow was not replaced with carbon dioxide gas in the manufacturing process of the sheet for application to the body (the gel sheet was kept in the aluminum pillow without carbon dioxide gas for 5 days). The obtained sheet for application to the body was used as a gel sheet for evaluation and evaluated in the same manner as in Example 1. The carbon dioxide gas concentration was 20 ppm. The evaluation results are shown in Table 3.

[0065] <Ball tack test> The ball tack test of the gel layer of each example of the body application sheet was carried out in accordance with JIS Z0237: 2009 under conditions of an inclined plate angle of 30°, a temperature of 23°C, and 50% RH. Each example of the body application sheet was removed from the aluminum pillow, and the release film was removed. It was then quickly placed in a ball tack tester to carry out the ball tack test. The maximum ball number that stopped in the adhesive area of ​​the gel layer for 5 seconds or more is shown in Tables 1 to 3.

[0066] <Loss tangent (tanδ)> The loss tangent (tan δ) of the gel layer of each example of the body patch sheet was measured using a rheometer (Anton Paar Physica MCR301). Each example of the body patch sheet was removed from the aluminum pillow, cut into a circle with a diameter of 25 mm, and the nonwoven fabric side was fixed to the sample part of the rheometer (parallel plate with a diameter of 25 mm) with double-sided tape. The release film was then peeled off, and the loss modulus and storage modulus of the gel layer were measured under the following conditions, and the loss tangent (tan δ) was calculated from these values. The measurement was performed multiple times (three or more times) and the average value was used. [Measurement conditions] Normal Force: 1N Gap Distance: 1~2mm Gel layer weight: 0.6g, 0.4g ·Measurement frequency: 0.1Hz, 10Hz ·Distortion: 2% ·Temperature: 25℃

[0067] <Motion tracking ability (calf)> The body patch sheet of each example was taken out of the aluminum pillow, and immediately after peeling off the release film, the sheet was applied to the calf of a specialist panelist so that the long side of the sheet was perpendicular to the circumference of the calf. 10 seconds after application, the specialist panelist performed 10 plantar and dorsiflexion movements of the ankle, and the area of ​​the part of the body patch sheet that was floating from the calf, that is, the part that was peeled off from the calf was measured. The ratio (%) of the area of ​​the part where the sheet was peeled off to the entire area of ​​the body patch sheet was calculated and evaluated according to the following criteria. The higher the evaluation value, the better the movement tracking ability of the calf. A rating of 5.5 or higher is considered acceptable for practical use. The evaluation by expert panelists in this example was carried out by three panelists, and the evaluation values ​​shown in the table are the average values ​​of the three panelists. [Evaluation Criteria] 7: The area of ​​peeled off sheet is 5% or less. 6: The area of ​​peeled off sheet is more than 5% but not exceeding 10%. 5: The area of ​​peeled off sheet is more than 10% but not exceeding 20%. 4: The area of ​​peeled off sheet is more than 20% but less than 30%. 3: The percentage of the area of ​​peeled off sheet is more than 30% but not exceeding 40%. 2: The area of ​​peeled off sheet is more than 40% but less than 50%. 1: The area of ​​peeled off sheet is more than 50%.

[0068] <Movement tracking ability (knee)> Immediately after removing the body application sheet of each example from the aluminum pillow and peeling off the release film, the sheet was applied to the knee of a specialist panelist so that the long side of the sheet was parallel to the circumference of the knee. 10 seconds after application, the specialist panelist performed 10 knee bending and straightening movements (90° to 180°) and measured the area of ​​the body application sheet floating from the knee, i.e., the area of ​​the part peeled off from the knee. The ratio (%) of the area of ​​the body application sheet to the total area of ​​the body application sheet was calculated. The evaluation criteria were the same as those for the movement tracking ability of the calf. The higher the evaluation value, the better the movement tracking ability of the knee. The evaluation by expert panelists in this example was carried out by three panelists, and the evaluation values ​​shown in the table are the average values ​​of the three panelists. An evaluation result of 4.5 or more is considered to be acceptable for practical use.

[0069] <Increase in blood flow> After 20 minutes of acclimation at approximately 25±1°C and humidity of approximately 50±5%, the blood flow on the inside of the forearm was measured using a laser speckle blood flow meter, and the value was recorded as the value before application. After each body patch sheet was applied to the inside of the forearm, the blood flow was measured 5 minutes and 60 minutes later, and the increase rate (%) was calculated when the blood flow rate before application was set at 100. The higher the blood flow increase rate, the higher the blood circulation promotion effect. It is considered that an increase in blood flow of 115% or more after 5 minutes and 110% or more after 60 minutes are practically acceptable.

[0070] <Easy to apply> Immediately after removing each example of the body patch sheet from the aluminum pillow and peeling off the release film, the sheet was applied to the calf of a specialist panelist so that the long side of the sheet was perpendicular to the circumference of the calf. The ease of application was evaluated on a 5-point scale (5 points: very easy to apply, 4 points: easy to apply, 3 points: somewhat easy to apply, 2 points: somewhat difficult to apply, 1 point: difficult to apply). The higher the evaluation value, the easier and neater the body patch sheet was to apply, and the lower the value, the stickier the adhesive surface (gel layer) was, and the more difficult it was to apply the body patch sheet due to stickiness to fingers or adhesion between adhesive surfaces. A rating of 2.0 or higher is considered acceptable for practical use.

[0071] [Table 1]

[0072] [Table 2]

[0073] [Table 3]

[0074] From Tables 1 to 3, the body patch sheets of the present embodiment have good adhesion (tackiness) to the body (skin), and have excellent movement tracking ability even when applied to parts of the body that move a lot, such as the calves and knees. In addition, the blood circulation promoting effect of carbon dioxide gas was also good even after a long time. The body patch sheets of Examples 8 and 11 have good movement tracking ability and blood circulation promoting effect, and there is no problem in use, but they remain sticky on the skin and some seepage was observed on the nonwoven fabric side. In contrast, the comparative example of the body application sheet did not achieve satisfactory results in all areas of adhesion to the body, movement tracking ability, and blood circulation promotion effect. [Industrial Applicability]

[0075] According to the present invention, it is possible to provide a sheet for application to the body which has good adhesion (tackiness) to the body, has excellent movement-following properties even when applied to areas with large movements, particularly joints such as elbows and knees, and has a high blood circulation promoting effect due to carbon dioxide gas.

Claims

1. A body adhesive sheet having a gel layer, The gel layer comprises the following components (A) to (D): (A) Carbon dioxide: 100 ppm or more and 20,000 ppm or less (B) Polyacrylic acid and / or its salt (C) Aluminum atom (D) Water 60% by mass or more and 90% by mass or less Contains the gel layer has a ball number of 15 or more and 30 or less in a ball tack test carried out in accordance with JIS Z0237:2009 under conditions of an inclined plate angle of 30°, a temperature of 23°C, and 50% R.H.; the gel layer has a loss tangent of 0.20 or more and 0.50 or less in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz; the gel layer has a loss tangent of 0.25 or more and 0.50 or less in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 10 Hz; The basis weight of the gel layer is 800 g / m ２ More than 2500g / m ２ Below is the Sheet for application to the body.

2. 2. The body patch sheet according to claim 1, wherein the gel layer further comprises at least one member selected from the group consisting of (E) carboxymethyl cellulose and / or a salt thereof, and (F) polyvinyl alcohol.

3. The body adhesive sheet according to claim 1 , wherein the gel layer further comprises (F) polyvinyl alcohol.

4. The body patch sheet according to any one of claims 1 to 3, wherein the mass ratio of component (B) to component (C) [(B) / (C)] is 250 or more and 900 or less.

5. The body adhesive sheet according to any one of claims 1 to 3, wherein the gel layer has a loss tangent in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz / loss tangent in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 10 Hz of less than 1.

3.

6. The body patch sheet according to any one of claims 1 to 3, wherein the content of component (B) in the total amount of the gel layer (excluding component (A)) is 3.0% by mass or more and 10.0% by mass or less.

7. The body patch sheet according to any one of claims 1 to 3, wherein the molar ratio of acrylic acid units to acrylate units (acrylic acid units / acrylate units) contained in the total amount of component (B) is 0.1 or more and 3.0 or less.