KR20240021754A - body attachment sheet - Google Patents

Abstract

A sheet for body application having a gel layer, wherein the gel layer contains (A) water, (B) carboxymethylcellulose or a salt thereof, (C) an aluminum atom, and (D) polyvinyl alcohol, and the components in the gel layer ( For use on the body, wherein the content of A) is 50 mass% or more and 85 mass% or less, the content of component (D) in the gel layer is 8 mass% or more, and the mass ratio [(B)/(C)] is 70 or more and 800 or less. Sheet.

Description

body attachment sheet

The present invention relates to a sheet for attaching to the body.

Patchy sheets that are manufactured using a water-containing gel composition and have various effects are being developed. As the main component other than water that constitutes the water-containing gel composition, a water-soluble polymer compound is usually used.

For example, Japanese Patent Application Laid-Open No. 2005-314290 (Patent Document 1) describes a patch comprising a support and an adhesive layer disposed on at least one side of the support, wherein the adhesive layer contains β-glucan. It is disclosed that a patch characterized by being formed of an adhesive base has excellent feeling of use and has sufficient adhesive strength.

In Japanese Patent Application Laid-Open No. 2013-79198 (Patent Document 2), a gel base layer having at least a gel base layer, a support layer, and an adhesive layer, and having a layer structure laminated in this order, is not in contact with other layers of the gel base layer. A cooling sheet for medical use that is used so that part or all of the side surface is in direct contact with the area to be cooled, wherein the gel base layer is formed of a cooling composition containing polyvinyl alcohol, and a predetermined amount of polyvinyl alcohol is added thereto. It is disclosed that a cooling sheet for medical wear containing a cooling sheet is not sticky even when it touches a part to be cooled, such as human skin, and has excellent cooling and cold storage effects.

Japanese Patent Laid-Open No. 2016-124870 (Patent Document 3) discloses an anionic water-soluble polymer compound containing a predetermined amount of water, carboxymethyl cellulose or a salt thereof, a cross-linking agent that forms an ionic cross-link with an anionic functional group, and It is disclosed that a water-containing gel composition containing a nonionic water-soluble polymer compound in a predetermined amount and with a predetermined structure exhibits excellent feeling of use and also has excellent gel stability.

In International Publication No. 2018/155310 (Patent Document 4), a base for a patch containing a predetermined amount of gelatin, polyvinyl alcohol, methyl acrylate/2-ethylhexyl acrylate copolymer, and L-menthyl glyceryl ether is provided as a refreshing material. It is disclosed that even in the case of using L-menthyl glyceryl ether as a topical agent, it is possible to provide a base for a patch and a patch using the same in which the adhesive force of the base is maintained and the generation of an unpleasant odor is suppressed.

The present invention relates to the following.

[1] A sheet for attaching to the body having a gel layer,

The gel layer contains the following components (A) to (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C) aluminum atom

(D) polyvinyl alcohol

Contains,

The content of component (A) in the gel layer is 50% by mass or more and 85% by mass or less,

The content of component (D) in the gel layer is 8% by mass or more,

A sheet for attaching to the body, wherein the mass ratio [(B)/(C)] is 70 or more and 800 or less.

[2] A method for producing a body patch sheet having a gel layer, comprising the following steps (I) to (III) in this order.

Process (I) Components (A), (B), (C1) and (D) following:

(A) water

(B) Carboxymethylcellulose or its salt

(C1) Aluminum-containing compounds

(D) polyvinyl alcohol

It is made by combining,

The compounding amount of component (A) is 50% by mass or more and 85% by mass or less,

The amount of component (D) is 8% by mass or more,

A process of preparing a gel-forming composition where the mass ratio [(B)/(C1)] is 25 or more and 140 or less.

Step (II) A step of filling the gel-forming composition between a base material and a release film and producing a laminated sheet having the base material, the gel-forming composition layer, and the release film in that order.

Step (III) A step of sealing the laminated sheet in a package and then crosslinking the gel-forming composition layer within the package.

Figure 1 is a graph showing the viscoelastic behavior (relationship between measurement frequency and loss tangent (tanδ)) of the gel layer of the body patch sheet obtained in Example 1 and Comparative Example 4.

In recent years, high functionality has been required for sheets for body application, and in addition to high adhesion and followability immediately after application, sheets for body application are required to have sufficient adhesive strength so that they are difficult to peel off even after various daily activities. It is becoming. For example, when applying to joints with high curvature such as elbows and knees and moving the applied area, when applying to the skin once and peeling it off to reapply, or when applying to the skin after applying body cream, There is a demand for sheets for attachment to the body that maintain adhesion to the skin even when applied for a long period of time and are difficult to peel off. This is because there is an increasing demand to obtain various physiological effects comfortably while using them in various life situations.

However, with conventional body attaching sheets, when applying the body attaching sheet to the skin, the adhesive surface of the sheet feels sticky to the fingers, or when the adhesive surfaces of the sheets are attached to each other after peeling off the release film, the adhesive surface sticks to the skin. Problems with handling, such as difficulty in returning it to its original state, may also occur. In other words, if you try to increase the adhesion, problems with handling will occur, and if you want to increase the adhesion, the result will be a deterioration in the adhesion. In light of the above, there is room for improvement in conventional body attachment sheets.

The object of the present invention is to provide a sheet for body application that has good adhesion to the skin, especially when applied to joints with high curvature such as elbows and knees, has good adhesion even when movement is applied to the applied portion, and is also excellent in handling when applied. It is about providing.

The present inventor describes a sheet for body application having a gel layer, wherein the gel layer contains a predetermined amount of water, carboxymethyl cellulose or its salt, an aluminum atom, and a predetermined amount of polyvinyl alcohol, and contains carboxymethyl cellulose or its salt and aluminum. It was found that the above problem could be solved by setting the mass ratio of the atoms to a predetermined range.

According to the present invention, a sheet for body application is provided that has good adhesion to the skin, especially when applied to joints such as elbows and knees with high curvature and has good adhesion even when movement is applied to the applied portion, and is also excellent in handling properties when applied. can be provided.

[Justice]

In the description below, “good adhesion to the skin (of the sheet for body application)” means that both the adhesion immediately after application to the skin and the adhesion under load conditions are both good. “Adhesion immediately after application” means adhesion when daily movements are performed immediately after the body application sheet is applied to a part other than a joint (for example, a calf). Additionally, “adhesion under load conditions” means adhesion when movement is applied to the attached portion immediately after attaching the body adhesive sheet to a highly curvature portion (for example, a joint portion such as the knee). Adhesion immediately after application to the skin and adhesion under load conditions can be evaluated by the method described in the Examples.

In addition, the sheet for body application of the present invention is difficult to peel when applied for a long time, has good adhesion to oily skin, and has good re-attachment properties.

In the present invention, “excellent handling properties (of a sheet for body application) when applied” means that at least the sheet for body application is easy to apply to the skin. The ease of applying the sheet to the skin can be evaluated by the method described in the Examples.

In addition, the sheet for attaching to the body of the present invention suppresses the stickiness of the adhesive surface of the sheet to the fingers and makes it easy to peel the adhesive surfaces of the sheets when they are attached (return to the original state). Easy) is also excellent.

In addition, the adhesive surface of the body patch sheet of the present invention means the gel layer surface of the sheet. In addition, in the description below, "when the adhesive surfaces of the sheets are attached to each other during attachment, the adhesive surfaces are easy to peel off (easy to return to the original state)" and "the adhesive surfaces can easily be returned to their original state even once they are attached to each other." They also say, “It’s easy.”

[Body attachment sheet]

The sheet for body application of the present invention (hereinafter also simply referred to as “the sheet of the present invention”) is a sheet for body application having a gel layer, and the gel layer contains the following components (A) to (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C) aluminum atom

(D) polyvinyl alcohol

Contains,

The content of component (A) in the gel layer is 50% by mass or more and 85% by mass or less,

The content of component (D) in the gel layer is 8% by mass or more,

The mass ratio [(B)/(C)] is 70 or more and 800 or less.

By having the above-described structure, the sheet for body application of the present invention has excellent adhesion to the skin and excellent handling properties when applying.

Although the reason why the sheet of the present invention exhibits the effect of the present invention by having the above configuration is not clear, it is inferred as follows.

Component (B) is a polymer having a carboxyl group, and can form a crosslinked structure through ionic interaction with trivalent aluminum ions, which are ionized products of component (C). That is, the aluminum ion can act as a crosslinking agent for component (B). Therefore, within the gel layer constituting the sheet of the present invention, component (B) is believed to have a crosslinked structure crosslinked by component (C).

On the other hand, component (D) is a polymer that does not have the ability to form crosslinks by aluminum ions, and within the gel layer, the polymer chains of component (D) are in a fluid state within the crosslinking matrix composed of component (B) and component (C). It is thought to exist.

And the gel layer constituting the sheet of the present invention contains component (B) and component (C) in a specific ratio and also contains component (D) in a predetermined amount, so that it has viscous properties in a wider frequency range than that of the conventional gel layer. It becomes what it represents. Additionally, the gel layer showed characteristic viscoelastic behavior in that the viscous properties were strong in the low-frequency region and the viscous properties became stronger as it transitioned to the high-frequency region. In addition, the gel layer exhibiting such viscoelastic behavior not only exhibits high adhesion to the skin and has excellent adhesion properties, but also suppresses stickiness during application, so that even if the adhesive surfaces (i.e. gel layers) are once attached to each other, I found out that it was easy to return it to its original state. The action mechanism by which such adhesive properties are expressed is by setting the mass ratio [(B)/(C)] in the gel layer to a predetermined value or less and increasing the presence ratio of component (D), so that there are few cross-linking points and deformation is possible. Because an easy gel structure is formed, it is believed that the adhesion of the sheet to the skin is improved. Additionally, increasing the presence ratio of component (D) in the gel layer improves the adhesiveness to the skin by improving the tackiness of the gel layer, but excessive improvement of tackiness can be prevented by setting the mass ratio [(B)/(C)] to a predetermined value or more. It is thought that by suppressing it, good handling properties can be maintained when sticking.

＜Gel layer＞

The sheet for body application of the present invention contains the following components (A) to (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C) aluminum atom

(D) polyvinyl alcohol

A gel layer containing, the content of component (A) is 50 mass% or more and 85 mass% or less, the content of component (D) is 8 mass% or more, and the mass ratio [(B)/(C)] is 70 or more and 800 or less. has

Within the gel layer, component (B) has a crosslinked structure crosslinked by component (C). The sheet of the present invention having the gel layer has excellent adhesion to the skin and excellent handling properties when applied.

(Physical properties of gel layer)

In the present invention, the viscous properties and elastic properties of the gel layer can be evaluated using the value of loss tangent (tanδ) as an index. A gel layer with a large loss tangent value means that the viscous properties are higher.

More specifically, from the viewpoint of improving adhesion to the skin, the gel layer constituting the sheet of the present invention has a loss tangent in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz, preferably 0.18 or more. Preferably it is 0.20 or more, more preferably 0.22 or more, even more preferably 0.25 or more, and even more preferably 0.28 or more. Furthermore, from the viewpoint of handling, especially from the viewpoint of suppressing stickiness when attaching sheets and from the viewpoint of making it easy to return the adhesive surfaces to their original state once they are attached, the ratio is preferably 0.70 or less, more preferably 0.60 or less, and even more preferably 0.70 or less. It is 0.58 or less, and even more preferably 0.50 or less. And, the loss tangent of the gel layer constituting the sheet of the present invention in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz is preferably 0.18 or more and 0.70 or less, more preferably 0.20 or more and 0.60 or less, even more preferably. Preferably it is 0.22 or more and 0.58 or less, more preferably 0.25 or more and 0.58 or less, and even more preferably 0.28 or more and 0.50 or less.

The loss tangent of the gel layer can be specifically measured by the method described in the Examples.

Additionally, the gel layer constituting the sheet of the present invention has high tack force. Tackiness is an indicator of short-term adhesion using light force. In other words, a sheet with high tackiness shows high adhesion immediately after application to the skin. More specifically, in accordance with JIS Z0237:2009, the gel layer was set at an inclined plate angle of 30°, temperature of 23°C, and 50% R.H. The ball number in the bolt tack test conducted under the conditions is preferably 15 or more, more preferably 18 or more, even more preferably 19 or more, and even more preferably 20 or more. Furthermore, from the viewpoint of handling, especially from the viewpoint of suppressing stickiness when attaching the sheet and from the viewpoint of making it easy to return the adhesive surfaces to their original state once they are attached, the ball number is preferably 32 or less, more preferably 30. or less, more preferably 28 or less, even more preferably 26 or less. And, the ball number is preferably 15 to 32, more preferably 15 to 30, even more preferably 18 to 28, even more preferably 19 to 28, and even more preferably 20 to 26. It is as follows.

The bolt-tack test can be specifically performed by the method described in the Examples.

The gel layer having the above physical properties contains the components (A) to (D), and the content of component (A), the content of component (D), and the mass ratio [(B)/(C)] in the gel layer are It is obtained by keeping it within a predetermined range. Hereinafter, each component contained in the gel layer will be explained.

(Ingredient (A): Water)

The gel layer constituting the sheet of the present invention contains water, allowing active ingredients such as medicinal ingredients and cooling ingredients to effectively penetrate the skin.

As component (A), for example, purified water such as deionized water, distilled water, high purity water, or ultrapure water can be used.

The content of component (A) in the gel layer is 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 65% by mass, from the viewpoint of effectively penetrating the active ingredient into the skin. It is more than ％. Furthermore, from the viewpoint of improving adhesion to the skin and ensuring the adhesion and stability of the gel layer, it is 85% by mass or less, preferably 80% by mass or less, more preferably 78% by mass or less, even more preferably 77% by mass. It is less than mass%. And, the content of component (A) in the gel layer is 50 mass% or more and 85 mass% or less, preferably 55 mass% or more and 80 mass% or less, more preferably 60 mass% or more and 78 mass% or less, even more preferably is 65 mass% or more and 77 mass% or less.

(Component (B): Carboxymethylcellulose or its salt)

The gel layer constituting the sheet of the present invention contains carboxymethylcellulose or a salt thereof as component (B). Component (B) is a polymer having a carboxyl group, and can form a crosslinked structure through ionic interaction with trivalent aluminum ions, which are ionized products of component (C).

Salts of carboxymethyl cellulose include alkali metal salts such as sodium salts and potassium salts, and ammonium salts. From the viewpoint of ease of availability, etc., the salt of carboxymethyl cellulose is preferably an alkali metal salt of carboxymethyl cellulose, and the sodium salt of carboxymethyl cellulose (sodium carboxymethyl cellulose) is more preferred.

The degree of etherification of component (B) is preferably 0.60 or more, more preferably 0.65 or more, and preferably 1.1 or less from the viewpoint of obtaining appropriate retention properties of the gel layer and ensuring storage stability of the gel layer. , more preferably 1.0 or less, even more preferably 0.95 or less.

Additionally, the degree of etherification of component (B) refers to the degree of substitution of the carboxymethyl group of the glucose unit sugar of component (B). When component (B) is sodium carboxymethyl cellulose, the degree of etherification can be measured by the following method, for example, according to the CMC Industrial Society analysis method (ashification method).

[Measurement of the degree of etherification of sodium carboxymethyl cellulose]

1 g of sodium carboxymethyl cellulose was precisely weighed, placed in a magnetic crucible and incinerated at 600°C, the sodium oxide produced by incineration was titrated with N/10 sulfuric acid using phenolphthalein as an indicator, and 1 g of sodium carboxymethyl cellulose was added. The appropriate amount of sugar Y mL can be calculated by entering the following formula, and the obtained degree of etherification can be expressed.

Degree of etherification = (162 × Y)/(10,000-80 × Y)

From the viewpoint of obtaining appropriate retention properties of the gel layer and ensuring the stability of the gel layer, component (B) has a viscosity at 25°C when measured as a 1% by mass aqueous solution with a type B viscometer, Preferably it is 1,000 mPa·s or more, more preferably 1,200 mPa·s or more, even more preferably 1,500 mPa·s or more, preferably 7,000 mPa·s or less, more preferably 6,000 mPa·s or less, further Preferably it is 5,000 mPa·s or less. The viscosity of component (B) as a 1% by mass aqueous solution at 25°C is preferably 1,000 mPa·s or more and 7,000 mPa·s or less, more preferably 1,200 mPa·s or more and 6,000 mPa·s. s or less, more preferably 1,500 mPa·s or more and 5,000 mPa·s or less.

Component (B) can be used singly or in combination of two or more. Among them, from the viewpoint of ease of availability, etc., the component (B) is preferably at least one selected from the group consisting of carboxymethyl cellulose and sodium carboxymethyl cellulose, and sodium carboxymethyl cellulose is more preferable. Commercially available sodium carboxymethyl cellulose used as component (B) includes, for example, the CMC Daicel series manufactured by Daicel Co., Ltd. and the Sunrose series manufactured by Nippon Paper Co., Ltd.

The content of component (B) in the gel layer is preferably 1.0 mass% or more, more preferably 1.5 mass% or more, further preferably 2.0 mass% or more, and even more preferably from the viewpoint of obtaining appropriate retention properties of the gel layer. is 2.3 mass% or more, and even more preferably 2.5 mass% or more. In addition, from the viewpoint of maintaining adhesion to the skin and ease of handling, especially from the viewpoint of suppressing stickiness when attaching the sheet, and from the viewpoint of making it easy to return the adhesive surfaces to their original state once they are attached, the amount is preferably 5.0% by mass or less. , more preferably 4.0 mass% or less, further preferably 3.8 mass% or less, and even more preferably 3.4 mass% or less. And, the content of component (B) in the gel layer is preferably 1.0 mass% or more and 5.0 mass% or less, more preferably 1.5 mass% or more and 4.0 mass% or less, further preferably 2.0 mass% or more and 3.8 mass% or less, Even more preferably, it is 2.3 mass% or more and 3.4 mass% or less, and even more preferably, it is 2.5 mass% or more and 3.4 mass% or less.

In addition, when component (B) is a salt of carboxymethyl cellulose, the content of component (B) in the gel layer means the content as a salt.

(Component (C): aluminum atom)

The gel layer constituting the sheet of the present invention contains aluminum atoms as component (C). The trivalent aluminum ion, which is an ionized product of component (C), can act as a crosslinking agent for component (B), and is believed to form a crosslinked structure within the gel layer through interaction between ions with component (B).

The source of aluminum atoms as 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), and Since it is water-soluble, it is preferably an inorganic metal salt containing aluminum.

Examples of aluminum-containing compounds (C1) that serve as a source of component (C) and that can act as a crosslinking agent for component (B) include aluminum hydroxide, magnesium aluminum hydroxide, sodium aluminate, aluminum sulfate, potassium aluminum sulfate, and sulfuric acid. Aluminum ammonium, aluminum carbonate, aluminum nitrate, aluminum chloride, magnesium (meth)aluminum silicate, aluminum acetate, aluminum lactate, aluminum stearate, aluminum myristate, aluminum glycinate, aluminum benzoate, allantoin chlorohydroxyaluminum, etc. and one or two or more of these may be used.

Among the above, from the viewpoint of ease of supply of aluminum ions and water solubility, the component (C1) is preferably at least one selected from the group consisting of aluminum hydroxide and magnesium aluminosilicate (meth)silicate. Furthermore, from the viewpoint of improving the storage stability of the gel layer, component (C1) preferably contains two or more aluminum-containing compounds, more preferably contains at least magnesium alumino(meth)silicate, aluminum hydroxide and ( It is more preferable that it is magnesium aluminate (meth)silicate.

The content of component (C) in the gel layer is determined from the viewpoint of handling, especially from the viewpoint of suppressing stickiness when attaching the sheet, from the viewpoint of making it easy to return the adhesive surfaces to their original state even once they are attached, and from the viewpoint of improving storage stability. Preferably it is 0.002 mass% or more, more preferably 0.003 mass% or more, further preferably 0.005 mass% or more, even more preferably 0.0062 mass% or more, and even more preferably 0.008 mass% or more. Additionally, from the viewpoint of forming a gel layer exhibiting viscous properties in a wide frequency range and improving adhesion to the skin, the amount is preferably 0.05 mass% or less, more preferably 0.04 mass% or less, and even more preferably 0.035 mass%. or less, and even more preferably 0.02% by mass or less. And, the content of component (C) in the gel layer is preferably 0.002 mass% or more and 0.05 mass% or less, more preferably 0.003 mass% or more and 0.05 mass% or less, further preferably 0.005 mass% or more and 0.04 mass% or less, Even more preferably, it is 0.0062 mass% or more and 0.035 mass% or less, and even more preferably, it is 0.008 mass% or more and 0.02 mass% or less.

In addition, the content of component (C) in the gel layer can be measured according to the Japanese Pharmacopoeia General Test Method inductively coupled plasma emission spectrometry and inductively coupled plasma mass spectrometry.

The mass ratio [(B)/(C)] in the gel layer is 70 or more, preferably 85 or more, more preferably 85 or more, from the viewpoint of forming a gel layer that exhibits viscous properties in a wide frequency range and improving adhesion to the skin. It is more than 100. In addition, from the viewpoint of improving handling, especially from the viewpoint of suppressing stickiness when attaching sheets, from the viewpoint of making it easy to return the adhesive surfaces to their original state once they are attached to each other, and from the viewpoint of improving storage stability, it is 800 or less, and is preferable. It is preferably 600 or less, more preferably 500 or less. And the mass ratio [(B)/(C)] in the gel layer is 70 or more and 800 or less, preferably 85 or more and 600 or less, and more preferably 100 or more and 500 or less.

(Component (D): polyvinyl alcohol)

The gel layer constituting the sheet of the present invention contains polyvinyl alcohol as component (D). By containing component (D) in addition to the component (B) and component (C), the tackiness of the gel layer and the viscous properties in the low frequency region are improved, thereby improving adhesion to the skin.

The weight average molecular weight of component (D) is not particularly limited, but from the viewpoint of obtaining appropriate retention properties of the gel layer, it is preferably 30,000 or more, more preferably 50,000 or more, and even more preferably 70,000 or more. Additionally, from the viewpoint of improving the adhesion of the sheet to the skin by improving the tackiness of the gel layer, the value is preferably 150,000 or less, more preferably 110,000 or less, and even more preferably 100,000 or less. And the weight average molecular weight of component (D) is preferably 30,000 or more and 150,000 or less, more preferably 50,000 or more and 110,000 or less, and even more preferably 70,000 or more and 100,000 or less.

If the weight average molecular weight of component (D) is preferably 150,000 or less, more preferably 110,000 or less, and even more preferably 100,000 or less, the polymer chains of component (D) in the gel layer will be less entangled and more prone to deformation. It is thought that a gel structure can be formed. This effect is expected to further improve the tackiness of the gel layer and improve adhesion to the skin.

The weight average molecular weight of the powder raw material of component (D) 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. In addition, “powder raw material of component (D)” means component (D) in a powder state before blending into the gel layer or the gel-forming composition described later. In addition, the weight average molecular weight of component (D) 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 Co., Ltd.

Eluent: 0.2 mol/L phosphate buffer/acetonitrile = 9/1 (V/V %)

Guard column: “PWXL (6 mm × 4 cm)” manufactured by Tosoh Co., Ltd.

Analytical column: manufactured by Tosoh Co., Ltd. “G4000PWxL+G2500PWxL (7.8 mm × 30 cm)

Flow rate: 1 mL/min

Column temperature: 40℃

Injection volume: 100 μL

Sample size: 1 mg/mL

Molecular weight conversion standard: PEO manufactured by Tosoh Co., Ltd. (SE-150 (977,000), SE-70 (580,000), SE-30 (394,000), SE-15 (14.30,000), SE-8 (10.10,000) , SE-2 (2.1 only))

Detector: RI

The degree of saponification of component (D) is preferably 75 mol% or more, more preferably 82 mol% or more, and still more preferably 85 mol% from the viewpoint of improving the adhesiveness of the sheet to the skin by improving the tackiness of the gel layer. It is more than ％. Additionally, the saponification degree of component (D) may be 100 mol% or less, and from the viewpoint of increasing the water solubility of component (D) and improving its handleability, preferably 98 mol% or less, more preferably 96 mol% or less. It is mol% or less. The degree of saponification of component (D) is preferably 75 mol% or more and 98 mol% or less, more preferably 82 mol% or more and 98 mol% or less, and further preferably 85 mol% or more and 96 mol% or less.

The saponification degree of component (D) can be measured according to JIS K6726:1994.

Component (D) is preferably undenatured polyvinyl alcohol, but if necessary, modified polyvinyl alcohol into which an ionic group or the like has been introduced can also be used.

However, as component (D), it is preferable that the content of functional groups capable of forming a crosslinked structure through ionic interaction with aluminum ions is low. This is because it does not inhibit the formation of the cross-linked structure of component (B). For example, the content of the carboxyl group in component (D) is preferably 0.1 mol% or less, more preferably 0.01 mol% or less, and even more preferably 0 mol%.

Commercially available polyvinyl alcohol used as component (D) includes, for example, the Gosenol series manufactured by Nippon Synthetic Chemicals Co., Ltd., the Kuraray Foval series manufactured by Kuraray Co., Ltd., and the Nippon Vinyl Acetate/Poval ( Examples include the J Foval series of Note).

The content of component (D) in the gel layer is 8 mass% or more, preferably 8.3 mass% or more, and more preferably 8.5 mass% or more from the viewpoint of improving adhesion to the skin. In addition, from the viewpoint of improving adhesion to the skin and ease of handling, especially from the viewpoint of suppressing stickiness when attaching the sheet and from the viewpoint of making it easy to return the adhesive surface to its original state, it is preferably 18% by mass or less. , more preferably 14 mass% or less, further preferably 12 mass% or less. And, the content of component (D) in the gel layer is 8 mass% or more, preferably 8 mass% or more and 18 mass% or less, more preferably 8.3 mass% or more and 14 mass% or less, and still more preferably 8.5 mass%. It is 12% by mass or less.

The content of component (D) in the gel layer is obtained by measuring the extract of the gel layer with ¹ H-NMR under the following conditions.

< ¹ H-NMR measurement conditions>

Measuring device: “MR-400” manufactured by JEOL

Observation nucleus: 1 H

Frequency: above 300 MHz

Pulse delay time: 25 seconds

Integration count: 32 times

Mode: Presaturation

Solvent: D ₂ O

Internal standard: 0.1% Na trimethylpropionate

Sample size: 10 mg/mL

In addition, the mass ratio [(D)/(B)] in the gel layer is preferably 2 or more, more preferably 2.4 or more, further preferably 2.8 or more, and even more preferably from the viewpoint of improving adhesion to the skin. is 3 or more. Furthermore, from the viewpoint of improving adhesion to the skin and from the viewpoint of handling, especially from the viewpoint of suppressing stickiness when attaching the sheet and from the viewpoint of making it easy to return the adhesive surfaces to their original state even once they are attached, it is preferably 8 or less. More preferably, it is 6 or less, further preferably is 5 or less, even more preferably is 4.5 or less, and even more preferably is 4 or less. And, the mass ratio [(D)/(B)] in the gel layer is preferably 2 or more and 8 or less, more preferably 2.4 or more and 6 or less, further preferably 2.8 or more and 5 or less, and even more preferably 3 or more and 4.5. Below, even more preferably 3 or more and 4 or less.

From the viewpoint of obtaining the effect of the present invention, the total content of the components (A) to (D) in the gel layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more. and is 100% by mass or less.

(Other ingredients)

The gel layer may contain components other than the components (A) to (D) as appropriate, as long as they do not impair the purpose of the present invention. Other ingredients include, for example, ingredients commonly used in cosmetics, cosmetics, pharmaceuticals, quasi-drugs, etc.

Ingredients commonly used in these products include, for example, water-soluble polymers other than component (B) and component (D), moisturizers, whitening agents, blood circulation promoters, anti-inflammatory agents, disinfectants, ultraviolet absorbers, colorants, preservatives, antioxidants, Fragrances, emulsions, pH adjusters, chelating agents, water retention agents, drugs, cooling agents, warming agents, alcohols, etc. are included.

In addition, the gel layer preferably has a low content of polyacrylic acid or its salt from the viewpoint of improving handling, especially suppressing stickiness when attaching the sheet, and making it easy to return the adhesive surfaces to their original state once they are attached. do. Specifically, the content of polyacrylic acid or its salt in the gel layer is preferably less than 4 mass%, more preferably less than 3 mass%, even more preferably 2 mass% or less, and even more preferably 1 mass%. It is below, and even more preferably, it is 0 mass%. Commercially available polyacrylic acid or its salts include, for example, the Aronvis series and Jurimer series manufactured by Toa Kosei Co., Ltd. and the Aqualic series manufactured by Nippon Shokubai Co., Ltd.

The thickness of the gel layer is preferably 0.1 mm or more, more preferably 0.3 mm or more, and still more preferably 0.5 mm or more from the viewpoint of ensuring strength, and also from the viewpoint of improving adhesion to the skin, preferably is 5 mm or less, more preferably 3 mm or less, and even more preferably 2 mm or less.

<Composition for gel formation>

The gel layer constituting the sheet of the present invention contains the following components (A) to (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C) aluminum atom

(D) polyvinyl alcohol

A gel containing, the content of component (A) is 50 mass% or more and 85 mass% or less, the content of component (D) is 8 mass% or more, and the mass ratio [(B)/(C)] is 70 or more and 800 or less. It can be formed using a forming composition. In addition, in the present invention, the content of each component in the gel layer can be considered to be the same as the content or blending amount of each component in the gel-forming composition used to form the gel layer.

Additionally, the gel layer constituting the sheet of the present invention contains the following components (A), (B), (C1), and (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C1) Aluminum-containing compounds

(D) polyvinyl alcohol

It is made by combining,

The compounding amount of component (A) is 50% by mass or more and 85% by mass or less,

The amount of component (D) is 8% by mass or more,

It is preferable to form using a gel-forming composition whose mass ratio [(B)/(C1)] is 25 or more and 140 or less.

Components (A), (B), (C1) and (D) and other components mixed in the gel-forming composition, and their suitable modes, are as described in the gel layer above, unless otherwise specified. same.

The amount of components (A), (B), and (D) mixed in the gel-forming composition and their suitable range are the content of components (A), (B), and (D) in the gel layer and their suitable range. Same as

When blending two or more types of polyvinyl alcohol as component (D), it is preferable that the weight average molecular weight of each polyvinyl alcohol is all within the above range. The two or more types of polyvinyl alcohol referred to herein mean polyvinyl alcohols that differ from each other in weight average molecular weight, degree of saponification, or both.

In the gel-forming composition, the amount of component (B) (mass ratio [(B)/(C1)]) relative to the amount of component (C1) forms a gel layer that exhibits viscous properties in a wide frequency range, and forms a gel layer that exhibits viscous properties in a wide frequency range, From the viewpoint of improving adhesion, the value is preferably 25 or more, more preferably 50 or more, and even more preferably 60 or more. In addition, from the viewpoint of improving handling, especially from the viewpoint of suppressing stickiness when attaching sheets, from the viewpoint of making it easy to return the adhesive surfaces to their original state once they are attached, and from the viewpoint of improving storage stability, it is preferably 140 or less. , more preferably 130 or less, further preferably 120 or less, even more preferably 100 or less, and even more preferably 95 or less. And, the mass ratio [(B)/(C1)] is preferably 25 or more and 140 or less, more preferably 25 or more and 130 or less, further preferably 50 or more and 120 or less, and even more preferably 50 or more and 100 or less, Even more preferably, it is 60 or more and 95 or less.

The amount of component (C1) mixed in the gel-forming composition may be such that the mass ratio [(B)/(C1)] is within the above range. From the viewpoint of improving handleability, especially from the viewpoint of suppressing stickiness when attaching sheets, from the viewpoint of making it easy to return the adhesive surfaces to their original state once they are attached, and from the viewpoint of improving storage stability, it is preferable among gel-forming compositions. The amount is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and even more preferably 0.02 mass% or more. Additionally, from the viewpoint of forming a gel layer exhibiting viscous properties in a wide frequency range and improving adhesion to the skin, the amount is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.06% by mass. Hereinafter, the amount is even more preferably 0.04% by mass or less. And, the amount of component (C1) mixed in the gel-forming composition is preferably 0.005 mass% or more and 0.2 mass% or less, more preferably 0.005 mass% or more and 0.1 mass% or less, and further preferably 0.01 mass% or more and 0.06 mass% or less. The amount is % by mass or less, more preferably 0.02% by mass or more and 0.04% by mass or less.

The total content of the components (A), (B), (C1), and (D) in the gel-forming composition is preferably 70% by mass or more, more preferably 80% by mass, from the viewpoint of obtaining the effect of the present invention. % or more, more preferably 85 mass% or more, and further preferably 100 mass% or less.

Crosslinking agent components other than component (C1) may be added to the gel-forming composition to the extent that they do not impair the effect of the present invention, but the amount of the mixing agent is preferably small. The compounding amount of crosslinking agent components other than component (C1) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 0% by mass, based on the total crosslinking agent components.

The preparation method of the gel-forming composition is not particularly limited, but for component (D), it is preferable to prepare an aqueous solution dissolved in water in advance and mix it with other components in the state of an aqueous solution. After that, all other components may be added to the kneader and mixed, or some components may be mixed or dispersed and then put into the kneader and mixed.

＜Composition of sheet for body attachment＞

The composition of the body patch sheet of the present invention is not particularly limited as long as it has the gel layer, but from the viewpoint of handling and strength of the sheet, it is preferable to have the gel layer and the base material. That is, the sheet for body application of the present invention can have a two-layer structure in which the gel layer and the base material are laminated. Additionally, a release film may be laminated on the side of the gel layer on which the substrate is not laminated. The release film is used to protect the gel layer, and is a film that is peeled off from the gel layer when attaching the sheet. For example, non-axis oriented polypropylene film, biaxially oriented polypropylene film, polyethylene terephthalate film, etc. can be used. Among these, from the viewpoint of providing excellent peelability, those that have been embossed are preferable, and axes-stretched polypropylene films that have been embossed are more preferable.

From the viewpoint of sheet handling, the sheet for body application of the present invention preferably has a three-layer structure having a base material, a gel layer, and a release film in this order.

(write)

As a base material constituting the sheet of the present invention, a sheet-shaped base material such as woven fabric, non-woven fabric, knitted fabric, synthetic resin film, or water-resistant resin can be used. Additionally, a laminated substrate formed by stacking a plurality of these sheet-like substrates can also be used.

Specifically, woven or non-woven fabrics of synthetic fibers made of nylon, polypropylene, polyester, polyethylene, polystyrene, polyurethane, polyolefin, etc.; Woven or non-woven fabrics of natural fibers made of silk, cotton, hemp, rayon, collagen, etc.; Films made of synthetic resins such as nylon, polypropylene, polyester, polyethylene, and polyurethane; Sheet-shaped substrate made of pullulan, starch, etc.; Or a laminated base material formed by stacking a plurality of these, etc. can be mentioned.

Among the above, from the viewpoint of sheet handling, ease of lamination of the gel layer, and followability, the base material is preferably a nonwoven fabric, and more preferably a nonwoven fabric made of nylon, polypropylene, polyester, or polyethylene.

The thickness of the base material is not particularly limited, but is preferably 0.1 mm or more from the viewpoint of sheet handling and ease of lamination of the gel layer, and is preferably 5 mm or less from the viewpoint of improving followability, more preferably It is 3 mm or less, more preferably 2 mm or less.

The basis weight of the base material is not particularly limited, but is preferably 10 g/m2 or more from the viewpoint of sheet handling and ease of lamination of the gel layer, and from the viewpoint of improving followability, preferably 200 g/m2 or less, More preferably, it is 150 g/m2 or less, and even more preferably, it is 120 g/m2 or less.

[Method of manufacturing sheet for body attachment]

The present invention provides a method for producing a body patch sheet having a gel layer, comprising the following steps (I) to (III) in this order. By this manufacturing method, the sheet for body attachment of the present invention can be efficiently manufactured.

Process (I) Components (A), (B), (C1) and (D) following:

(A) water

(B) Carboxymethylcellulose or its salt

(C1) Aluminum-containing compounds

(D) polyvinyl alcohol

It is made by combining,

The compounding amount of component (A) is 50% by mass or more and 85% by mass or less,

The amount of component (D) is 8% by mass or more,

A process of preparing a gel-forming composition where the mass ratio [(B)/(C1)] is 25 or more and 140 or less.

Step (II) A step of filling the gel-forming composition between a base material and a release film and producing a laminated sheet having the base material, the gel-forming composition layer, and the release film in that order.

Step (III) A step of sealing the laminated sheet in a package and then crosslinking the gel-forming composition layer within the package.

＜Process (I)＞

In step (I), the following components (A), (B), (C1) and (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C1) Aluminum-containing compounds

(D) polyvinyl alcohol

It is made by combining,

The compounding amount of component (A) is 50% by mass or more and 85% by mass or less,

The amount of component (D) is 8% by mass or more,

A composition for gel formation with a mass ratio [(B)/(C1)] of 25 or more and 140 or less is prepared. The composition for forming a gel, its preparation method, and its suitable aspects are as described above.

＜Process (II)＞

In step (II), the gel-forming composition is filled between the base material and the release film, and a laminated sheet having the base material, the gel-forming composition layer, and the release film in that order is produced. The base material and release film are the same as above.

As a method of filling and laminating a gel-forming composition between a base material and a release film, for example, the gel-forming composition is sandwiched between a base material and a release film, and then applied to a desired thickness using a Baker-type applicator or the like. How to conduct an exhibition; A method of coating a gel-forming composition on a release film to a desired thickness and then laminating a base material; etc. can be mentioned. Alternatively, the base material and the release film can be placed face to face, each is driven by a conveyance roll, the space between the base material and the release film is filled with the gel-forming composition, and the composition is fed out while pressing with the roll to form a laminated sheet. At this time, by adjusting the distance between the two rolls, the gel forming composition layer can be adjusted to a desired thickness.

The laminated sheet obtained in step (II) is cut into desired sizes as needed and then provided to step (III).

＜Process (III)＞

In step (III), the laminated sheet obtained in step (II) is sealed in a package, and then the gel-forming composition layer is crosslinked in the package. As a result, a gel layer with a crosslinked structure can be formed.

The package used in step (III) preferably has moisture barrier properties, and from the viewpoint of suppressing volatilization of volatile components in the package and from the viewpoint of storage stability, it is more preferable that the package has gas barrier properties. . Specific examples of the package include a package having at least a layer made of silicon, aluminum, or these oxides. From the viewpoints of moisture barrier properties, gas barrier properties, and economic efficiency, a package containing a layer of aluminum is preferable.

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. The temperature is preferably 15 to 30°C, and the crosslinking time (ripening time) is preferably 1 to 21 days, more preferably 1 to 14 days.

The sheet for body attachment obtained by performing steps (I) to (III) can be used as a product while being sealed in a package. At the time of use, the sheet for body application is taken out from the package, the release film is peeled off, and the gel layer is applied to the body.

The sheet for body application of the present invention is used by attaching it to the outer skin (excluding the scalp). There are no particular restrictions on the body part, and even when applied to highly curvature areas such as elbows and knees, it follows movement and is difficult to peel off, is resistant to oil, and has good re-attachment properties and long-term application properties.

Hereinafter, with respect to the above-described embodiments, the present invention further discloses the following.

＜1＞

A sheet for attaching to the body having a gel layer,

The gel layer contains the following components (A) to (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C) aluminum atom

(D) polyvinyl alcohol

Contains,

The content of component (A) in the gel layer is 50% by mass or more and 85% by mass or less,

The content of component (D) in the gel layer is 8% by mass or more,

A sheet for attaching to the body, wherein the mass ratio [(B)/(C)] is 70 or more and 800 or less.

＜2＞

The content of component (A) in the gel layer is preferably 55 mass% or more, more preferably 60 mass% or more, further preferably 65 mass% or more, preferably 80 mass% or less, more preferably The sheet for body attachment of <1>, which is 78% by mass or less, more preferably 77% by mass or less.

＜3＞

The content of component (B) in the gel layer is preferably 1.0 mass% or more, more preferably 1.5 mass% or more, further preferably 2.0 mass% or more, even more preferably 2.3 mass% or more, and even more preferably <1> or <2, preferably 2.5 mass% or more, preferably 5.0 mass% or less, more preferably 4.0 mass% or less, even more preferably 3.8 mass% or less, and even more preferably 3.4 mass% or less. ＞ Sheet for attaching to the body.

＜4＞

The content of component (C) in the gel layer is preferably 0.002 mass% or more, more preferably 0.003 mass% or more, further preferably 0.005 mass% or more, even more preferably 0.0062 mass% or more, and even more preferably <1> to <3, which is preferably 0.008 mass% or more, preferably 0.05 mass% or less, more preferably 0.04 mass% or less, even more preferably 0.035 mass% or less, and even more preferably 0.02 mass% or less. ＞ Any one of the following sheets for attaching to the body.

＜5＞

The mass ratio [(B)/(C)] is preferably 85 or more, more preferably 100 or more, preferably 600 or less, more preferably 550 or less, even more preferably 500 or less, <1> The sheet for attaching to the body according to any one of ~ <4>.

＜6＞

The weight average molecular weight of the component (D) is preferably 30,000 or more, more preferably 50,000 or more, still more preferably 70,000 or more, preferably 150,000 or less, more preferably 120,000 or less, even more preferably 100,000. The sheet for attaching to the body according to any one of <1> to <5> below.

＜7＞

The saponification degree of the component (D) is preferably 75 mol% or more, more preferably 82 mol% or more, further preferably 85 mol% or more, preferably 98 mol% or less, more preferably 96 mol% or more. The sheet for attaching to the body according to any one of <1> to <6>, mol% or less.

＜8＞

The content of component (D) in the gel layer is preferably 8.3 mass% or more, more preferably 8.5 mass% or more, preferably 18 mass% or less, more preferably 14 mass% or less, even more preferably The sheet for attaching to the body according to any one of <1> to <7>, which is 12% by mass or less.

＜9＞

The mass ratio [(D)/(B)] in the gel layer is preferably 2 or more, more preferably 2.4 or more, even more preferably 2.8 or more, even more preferably 3 or more, and preferably 8 or less, The body attaching sheet according to any one of <1> to <8>, wherein the weight is more preferably 6 or less, further preferably 5 or less, even more preferably 4.5 or less, and even more preferably 4 or less.

＜10＞

The total content of the components (A) to (D) in the gel layer is preferably 70 mass% or more, more preferably 80 mass% or more, further preferably 85 mass% or more, and further preferably 100 mass% or less. , The sheet for attaching to the body according to any one of <1> to <9>.

＜11＞

The content of polyacrylic acid or its salt in the gel layer is preferably less than 4 mass%, more preferably less than 3 mass%, even more preferably 2 mass% or less, and even more preferably 1 mass% or less, Even more preferably, the sheet for attaching to the body according to any one of <1> to <10> is 0% by mass.

＜12＞

The body attaching sheet according to any one of <1> to <11>, wherein the component (B) has a crosslinked structure in which the component (C) is crosslinked by the component (C) in the gel layer.

＜13＞

In the gel layer, according to JIS Z0237:2009, the angle of the inclined plate is 30°, the temperature is 23°C, and the temperature is 50% R.H. The ball number in the bolt tack test conducted under the conditions is preferably 15 or more, more preferably 18 or more, even more preferably 19 or more, even more preferably 20 or more, preferably 32 or less, more preferably 32 or less. The sheet for attaching to the body according to any one of <1> to <12>, preferably 30 or less, more preferably 28 or less, and even more preferably 26 or less.

＜14＞

The loss tangent of the gel layer in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz is preferably 0.18 or more, more preferably 0.20 or more, even more preferably 0.22 or more, even more preferably 0.25 or more, Even more preferably, it is 0.28 or more, preferably 0.60 or less, more preferably 0.58 or less, and even more preferably 0.50 or less. The sheet for attaching to the body according to any one of <1> to <13>.

＜15＞

The thickness of the gel layer is preferably 0.1 mm or more, more preferably 0.3 mm or more, further preferably 0.5 mm or more, preferably 5 mm or less, more preferably 3 mm or less, and even more preferably 2 A sheet for attaching to the body of any one of <1> to <14>, which is ㎜ or less.

＜16＞

The body patch according to any one of <1> to <15>, wherein the body patch sheet has a two-layer structure in which the gel layer and the base material are laminated, or a three-layer structure having the base material, the gel layer, and the release film in this order. dragon sheet.

＜17＞

The body attachment sheet of <16>, wherein the base material is preferably a non-woven fabric, more preferably a non-woven fabric made of nylon, polypropylene, polyester, or polyethylene.

＜18＞

A sheet for attaching to the body having a gel layer,

The gel layer contains the following components (A), (B), (C1) and (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C1) Aluminum-containing compounds

(D) polyvinyl alcohol

A gel-forming composition obtained by mixing the following, wherein the amount of component (A) is 50% by mass or more and 85% by mass or less, the amount of component (D) is 8% by mass or more, and the mass ratio (B)/(C1) is 25%. It is formed using a gel-forming composition having a temperature of not less than 140,

A sheet for attaching to the body, wherein component (B) is crosslinked with component (C1).

＜19＞

The following components (A) to (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C) aluminum atom

(D) polyvinyl alcohol

Contains, the content of component (A) is 50 mass% or more and 85 mass% or less, the content of component (D) is 8 mass% or more, and the mass ratio [(B)/(C)] is 60 or more and 800 or less, Composition for gel formation.

＜20＞

The following components (A), (B), (C1) and (D):

(A) water

(B) Carboxymethylcellulose or its salt

(C1) Aluminum-containing compounds

(D) polyvinyl alcohol

It is made by combining,

The compounding amount of component (A) is 50% by mass or more and 85% by mass or less,

The amount of component (D) is 8% by mass or more,

A composition for forming a gel, wherein the mass ratio [(B)/(C1)] is 25 or more and 140 or less.

＜21＞

The amount of component (C1) mixed in the gel-forming composition is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, further preferably 0.02 mass% or more, and preferably 0.2 mass% or less. , more preferably 0.1 mass% or less, further preferably 0.06 mass% or less, and even more preferably 0.04 mass% or less. The sheet for body application of <18> or the gel-forming composition of <20>.

＜22＞

The mixing amount of component (B) relative to the mixing amount of component (C1) (mass ratio [(B)/(C1)]) is more preferably 50 or more, further preferably 60 or more, and even more preferably 130 or less. , more preferably 120 or less, even more preferably 100 or less, even more preferably 95 or less, the sheet for body application of <18>, the gel-forming composition of <20> or <21>.

＜23＞

The component (C1) is preferably aluminum hydroxide, magnesium aluminum hydroxide, sodium aluminate, aluminum sulfate, potassium aluminum sulfate, ammonium aluminum sulfate, aluminum carbonate, aluminum nitrate, aluminum chloride, magnesium alumino(meth)silicate, and acetic acid. At least one selected from the group consisting of aluminum, aluminum lactate, aluminum stearate, aluminum myristic acid, aluminum glycinate, aluminum benzoate, and allantoin chlorohydroxyaluminum, more preferably aluminum hydroxide and (meth)aluminosilicate. The body patch of <18>, containing at least one selected from the group consisting of magnesium, more preferably magnesium alumino(meth)silicate, and even more preferably aluminum hydroxide and magnesium alumino(meth)silicate. Sheet, the composition for forming a gel according to any one of <20> to <22>.

＜24＞

A method for producing a body patch sheet having a gel layer, comprising the following steps (I) to (III) in this order.

Process (I) Components (A), (B), (C1) and (D) following:

(A) water

(B) Carboxymethylcellulose or its salt

(C1) Aluminum-containing compounds

(D) polyvinyl alcohol

It is made by combining,

The compounding amount of component (A) is 50% by mass or more and 85% by mass or less,

The amount of component (D) is 8% by mass or more,

A process of preparing a gel-forming composition where the mass ratio [(B)/(C1)] is 25 or more and 140 or less.

Step (II) A step of filling the gel-forming composition between a base material and a release film and producing a laminated sheet having the base material, the gel-forming composition layer, and the release film in that order.

Step (III) A step of sealing the laminated sheet in a package and then crosslinking the gel-forming composition layer within the package.

Example

Hereinafter, the present invention will be explained by way of examples, but the present invention is not limited to the scope of the examples. In addition, various measurements in this example were performed by the following method.

<Viscosity of 1% by mass aqueous solution of component (B)>

The viscosity of the 1% by mass aqueous solution of component (B) was measured using a B-type viscometer (“TVB-10” manufactured by Toki Sangyo Co., Ltd.) at 25°C.

<Weight average molecular weight of component (D)>

The weight average molecular weight of the powder raw material of component (D) was determined by measuring an aqueous solution in which the powder raw material was dissolved in water by size exclusion chromatography (SEC) under the following conditions. Additionally, the weight average molecular weight of component (D) in the gel layer was determined by measuring the extract of the gel layer by size exclusion chromatography (SEC) under the following conditions. The weight average molecular weight of component (D) described in the table is the weight average molecular weight of component (D) in the powder raw material and the gel layer.

＜SEC measurement conditions＞

Measuring device: “SEC-8320” manufactured by Tosoh Co., Ltd.

Eluent: 0.2 mol/L phosphate buffer/acetonitrile = 9/1 (V/V %)

Guard column: “PWXL (6 mm × 4 cm)” manufactured by Tosoh Co., Ltd.

Analytical column: “G4000PWxL+G2500PWxL (7.8 mm × 30 cm)” manufactured by Tosoh Co., Ltd.

Flow rate: 1 mL/min

Column temperature: 40℃

Injection volume: 100 μL

Sample size: 1 mg/mL

Molecular weight conversion standard: PEO manufactured by Tosoh Co., Ltd. (SE-150 (977,000), SE-70 (580,000), SE-30 (394,000), SE-15 (14.30,000), SE-8 (10.10,000) , SE-2 (2.1 only))

Detector: RI

Examples 1 to 27, Comparative Examples 1 to 9 (Preparation of gel-forming composition, production and evaluation of sheet for body application)

(Preparation of composition for gel formation)

A gel-forming composition was prepared according to the prescription shown in the table. Specifically, a solution obtained by dissolving methyl paraoxybenzoate and menthol in propylene glycol by heating, and an aqueous solution containing polyvinyl alcohol and a pH adjuster were prepared in advance. An aqueous solution containing polyvinyl alcohol and a pH adjuster was put into a kneader, and then all other ingredients were added and mixed to prepare a gel-forming composition. In addition, the compounding quantity described in the table is the amount of active ingredient (mass %) of each component. In addition, in the table, polymers that have the ability to form crosslinks by aluminum ions and do not belong to component (B) are indicated as "component (B')."

(Manufacture of sheets for body attachment)

The gel-forming composition is sandwiched between a polyester nonwoven fabric (thickness 0.7 mm) as a base material and a polypropylene release film, and the thickness of the gel-forming composition layer is adjusted to 1.5 mm using a Baker-type applicator and rolled to form a nonwoven fabric. , a gel-forming composition layer, and a release film were sequentially laminated to obtain a sheet. The sheet was cut into 12.5 cm A sheet for body application with a three-layer structure having , a gel layer, and a release film in this order was manufactured.

Using the obtained body patch sheet, evaluation was performed by the following method. The results are shown in Tables 1 to 5.

＜Boltack test＞

The bolt-tack test of the gel layer of the body attaching sheet in each example was based on JIS Z0237:2009, at an inclined plate angle of 30°, a temperature of 23°C, and 50% R.H. It was carried out under the conditions. The body adhesive sheet of each example was taken out of the aluminum pillow, and after peeling off the release film, it was quickly installed in a bolt-tack tester and a bolt-tack test was performed. The maximum ball number that stops for more than 5 seconds in the adhesive area of the gel layer is shown in the table. .

＜Loss tangent (tanδ)＞

The loss tangent (tanδ) of the gel layer of the body patch sheet of each example was measured using a rheometer (“Physica MCR301” manufactured by Anton Paar Co., Ltd.). The sheet for body attachment in each example was cut into a circle with a diameter of 25 mm, and the nonwoven fabric side was fixed to the sample section of the rheometer (parallel plate with a diameter of 25 mm) with double-sided tape. Next, the peeling film was peeled, the loss modulus and storage modulus of the gel layer were measured under the following conditions, and the loss tangent (tanδ) was calculated from these values. Measurements were performed multiple times (three or more times), and the average value was adopted.

〔Measuring conditions〕

·Normal force: 1 N

·Gap interval: 1 ~ 2 mm

· Mass of gel layer: 0.5 to 1.0 g

·Measurement frequency: 0.1 Hz

·Deformation: 2%

·Temperature: 25℃

＜Adhesion (calf)＞

Adhesion immediately after application

The body attaching sheet of each example was taken out from the aluminum pillow, and immediately after peeling off the release film, it was attached to the professional panelist's calf so that the long side of the sheet was perpendicular to the circumferential direction of the calf. Ten seconds after application, an expert panelist performed an ankle dorsiflexion exercise 10 times and measured the area of the area where the body application sheet was floating on the calf, that is, the area where the body application sheet was peeled off from the calf. The ratio (%) of the area of the peeled portion of the sheet to the entire area of the body adhesive sheet was determined and evaluated according to the following criteria. The higher the evaluation value, the better the adhesion immediately after sticking.

In addition, all evaluations by professional panelists in this example were performed by three panelists, and the evaluation values shown in the table are the average values of the three panelists.

〔Evaluation standard〕

7: The area ratio of the portion where the sheet is peeled is 5% or less.

6: The area ratio of the portion where the sheet is peeled is more than 5% and 10% or less.

5: The area ratio of the portion where the sheet is peeled is more than 10% and 20% or less.

4: The area ratio of the portion where the sheet is peeled is more than 20% and 30% or less.

3: The area ratio of the portion where the sheet is peeled is more than 30% and 40% or less.

2: The area ratio of the portion where the sheet is peeled is more than 40% and 50% or less.

1: The area ratio of the portion where the sheet is peeled exceeds 50%.

reattachment

The body adhesive sheet for each example was affixed to the calf of the expert panelist in the same manner as above, and peeled off after 10 seconds. After performing the same trial again, the peeled body patch sheet was applied again to the expert panelist's other calf in the same manner as above, and after 10 seconds, the ankle dorsiflexion exercise was performed 10 times. The area of the area where the body patch sheet was peeled off from the calf was measured in the same manner as above, and evaluated according to the above criteria. The higher the evaluation value, the better the adhesion after re-attachment.

Adhesion after applying cream

A commercially available body cream (emulsion: 11%, emulsifier: 2.5%, polyol: 12%, water: 72%, others: 2.5%) was applied to the calf of an expert panelist. Next, in the same manner as above, the body attachment sheet of each example was attached to the calf of the expert panelist, and 10 seconds after attachment, the expert panelist performed 10 times of ankle dorsiflexion. The area of the area where the body patch sheet was peeled off from the calf was measured in the same manner as above, and evaluated according to the above criteria. The higher the evaluation value, the better the adhesion after applying the body cream.

Long-term adhesion

The body attachment sheet for each example was attached to the calf of the expert panelist in the same manner as above. The difficulty of peeling after sticking for 3 hours is graded into 5 levels (5 points: very difficult to peel, 4 points: difficult to peel, 3 points: somewhat difficult to peel, 2 points: somewhat easy to peel, 1 point: easy to peel). evaluated. The higher the evaluation value, the better the adhesion after sticking for a long time.

＜Adhesion (knee)＞

Adhesion under load conditions

Adhesion was evaluated under load conditions. This load condition involves attaching a body patch sheet to a highly curvature part and then moving the affixed part, so that the adhesion and followability immediately after application to the highly curvature part can be evaluated.

The body attaching sheet of each example was taken out from the aluminum pillow, and immediately after peeling off the release film, it was attached to the expert panelist's knee so that the long side of the sheet was parallel to the circumferential direction of the knee. After 10 seconds of application, the expert panelist bends and straightens the knee 10 times (90° to 180°) to determine the area of the area where the body application sheet is floating on the knee, that is, the area where the sheet has been peeled off from the knee. was measured. The area ratio (%) of the area where the sheet was peeled off to the entire area of the body adhesive sheet was determined. The evaluation criteria are the same as for adhesion to the calf. The higher the evaluation value, the better the adhesion under load conditions.

＜Handability＞

(Ease of attachment)

The body attaching sheet of each example was taken out from the aluminum pillow, and immediately after peeling off the release film, it was attached to the professional panelist's calf so that the long side of the sheet was perpendicular to the circumferential direction of the calf. The ease of attachment at that time was evaluated on a 5-level 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 it is to stick the body patch sheet easily and cleanly. The lower the value, the more wrinkles etc. appear and the more difficult it is to stick the body stick sheet cleanly.

(sticky to fingers)

The stickiness of the adhesive surface (gel layer) to the fingers when the body adhesive sheet of each example was applied in the same manner as above was rated in 5 levels (5 points: not sticky, 4 points: not very sticky, 3 points: somewhat sticky) , 2 points: sticky, 1 point: very sticky). The higher the evaluation value, the lower the degree of stickiness to the fingers.

(Ease of peeling between adhesive surfaces)

The body attachment sheet of each example was taken out from the aluminum pillow, the release film was peeled off, the sheet was folded in half, and the adhesive surfaces were adhered to each other. Next, the ease of peeling when peeling off the adhesive surface was ranked in 5 levels (5 points: easy to peel, 4 points: somewhat easy to peel, 3 points: somewhat difficult to peel, 2 points: difficult to peel, 1 point: very easy to peel) It was evaluated as “difficult to do.” The higher the evaluation value, the easier it is to peel off the adhesive surfaces even once they are attached to each other (easier to return them to their original state), indicating that the handleability is good.

＜Storage stability＞

The body patch sheet in each case was stored in a constant temperature bath at 50°C for 1 month while encapsulated in an aluminum pillow, and then returned to 25°C. The body patch sheet was taken out from the aluminum pillow, and the storage stability of the appearance and gel properties was evaluated in five stages based on the following criteria. The higher the evaluation value, the higher the storage stability.

(Exterior)

5: Equivalent to the state before preservation

4: Discoloration of the gel and slight oozing of the non-woven fabric are visible.

3: Discoloration of the gel and some oozing of the non-woven fabric are visible.

2: Discoloration of the gel and oozing into the non-woven fabric are visible.

1: Difficult to use as a sheet

(Gel appearance)

The sheet for body application in each example was taken out of the aluminum pillow, and the remaining gel on the skin when peeled off after application to the forearm of an expert panelist for 30 minutes was evaluated in 5 grades.

5: Equivalent to the state before preservation (gel does not remain on the skin)

4: A little bit of gel remains on the skin

3: Some gel remains on the skin

2: The gel is soft, and a large amount of gel remains on the skin.

1: Difficult to use as a sheet

From Tables 1 to 5, the sheet for body application of the present example has good adhesion immediately after application to the skin and adhesion under load conditions, difficulty in peeling when applied for a long time, adhesion to oily skin, and re-application property. is also good. In addition, it has excellent handling properties when sticking, has little deterioration of the gel layer over time, and has good storage stability. On the other hand, the sheet for body application of this comparative example could not satisfy all of the adhesion immediately after application to the skin, adhesion under load conditions, and ease of application to the skin.

Additionally, Figure 1 is a graph showing the viscoelastic behavior (relationship between measurement frequency and loss tangent (tanδ)) of the gel layer of the body patch sheet obtained in Example 1 and Comparative Example 4. As shown in Figure 1, it can be seen that the gel layer of Example 1 has a loss tangent of 0.20 or more in a wider frequency range compared to Comparative Example 4 and has viscous properties.

According to the present invention, a sheet for body application is provided that has good adhesion to the skin, especially when applied to joints such as elbows and knees with high curvature and has good adhesion even when movement is applied to the applied portion, and is also excellent in handling properties when applied. can be provided.

Claims (7)

A sheet for attaching to the body having a gel layer,
The gel layer contains the following components (A) to (D):
(A) water
(B) Carboxymethylcellulose or its salt
(C) aluminum atom
(D) contains polyvinyl alcohol,
The content of component (A) in the gel layer is 50% by mass or more and 85% by mass or less,
The content of component (D) in the gel layer is 8% by mass or more,
A sheet for attaching to the body, wherein the mass ratio [(B)/(C)] is 70 or more and 800 or less. According to claim 1,
A body patch having a cross-linked structure in which the component (B) is cross-linked by the component (C) in the gel layer. The method of claim 1 or 2,
A sheet for body application, wherein the weight average molecular weight of the component (D) is 150,000 or less. The method according to any one of claims 1 to 3,
A sheet for body application, wherein the degree of saponification of the component (D) is 75 mol% or more. The method according to any one of claims 1 to 4,
A sheet for attaching to the body, wherein the gel layer has a ball number of 15 to 30 in a bolt-tack test conducted under the conditions of an inclined plate angle of 30°, a temperature of 23°C, and 50% RH in accordance with JIS Z0237:2009. The method according to any one of claims 1 to 5,
A sheet for body application, wherein the gel layer has a loss tangent of 0.20 or more in dynamic viscoelasticity measurement at a temperature of 25°C and a frequency of 0.1 Hz. A method for producing a sheet for body patch having a gel layer, comprising the following steps (I) to (III) in this order.
Process (I) Components (A), (B), (C1) and (D) following:
(A) water
(B) Carboxymethylcellulose or its salt
(C1) Aluminum-containing compounds
(D) It is made by mixing polyvinyl alcohol,
The compounding amount of component (A) is 50% by mass or more and 85% by mass or less,
The compounding amount of component (D) is 8% by mass or more,
Process of preparing a gel-forming composition with a mass ratio [(B)/(C1)] of 25 or more and 140 or less.
Step (II) A process of filling the gel-forming composition between a base material and a release film and producing a laminated sheet having the base material, the gel-forming composition layer, and the release film in that order.
Step (III) A step of sealing the laminated sheet in a package and then crosslinking the gel-forming composition layer within the package.

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