WO2022264653A1

WO2022264653A1 - Sheet for application to body

Info

Publication number: WO2022264653A1
Application number: PCT/JP2022/016558
Authority: WO
Inventors: 翔平木村
Original assignee: 花王株式会社
Priority date: 2021-06-15
Filing date: 2022-03-31
Publication date: 2022-12-22
Also published as: JP7301190B2; TW202306595A; JP2022191154A; CN117479959A; KR20240021754A

Abstract

A sheet for application to the body which includes a gel layer, wherein the gel layer comprises (A) water, (B) carboxymethyl cellulose or a salt thereof, (C) aluminum atoms, and (D) poly(vinyl alcohol) and the gel layer has a content of the component (A) of 50-85 mass%, a content of the component (D) of 8 mass% or higher, and a (B)/(C) mass ratio of 70-800.

Description

Body paste sheet

The present invention relates to a body patch sheet.

Adhesive sheets have been developed which are produced using hydrous gel compositions and which are imparted with various efficacies. A water-soluble polymer compound is usually used as a main component other than water constituting the hydrous gel composition.
For example, Japanese Patent Application Laid-Open No. 2005-314290 (Patent Document 1) discloses a patch comprising a support and an adhesive layer disposed on at least one surface of the support, wherein the adhesive layer is formed from an adhesive base containing β-glucan.
Japanese Patent Application Laid-Open No. 2013-79198 (Patent Document 2) discloses another layer of the gel base layer, which has at least a gel base layer, a support layer, and an adhesive layer, and has a layer structure laminated in this order. A cooling sheet for clothing to be worn so that part or all of the surface on the side not in contact with the part to be cooled is in direct contact, wherein the gel base layer is formed from a cooling composition containing polyvinyl alcohol It is disclosed that a cooling sheet for clothing containing a predetermined amount of polyvinyl alcohol is non-sticky and has excellent cooling and cold-retaining effects even when it comes into contact with a part to be cooled such as the skin of the human body.

Japanese Patent Application Laid-Open No. 2016-124870 (Patent Document 3) discloses a predetermined amount of water, an anionic water-soluble polymer compound containing a predetermined amount or more of carboxymethyl cellulose or a salt thereof, and a cross-linking agent that forms an ionic cross-link with an anionic functional group. , and a nonionic water-soluble polymer compound having a predetermined amount and a predetermined structure.
International Publication No. WO 2018/155310 (Patent Document 4) describes a patch base containing predetermined amounts of gelatin, polyvinyl alcohol, methyl acrylate/2-ethylhexyl acrylate copolymer, and L-menthyl glyceryl ether. However, even when L-menthyl glyceryl ether is used as a cooling agent, there is provided a base for a patch that suppresses the generation of an unpleasant odor while maintaining the adhesive strength of the base, and a patch using the same It is disclosed that agents can be provided.

The present invention relates to the following.
[1] A body patch sheet having a gel layer,
The gel layer comprises the following components (A)-(D):
(A) water (B) carboxymethyl cellulose or a salt thereof (C) an aluminum atom (D) containing 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 body patch sheet having a mass ratio [(B)/(C)] of 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.
Step (I) The following components (A), (B), (C1) and (D):
(A) water (B) carboxymethyl cellulose or its salt (C1) an aluminum-containing compound (D) polyvinyl alcohol,
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,
Step (II) of preparing a gel-forming composition having a mass ratio [(B)/(C1)] of 25 or more and 140 or less Filling the gel-forming composition between the substrate and the release film, Step (III): The laminated sheet is sealed in a package, and then the gel-forming composition layer is crosslinked in the package. the process of causing

2 is a graph showing viscoelastic behavior (relationship between measurement frequency and loss tangent (tan δ)) of the gel layers of the body patch sheets obtained in Example 1 and Comparative Example 4. FIG.

In recent years, there has been a demand for high functionality in body patch sheets. Body patch sheets have high adhesiveness and followability immediately after application, and sufficient adhesive strength to prevent them from peeling off even after a variety of daily activities. It has become desirable to provide For example, when applying to joints with high curvature such as elbows and knees and adding movement to the applied part, when removing and reapplying after applying to the skin, and when applying to the skin after applying body cream. Also, there is a demand for a body application sheet that maintains adhesion to the skin even when applied for a long period of time and that is not easily peeled off. This is because there is an increasing demand for comfortably obtaining various physiological effects during use in various life situations.
However, with conventional body patch sheets, when the body patch sheet is attached to the skin, the adhesive surface of the sheet feels sticky to fingers, and when the adhesive surfaces of the sheet stick to each other after peeling off the release film, , it is difficult to return to its original state. That is, an attempt to improve the adhesion results in a problem of handleability, and an attempt to improve the handleability results in poor adhesion. In view of the above points, there is room for improvement in the conventional body patch sheet.

The object of the present invention is to achieve good adhesion to the skin, especially when applied to joints with high curvature, such as elbows and knees, and when the applied part is moved, the adhesion is good, and handling at the time of application is easy. To provide an excellent body sticking sheet.

The present inventors have proposed a body patch sheet having a gel layer, wherein the gel layer contains a predetermined amount of water, carboxymethylcellulose or its salt, aluminum atoms, and a predetermined amount of polyvinyl alcohol, and carboxymethylcellulose or its salt. The present inventors have found that the above problem can be solved by setting the mass ratio of aluminum to aluminum atoms within a predetermined range.

According to the present invention, the adhesiveness to the skin is good, especially when the adhesiveness is applied to joints with high curvature such as elbows and knees and the applied part is moved, and the handleability at the time of application is good. An excellent body application sheet can be provided.

[definition]
In the following description, "(the body patch sheet) has good adhesion to the skin" means that at least both the adhesion immediately after application to the skin and the adhesion under load conditions are good. Say something. The “adherence immediately after application” means the adhesion when daily activities are performed immediately after the body application sheet is applied to a part other than joints (for example, calves). The term "adherence under load" refers to the adhesion when a movement is applied to the body application sheet immediately after the body application sheet is applied to a portion with a high curvature (for example, a joint portion such as a knee). . Adhesion immediately after application to the skin and adhesion under load conditions can be evaluated by the method described in Examples.
Furthermore, the body patch sheet of the present invention is difficult to peel off after being applied for a long period of time, has good adhesion to oily skin, and has good re-application properties.
In the present invention, "excellent handleability at the time of application (of the body patch sheet)" means at least that the body patch sheet can be easily attached to the skin. The ease of application of the sheet to the skin can be evaluated by the method described in Examples.
Furthermore, the body patch sheet of the present invention suppresses the stickiness of the adhesive surface of the sheet to fingers, and when the adhesive surfaces of the sheet stick to each other during application, the adhesive surfaces can be easily separated (in the original state). It is also excellent in that it is easy to return to
The adhesive surface of the sheet for body application of the present invention means the gel layer surface of the sheet. In addition, in the following description, "When the adhesive surfaces of the sheet are attached to each other at the time of application, the adhesive surfaces should be easy to separate (easy to return to their original state)"It's easy to get back in shape," he said.

[Body attachment sheet]
The body patch sheet of the present invention (hereinafter also simply referred to as "the sheet of the present invention") is a body patch sheet having a gel layer, the gel layer comprising the following components (A) to (D):
(A) water (B) carboxymethyl cellulose or a salt thereof (C) an aluminum atom (D) containing 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,
The mass ratio [(B)/(C)] is 70 or more and 800 or less.
By having the above structure, the body patch sheet of the present invention has excellent adhesion to the skin and excellent handleability at the time of application.

Although it is not clear why the sheet of the present invention having the above-described structure exhibits the effects of the present invention, it is speculated 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 ions can act as a cross-linking agent for component (B). Therefore, in the gel layer constituting the sheet of the present invention, component (B) is considered 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 with aluminum ions. It is considered that the molecular chains are present in a state in which they can flow.
The gel layer constituting the sheet of the present invention contains the component (B) and the component (C) in a specific ratio, and contains a predetermined amount of the component (D), so that it is wider than the conventional gel layer. It exhibits viscous properties in the frequency domain. Furthermore, the gel layer exhibited a characteristic viscoelastic behavior in which the viscous property was strong in the low frequency region and the viscous property became stronger as it shifted to the high frequency region. Then, the gel layer exhibiting such viscoelastic behavior exhibits high adhesion to the skin, and not only is it excellent in stickiness when applied, but also suppresses stickiness when applied, and the adhesive surface (i.e., the gel layer) ) were found to be easily restored to their original state even if they were once attached to each other. As an action mechanism by which such adhesive physical properties are expressed, the mass ratio [(B) / (C)] in the gel layer is set to a predetermined value or less, and by increasing the proportion of component (D), the cross-linking point is It is thought that the adhesiveness of the sheet to the skin is improved because a gel structure that is less deformable is formed. In addition, increasing the content of component (D) in the gel layer improves the tackiness of the gel layer, thereby improving adhesion to the skin. It is thought that by doing so, excessive improvement in tackiness was suppressed, and good handleability during application could be maintained.

<Gel layer>
The body patch sheet of the present invention comprises the following components (A) to (D):
(A) water (B) carboxymethyl cellulose or a salt thereof (C) an aluminum atom (D) containing polyvinyl alcohol, the content of component (A) is 50% by mass or more and 85% by mass or less, and the content of component (D) is It has a gel layer with a content of 8% by mass or more and a mass ratio [(B)/(C)] of 70 or more and 800 or less.
In 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 is easy to handle when applied.

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

More specifically, the gel layer constituting the sheet of the present invention preferably has a loss tangent of 0 in dynamic viscoelasticity measurement at a temperature of 25° C. and a frequency of 0.1 Hz, from the viewpoint of improving adhesion to the skin. 0.18 or more, more preferably 0.20 or more, still more preferably 0.22 or more, still more preferably 0.25 or more, and even more preferably 0.28 or more. In addition, from the viewpoint of handleability, particularly from the viewpoint of suppressing stickiness at the time of sticking the sheet and from the viewpoint of making it easy to restore the original state even if the adhesive surfaces are once stuck, it is preferably 0.70 or less, more preferably 0.60. Below, more preferably 0.58 or less, still more preferably 0.50 or less. 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. 0.60 or less, more preferably 0.22 or more and 0.58 or less, still more preferably 0.25 or more and 0.58 or less, still more preferably 0.28 or more and 0.50 or less.
Specifically, the loss tangent of the gel layer can be measured by the method described in Examples.

Further, the gel layer constituting the sheet of the present invention has high tack strength. The tack strength is an index of developing short-term adhesive strength with a light force. In other words, a sheet with high tack strength exhibits high adhesion immediately after application to the skin. More specifically, the gel layer was subjected to a tilt angle of 30°, a temperature of 23°C, and a 50% R.I. according to JIS Z0237:2009. H. The ball number in a ball tack test conducted under the conditions of is preferably 15 or higher, more preferably 18 or higher, even more preferably 19 or higher, and even more preferably 20 or higher. In addition, from the viewpoint of handleability, in particular, from the viewpoint of suppressing stickiness at the time of sticking the sheet and making it easy to restore the original state even if the adhesive surfaces are once stuck, the ball number is preferably 32 or less, or more. It is preferably 30 or less, more preferably 28 or less, and even more preferably 26 or less. The ball number is preferably 15 or more and 32 or less, more preferably 15 or more and 30 or less, still more preferably 18 or more and 28 or less, still more preferably 19 or more and 28 or less, still more preferably 20 or more and 26 or less.
The ball tack test can be specifically performed by the method described in Examples.

The gel layer having the physical properties contains the components (A) to (D), and the content of component (A) in the gel layer, the content of component (D), and the mass ratio [(B) /(C)] within a predetermined range. Each component contained in the gel layer will be described below.

(Component (A): water)
By containing water in the gel layer constituting the sheet of the present invention, it is possible to effectively permeate active ingredients such as medicinal ingredients and cooling sensation ingredients into the skin.
As component (A), for example, purified water such as deionized water, distilled water, highly pure water, and 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, from the viewpoint of effective penetration of the active ingredient into the skin. is 65% by mass or more. In addition, from the viewpoint of improving the 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, and even more preferably 78% by mass or less. is 77% by mass or less. The content of component (A) in the gel layer is 50% by mass or more and 85% by mass or less, preferably 55% by mass or more and 80% by mass or less, more preferably 60% by mass or more and 78% by mass or less, and further It is preferably 65% by mass or more and 77% by 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 carboxy group and can form a crosslinked structure through ionic interaction with trivalent aluminum ions, which are ionized products of component (C).
Salts of carboxymethylcellulose include alkali metal salts such as sodium salts and potassium salts, and ammonium salts. From the viewpoint of availability and the like, the salt of carboxymethylcellulose is preferably an alkali metal salt of carboxymethylcellulose, and more preferably a sodium salt of carboxymethylcellulose (sodium carboxymethylcellulose).

The degree of etherification of component (B) is preferably 0.60 or more, more preferably 0.65 or more, from the viewpoint of obtaining an appropriate shape retention property of the gel layer and ensuring the storage stability of the gel layer. It is preferably 1.1 or less, more preferably 1.0 or less, and still more preferably 0.95 or less.
The degree of etherification of component (B) refers to the degree of substitution of carboxymethyl groups per glucose unit of component (B). When the component (B) is sodium carboxymethylcellulose, its degree of etherification can be measured by the following method, for example, according to the CMC Industrial Association analysis method (ashing method).
[Measurement of degree of etherification of sodium carboxymethylcellulose]
1 g of carboxymethylcellulose sodium was precisely weighed, placed in a magnetic crucible and incinerated at 600° C. The sodium oxide produced by the incineration was titrated with N/10 sulfuric acid using phenolphthalein as an indicator, and the titration amount per 1 g of sodium carboxymethylcellulose was obtained. YmL can be calculated by entering the following formula to indicate the obtained degree of etherification.
Degree of etherification = (162 x Y) / (10,000-80 x Y)

Component (B), from the viewpoint of obtaining an appropriate shape retention property of the gel layer and from the viewpoint of ensuring the stability of the gel layer, the viscosity at 25 ° C. when made into a 1% by mass aqueous solution is measured with a Brookfield viscometer. , preferably 1,000 mPa s or more, more preferably 1,200 mPa s or more, still more preferably 1,500 mPa s or more, preferably 7,000 mPa s or less, more preferably 6,000 mPa s. Below, more preferably 5,000 mPa·s or less. The viscosity at 25° C. of a 1% by mass aqueous solution of component (B) 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 less, 5,000 mPa·s or less.

　Component (B) can be used alone or in combination of two or more. Among them, from the viewpoint of availability and the like, the component (B) is preferably one or more selected from the group consisting of carboxymethylcellulose and sodium carboxymethylcellulose, more preferably sodium carboxymethylcellulose. Commercially available carboxymethylcellulose sodium used as component (B) includes, for example, CMC Daicel series manufactured by Daicel Co., Ltd., Sunrose series manufactured by Nippon Paper Industries Co., Ltd., and the like.

The content of component (B) in the gel layer is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2.5% by mass or more, from the viewpoint of obtaining an appropriate shape-retaining property of the gel layer. It is 0% by mass or more, more preferably 2.3% by mass or more, and even more preferably 2.5% by mass or more. In addition, from the viewpoint of maintaining the adhesion to the skin and the viewpoint of handling, especially from the viewpoint of suppressing stickiness at the time of sticking the sheet and from the viewpoint of making it easy to restore the original state even if the adhesive surfaces are once stuck, It is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, still more preferably 3.8% by mass or less, and even more preferably 3.4% by mass or less. The content of component (B) in the gel layer is preferably 1.0% by mass or more and 5.0% by mass or less, more preferably 1.5% by mass or more and 4.0% by mass or less, still more preferably 2 0% by mass or more and 3.8% by mass or less, more preferably 2.3% by mass or more and 3.4% by mass or less, and even more preferably 2.5% by mass or more and 3.4% by mass or less.
When the component (B) is a salt of carboxymethylcellulose, the content of the 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 cross-linking agent for component (B), and forms a cross-linked structure in the gel layer through ionic interaction with component (B). it is conceivable that.
The supply 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 it is easy to supply as aluminum ions that can crosslink component (B). Inorganic metal salts containing aluminum are preferable from the viewpoint of hardness and water solubility.

Examples of the aluminum-containing compound (C1) that can act as a cross-linking agent for component (B), which is the source of component (C), include aluminum hydroxide, magnesium aluminum hydroxide, sodium aluminate, aluminum sulfate, and aluminum sulfate. Potassium, Aluminum Ammonium Sulfate, Aluminum Carbonate, Aluminum Nitrate, Aluminum Chloride, Magnesium Aluminate (Meth) Silicate, Aluminum Acetate, Aluminum Lactate, Aluminum Stearate, Aluminum Myristate, Aluminum Glycinate, Aluminum Benzoate, Allantoin ChloroHydroxy Aluminum etc., and one or more of these can be used.
Among the above, one or more selected from the group consisting of aluminum hydroxide and magnesium aluminosilicate (meth) as the component (C1) from the viewpoint of ease of supply of aluminum ions and water solubility. is preferred. Further, from the viewpoint of improving the storage stability of the gel layer, the component (C1) preferably contains two or more kinds of aluminum-containing compounds, more preferably at least magnesium (meth)silicate aluminate. More preferred are aluminum and magnesium alumino(meth)silicate.

The content of the component (C) in the gel layer is determined from the viewpoint of handleability, particularly from the viewpoint of suppressing stickiness at the time of sticking the sheet, and from the viewpoint of making it easy to restore the original state even if the adhesive surfaces are once stuck together, and storage. From the viewpoint of improving stability, it is preferably 0.002% by mass or more, more preferably 0.003% by mass or more, still more preferably 0.005% by mass or more, still more preferably 0.0062% by mass or more, and still more Preferably, it is 0.008% by mass or more. In addition, from the viewpoint of forming a gel layer that exhibits viscous properties in a wide frequency range and improving adhesion to the skin, the content is preferably 0.05% by mass or less, more preferably 0.04% by mass or less, and further preferably 0.04% by mass or less. It is preferably 0.035% by mass or less, and more preferably 0.02% by mass or less. The content of component (C) in the gel layer is preferably 0.002% by mass or more and 0.05% by mass or less, more preferably 0.003% by mass or more and 0.05% by mass or less, further preferably 0 0.005% by mass or more and 0.04% by mass or less, more preferably 0.0062% by mass or more and 0.035% by mass or less, and even more preferably 0.008% by mass or more and 0.02% by mass or less.
In addition, the content of the component (C) in the gel layer can be measured according to the Japanese Pharmacopoeia General Test Methods Inductively Coupled Plasma Atomic Emission Spectrometry and Inductively Coupled Plasma Mass Spectrometry.

The mass ratio [(B)/(C)] in the gel layer is preferably 70 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. is 85 or more, more preferably 100 or more. In addition, from the viewpoint of improving handleability, in particular, from the viewpoint of suppressing stickiness at the time of sticking the sheet, from the viewpoint of making it easy to restore the original state even if the adhesive surfaces are once stuck together, and from the viewpoint of improving storage stability, 800 or less, preferably 600 or less, more preferably 500 or less. 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, 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 including the component (D) in addition to the components (B) and (C), the tackiness of the gel layer and the viscous properties in the low frequency region are improved, thereby improving the adhesion to the skin. be able to.

Although the weight average molecular weight of component (D) is not particularly limited, it is preferably 30,000 or more, more preferably 50,000 or more, and still more preferably 70,000 or more from the viewpoint of obtaining an appropriate shape retention property of the gel layer. be. From the viewpoint of improving the adhesion of the sheet to the skin by improving the tackiness of the gel layer, it is preferably 150,000 or less, more preferably 110,000 or less, even more preferably 100,000 or less. The weight average molecular weight of component (D) is preferably from 30,000 to 150,000, more preferably from 50,000 to 110,000, even more preferably from 70,000 to 100,000.
When the weight average molecular weight of component (D) is preferably 150,000 or less, more preferably 110,000 or less, and still more preferably 100,000 or less, the entanglement of the polymer chains of component (D) in the gel layer It is thought that a more easily deformable gel structure can be formed. It is believed that this effect further improves the tackiness of the gel layer and improves the adhesion to the skin.
The weight average molecular weight of the raw material powder of component (D) can be obtained by measuring an aqueous solution obtained by dissolving the raw material powder in water by size exclusion chromatography (SEC) under the following conditions. The "powder raw material of component (D)" means powdery component (D) before being mixed with the gel layer or the gel-forming composition described below. Moreover, the weight average molecular weight of the component (D) in the gel layer is obtained by measuring the extract of the gel layer with 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: "PWXL (6 mm x 4 cm)" manufactured by Tosoh Corporation
Analysis column: Tosoh Corporation "G4000PWxL + G2500PWxL (7.8 mm × 30 cm)
Flow rate: 1mL/min
Column temperature: 40°C
Injection volume: 100 μL
Sample size: 1 mg/mL
Molecular weight conversion standard: Tosoh Corporation PEO (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

The degree of saponification of component (D) is preferably 75 mol% or more, more preferably 82 mol% or more, and even more preferably 82 mol% or more, from the viewpoint of improving the adhesion of the sheet to the skin by improving the tackiness of the gel layer. is 85 mol % or more. In addition, the degree of saponification of component (D) may be 100 mol% or less, preferably 98 mol% or less, more preferably 98 mol% or less, from the viewpoint of enhancing the water solubility of component (D) and improving its handleability. is 96 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 still more preferably 85 mol% or more and 96 mol% or less.
The degree of saponification of component (D) can be measured according to JIS K6726:1994.

Component (D) is preferably unmodified polyvinyl alcohol, but modified polyvinyl alcohol into which an ionic group or the like has been introduced can also be used, if necessary.
However, the component (D) preferably contains a small amount of functional groups capable of forming a crosslinked structure through ionic interaction with aluminum ions. This is because the formation of the crosslinked structure of the component (B) is not inhibited. For example, the content of carboxy groups in component (D) is preferably 0.1 mol % or less, more preferably 0.01 mol % or less, and still more preferably 0 mol %.

Commercially available polyvinyl alcohols used as component (D) include, for example, the Gohsenol series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., the Kuraray Poval series manufactured by Kuraray Co., Ltd., and the J vinyl alcohol manufactured by Japan Vinyl Acetate & Poval Co., Ltd. Poval series can be mentioned.

The content of component (D) in the gel layer is 8% by mass or more, preferably 8.3% by mass or more, more preferably 8.5% by mass or more, from the viewpoint of improving adhesion to the skin. be. In addition, from the viewpoint of improving the adhesion to the skin and the viewpoint of handleability, in particular, from the viewpoint of suppressing stickiness at the time of sticking the sheet and from the viewpoint of making it easy to restore the sticking between the adhesive surfaces to the original state, it is preferable. It is 18% by mass or less, more preferably 14% by mass or less, and still more preferably 12% by mass or less. The content of component (D) in the gel layer is 8% by mass or more, preferably 8% by mass or more and 18% by mass or less, more preferably 8.3% by mass or more and 14% by mass or less, and even more preferably It is 8.5 mass % or more and 12 mass % or less.
The content of component (D) in the gel layer can be obtained by measuring the extract of the gel layer with ¹ H-NMR under the following conditions.
< ¹ H-NMR measurement conditions>
Measuring device: JEOL "MR-400"
Observation nucleus: 1H
Frequency: 300MHz or more Pulse delay time: 25 seconds Accumulation times: 32 times Mode: Presaturation
Solvent: _D2O
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, and still more preferably 2.8 or more, from the viewpoint of improving adhesion to the skin. , and more preferably 3 or more. In addition, from the viewpoint of improving the adhesion to the skin and the viewpoint of handling, especially from the viewpoint of suppressing stickiness at the time of sticking the sheet and making it easy to restore the original state even if the adhesive surfaces are once stuck, It is preferably 8 or less, more preferably 6 or less, even more preferably 5 or less, even more preferably 4.5 or less, and even more preferably 4 or less. 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, still more preferably 2.8 or more and 5 or less, and even more preferably 3 or more and 4.5 or less, more preferably 3 or more and 4 or less.

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 still more preferably 85% by mass or more, from the viewpoint of obtaining the effects of the present invention. and is 100% by mass or less.

(other ingredients)
The gel layer may appropriately contain components other than the components (A) to (D) as long as the objects of the present invention are not impaired. Other ingredients include, for example, ingredients commonly used in cosmetics, cosmetics, pharmaceuticals, quasi-drugs, and the like.
Components commonly used in these products include, for example, water-soluble polymers other than component (B) and component (D), moisturizing agents, whitening agents, blood circulation promoters, antiphlogistic agents, bactericides, and ultraviolet absorbers. , coloring agents, preservatives, antioxidants, perfumes, oils, pH adjusters, chelating agents, water retention agents, chemicals, cooling agents, warming agents, alcohols, and the like.

In addition, the gel layer is a polyacrylic acid or a salt thereof from the viewpoint of improving handleability, in particular, from the viewpoint of suppressing stickiness at the time of sticking the sheet and from the viewpoint of making it easy to return to the original state even if the adhesive surfaces are once stuck. It is preferable that the content of Specifically, the content of polyacrylic acid or a salt thereof in the gel layer is preferably less than 4% by mass, more preferably less than 3% by mass, still more preferably 2% by mass or less, and even more preferably is 1% by mass or less, and more preferably 0% by mass. Commercially available polyacrylic acid or salts thereof include, for example, Aronbis series and Julimer series manufactured by Toagosei Co., Ltd., and 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. Therefore, it is preferably 5 mm or less, more preferably 3 mm or less, still more preferably 2 mm or less.

<Gel-forming composition>
The gel layer constituting the sheet of the present invention contains the following components (A) to (D):
(A) water (B) carboxymethyl cellulose or a salt thereof (C) an aluminum atom (D) containing polyvinyl alcohol, the content of component (A) is 50% by mass or more and 85% by mass or less, and the content of component (D) is It can be formed using a gel-forming composition having a content of 8% by mass or more and a mass ratio [(B)/(C)] of 70 or more and 800 or less. 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.

Further, the gel layer constituting the sheet of the present invention contains the following components (A), (B), (C1) and (D):
(A) water (B) carboxymethyl cellulose or its salt (C1) an aluminum-containing compound (D) polyvinyl alcohol,
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,
It is preferable to use a gel-forming composition having a mass ratio [(B)/(C1)] of 25 or more and 140 or less.
Unless otherwise specified, the components (A), (B), (C1) and (D) to be mixed in the gel-forming composition, other components, and preferred embodiments thereof are described in the gel layer. Same as content.

The amounts of components (A), (B) and (D) blended in the gel-forming composition and their preferred ranges are determined by the contents of components (A), (B) and (D) in the gel layer. It is the same as the amount and its preferred range.

When two or more types of polyvinyl alcohol are blended as the component (D), the weight average molecular weight of each polyvinyl alcohol is preferably within the above range. The two or more polyvinyl alcohols referred to here mean polyvinyl alcohols different from each other in weight average molecular weight, degree of saponification, or both.

In the gel-forming composition, the blending amount of component (B) relative to the blending amount of component (C1) (mass ratio [(B)/(C1)]) forms a gel layer that exhibits viscous properties in a wide frequency range. , preferably 25 or more, more preferably 50 or more, and even more preferably 60 or more, from the viewpoint of improving adhesion to the skin. In addition, from the viewpoint of improving handleability, in particular, from the viewpoint of suppressing stickiness at the time of sticking the sheet, from the viewpoint of making it easy to restore the original state even if the adhesive surfaces are once stuck together, and from the viewpoint of improving storage stability, It is preferably 140 or less, more preferably 130 or less, even more preferably 120 or less, even more preferably 100 or less, and even more preferably 95 or less. The mass ratio [(B)/(C1)] is preferably 25 or more and 140 or less, more preferably 25 or more and 130 or less, still more preferably 50 or more and 120 or less, still more preferably 50 or more and 100 or less, and even more preferably is 60 or more and 95 or less.

The amount of the component (C1) blended in the gel-forming composition should be such that the mass ratio [(B)/(C1)] falls within the above range. From the viewpoint of improving handleability, in particular, from the viewpoint of suppressing stickiness at the time of sticking the sheet, from the viewpoint of making it easy to restore the original state even if the adhesive surfaces are once stuck together, and from the viewpoint of improving storage stability. The amount is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass or more in the composition. In addition, from the viewpoint of forming a gel layer that exhibits viscous properties in a wide frequency range and improving the adhesion to the skin, the content is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and furthermore preferably 0.1% by mass or less. The amount is preferably 0.06% by mass or less, and more preferably 0.04% by mass or less. The amount of component (C1) blended in the gel-forming composition is preferably 0.005% by mass or more and 0.2% by mass or less, more preferably 0.005% by mass or more and 0.1% by mass or less, The amount is more preferably 0.01% by mass or more and 0.06% by mass or less, and still more preferably 0.02% by mass or more and 0.04% by mass or less.

From the viewpoint of obtaining the effects of the present invention, 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. % by mass or more, more preferably 85% by mass or more, and 100% by mass or less.

A cross-linking agent component other than the component (C1) may be added to the gel-forming composition as long as it does not impair the effects of the present invention, but the amount thereof is preferably small. The amount of the cross-linking component other than component (C1) is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 0% by mass of the total cross-linking agent component.

Although the method for preparing the gel-forming composition is not particularly limited, it is preferable to prepare an aqueous solution by previously dissolving the component (D) in water, and then mix the component (D) with other components in the form of an aqueous solution. After that, all the other components may be put into a kneader and mixed, or some components may be mixed or dispersed and then put into a kneader and mixed.

<Structure of Body Adhesion Sheet>
The configuration 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 the sheet's handleability and strength, it preferably has the gel layer and a base material. That is, the body patch sheet 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. The peel film is used to protect the gel layer, and is a film that is peeled off from the gel layer when the sheet is attached. . Among these, from the viewpoint of imparting excellent peelability, embossed films are preferred, and embossed non-axially stretched polypropylene films are more preferred.
From the standpoint of sheet handling, the body patch sheet of the present invention preferably has a three-layer structure comprising a substrate, a gel layer, and a release film in this order.

(Base material)
As the substrate constituting the sheet of the present invention, sheet-like substrates such as woven fabrics, nonwoven fabrics, woven fabrics, synthetic resin films, and water-resistant papers can be used. Moreover, a laminated base material in which a plurality of these sheet-like base materials are laminated can also be used.
Specifically, synthetic fiber woven or non-woven fabrics made of nylon, polypropylene, polyester, polyethylene, polystyrene, polyurethane, polyolefin, etc.; natural fiber woven or non-woven fabrics made of silk, cotton, hemp, rayon, collagen, etc.; nylon films made of synthetic resins such as , polypropylene, polyester, polyethylene, and polyurethane; sheet-like substrates made of pullulan, starch, etc.;
Among the above, the substrate is preferably a nonwoven fabric, and more preferably a nonwoven fabric made of nylon, polypropylene, polyester, or polyethylene, from the viewpoint of sheet handling, ease of lamination of the gel layer, and followability. .

Although the thickness of the base material is not particularly limited, it is preferably 0.1 mm or more from the viewpoint of sheet handling property and ease of stacking the gel layer, and preferably 5 mm or less from the viewpoint of improving followability. , more preferably 3 mm or less, and still more preferably 2 mm or less.
Although the basis weight of the substrate is not particularly limited, it is preferably 10 g/m ² or more from the viewpoint of sheet handling and ease of stacking the gel layer, and preferably 200 g from the viewpoint of improving followability. /m ² or less, more preferably 150 g/m ² or less, and even more preferably 120 g/m ² or less.

[Manufacturing method of body patch sheet]
The present invention provides a method for producing a body adhesive sheet having a gel layer, comprising the following steps (I) to (III) in this order. By this production method, the body patch sheet of the present invention can be produced efficiently.
Step (I) The following components (A), (B), (C1) and (D):
(A) water (B) carboxymethyl cellulose or its salt (C1) an aluminum-containing compound (D) polyvinyl alcohol,
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,
Step (II) of preparing a gel-forming composition having a mass ratio [(B)/(C1)] of 25 or more and 140 or less Filling the gel-forming composition between the substrate and the release film, Step (III): The laminated sheet is sealed in a package, and then the gel-forming composition layer is crosslinked in the package. the process of causing

<Process (I)>
In step (I), the following components (A), (B), (C1) and (D):
(A) water (B) carboxymethyl cellulose or its salt (C1) an aluminum-containing compound (D) polyvinyl alcohol,
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,
A gel-forming composition having a mass ratio [(B)/(C1)] of 25 or more and 140 or less is prepared. The gel-forming composition, its preparation method, and its preferred embodiments are as described above.

<Step (II)>
In step (II), the gel-forming composition is filled between the substrate and the release film to produce a laminated sheet having the substrate, the gel-forming composition layer, and the release film in this order. The substrate and release film are as described above.
As a method of filling the gel-forming composition between the base material and the release film and laminating, for example, the gel-forming composition is sandwiched between the base material and the release film, and then a baker-type applicator or the like is applied. a method of applying a gel-forming composition to a desired thickness on a release film, and then laminating a base material; and the like. Alternatively, the base material and the release film are made to face each other and run on transport rolls, respectively, the gel-forming composition is filled between the base material and the release film, and the mixture is sent out while being pressed by the rolls to form a laminated sheet. can also At this time, the thickness of the gel-forming composition layer can be adjusted to a desired thickness by adjusting the distance between the two rolls.
If necessary, the laminated sheet obtained in step (II) is cut into a desired size before being subjected to step (III).

<Step (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. Thereby, a gel layer having 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, the package should have gas barrier properties. is more preferred. A specific example of the package includes a package having at least a layer made of silicon, aluminum, or oxides thereof. From the viewpoint of moisture barrier properties, gas barrier properties, and economy, the package body preferably contains an aluminum layer.

The cross-linking conditions for the gel-forming composition layer are not particularly limited, but from the viewpoint of improving the productivity of the body patch sheet having the gel-forming composition and the gel layer comprising the composition, the cross-linking 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.

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

The body patch sheet of the present invention is used by being attached to the outer skin (excluding the scalp). The body part is not particularly limited, and even when applied to a highly curved part such as an elbow or knee, it follows movement and does not peel off easily, is resistant to oil, and has good re-applicability and long-term application properties.

Hereinafter, the present invention further discloses the following regarding the above-described embodiments.
<1>
A body patch sheet having a gel layer,
The gel layer comprises the following components (A)-(D):
(A) water (B) carboxymethyl cellulose or a salt thereof (C) an aluminum atom (D) containing 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 body patch sheet having a mass ratio [(B)/(C)] of 70 or more and 800 or less.
<2>
The content of component (A) in the gel layer is preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and preferably 80% by mass or less, more preferably 78% by mass. The body patch sheet of <1>, which is 77% 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% by mass or more, more preferably 1.5% by mass or more, still more preferably 2.0% by mass or more, and even more preferably 2.3% by mass. % by mass or more, more preferably 2.5% by mass or more, preferably 5.0% by mass or less, more preferably 4.0% by mass or less, even more preferably 3.8% by mass or less, still more preferably The body patch sheet of <1> or <2>, which is 3.4% by mass or less.
<4>
The content of component (C) in the gel layer is preferably 0.002% by mass or more, more preferably 0.003% by mass or more, still more preferably 0.005% by mass or more, and even more preferably 0.0062% by mass. % by mass or more, more preferably 0.008% by mass or more, preferably 0.05% by mass or less, more preferably 0.04% by mass or less, even more preferably 0.035% by mass or less, still more preferably The body patch sheet according to any one of <1> to <3>, which is 0.02% by mass or less.
<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, and still more preferably 500 or less. The body patch sheet according to any one of <4>.
<6>
The weight average molecular weight of component (D) is preferably 30,000 or more, more preferably 50,000 or more, still more preferably 70,000 or more, and preferably 150,000 or less, more preferably 120,000 or less. , and more preferably 100,000 or less, the body patch sheet according to any one of <1> to <5>.
<7>
The degree of saponification of component (D) is preferably 75 mol% or more, more preferably 82 mol% or more, still more preferably 85 mol% or more, and preferably 98 mol% or less, more preferably 96 mol% or less. The body patch sheet according to any one of <1> to <6>.
<8>
The content of component (D) in the gel layer is preferably 8.3% by mass or more, more preferably 8.5% by mass or more, and preferably 18% by mass or less, more preferably 14% by mass or less, The body patch sheet according to any one of <1> to <7>, which is more preferably 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, still more preferably 2.8 or more, still more preferably 3 or more, preferably The body patch sheet according to any one of <1> to <8>, which is 8 or less, more preferably 6 or less, still more 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% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more, and is 100% by mass. A body patch sheet according to any one of <1> to <9> below.

<11>
The content of polyacrylic acid or a salt thereof in the gel layer is preferably less than 4% by mass, more preferably less than 3% by mass, still more preferably 2% by mass or less, and even more preferably 1% by mass. The body patch sheet according to any one of <1> to <10>, which is less than or equal to 0 mass%, and more preferably 0% by mass.
<12>
The body patch sheet according to any one of <1> to <11>, wherein the gel layer has a crosslinked structure in which the component (B) is crosslinked by the component (C).
<13>
In accordance with JIS Z0237:2009, the gel layer was slanted at an angle of 30°, at a temperature of 23°C, and subjected to 50% R.I. H. The ball number in the ball tack test conducted under the conditions is preferably 15 or more, more preferably 18 or more, still more preferably 19 or more, still more preferably 20 or more, preferably 32 or less, more preferably 30 or less, The body patch sheet according to any one of <1> to <12>, which is more preferably 28 or less, still 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, still more preferably 0.22 or more, and even more preferably. is 0.25 or more, still more preferably 0.28 or more, preferably 0.60 or less, more preferably 0.58 or less, still more preferably 0.50 or less, <1> to <13> Any 1 body sticking sheet.
<15>
The thickness of the gel layer is preferably 0.1 mm or more, more preferably 0.3 mm or more, still more preferably 0.5 mm or more, and preferably 5 mm or less, more preferably 3 mm or less, still more preferably 2 mm or less. The body patch sheet according to any one of <1> to <14>.
<16>
<1> to <15, wherein the body patch sheet has a two-layer structure in which the gel layer and the substrate are laminated, or a three-layer structure in which the substrate, the gel layer, and the release film are arranged in this order. The sheet for body application according to any one of >.
<17>
The body adhesive sheet of <16>, wherein the substrate is preferably a nonwoven fabric, more preferably a nonwoven fabric made of nylon, polypropylene, polyester, or polyethylene.
<18>
A body patch sheet having a gel layer,
The gel layer comprises the following components (A), (B), (C1) and (D):
(A) Water (B) Carboxymethylcellulose or its salt (C1) Aluminum-containing compound (D) A gel-forming composition containing polyvinyl alcohol, wherein the content of component (A) is 50% by mass or more 85 % by mass or less, the amount of component (D) is 8% by mass or more, and the mass ratio (B)/(C1) is 25 or more and 140 or less,
A body application sheet, comprising component (B) crosslinked with component (C1).
<19>
The following components (A)-(D):
(A) water (B) carboxymethyl cellulose or a salt thereof (C) an aluminum atom (D) containing polyvinyl alcohol, the content of component (A) is 50% by mass or more and 85% by mass or less, and the content of component (D) is A gel-forming composition having a content of 8% by mass or more and a mass ratio [(B)/(C)] of 60 or more and 800 or less.
<20>
The following components (A), (B), (C1) and (D):
(A) water (B) carboxymethyl cellulose or its salt (C1) an aluminum-containing compound (D) polyvinyl alcohol,
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,
A gel-forming composition having a mass ratio [(B)/(C1)] of 25 or more and 140 or less.
<21>
The amount of component (C1) blended in the gel-forming composition is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass or more, and is preferred. <18> body patch sheet or The gel-forming composition of <20>.
<22>
The amount of component (B) blended with respect to the blended amount of component (C1) (mass ratio [(B)/(C1)]) is more preferably 50 or more, still more preferably 60 or more, and more preferably 130 or less. , more preferably 120 or less, still more preferably 100 or less, still more preferably 95 or less, the body patch sheet of <18> or 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 aluminosilicate (meth)silicate , aluminum acetate, aluminum lactate, aluminum stearate, aluminum myristate, aluminum glycinate, aluminum benzoate, one or more selected from the group consisting of allantoin chlorohydroxyaluminum, more preferably aluminum hydroxide and aluminum (meth)silicate The body of <18> containing one or more selected from the group consisting of magnesium acid, more preferably magnesium (meth)silicate aluminate, and still more preferably aluminum hydroxide and magnesium (meth)silicate aluminate A patch sheet, and the gel-forming composition according to any one of <20> to <22>.

<24>
A method for producing a body adhesive sheet having a gel layer, comprising the following steps (I) to (III) in this order.
Step (I) The following components (A), (B), (C1) and (D):
(A) water (B) carboxymethyl cellulose or its salt (C1) an aluminum-containing compound (D) polyvinyl alcohol,
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,
Step (II) of preparing a gel-forming composition having a mass ratio [(B)/(C1)] of 25 or more and 140 or less Filling the gel-forming composition between the substrate and the release film, Step (III): The laminated sheet is sealed in a package, and then the gel-forming composition layer is crosslinked in the package. the process of causing

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 performed by the following methods.

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

<Weight Average Molecular Weight of Component (D)>
The weight average molecular weight of the raw material powder of component (D) was determined by measuring an aqueous solution obtained by dissolving the raw material powder in water by size exclusion chromatography (SEC) under the following conditions. The weight average molecular weight of the component (D) in the gel layer was obtained by measuring the gel layer extract 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 gel layer.
<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: "PWXL (6 mm x 4 cm)" manufactured by Tosoh Corporation
Analysis column: "G4000PWxL + G2500PWxL (7.8 mm x 30 cm)" manufactured by Tosoh Corporation
Flow rate: 1mL/min
Column temperature: 40°C
Injection volume: 100 μL
Sample size: 1 mg/mL
Molecular weight conversion standard: Tosoh Corporation PEO (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

Examples 1 to 27, Comparative Examples 1 to 9 (preparation of gel-forming composition, production and evaluation of body patch sheet)
(Preparation of gel-forming composition)
A gel-forming composition was prepared according to the formulation shown in the table. Specifically, a solution in which methyl p-hydroxybenzoate and menthol were heated and dissolved in propylene glycol 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 charged into a kneader, then all other components were added and mixed to prepare a gel-forming composition. In addition, the compounding quantity described in the table|surface is the active-ingredient amount (mass %) of each component. In the table, a polymer having cross-linking ability by aluminum ions and not belonging to component (B) is indicated as "component (B')".

(Manufacturing of Body Adhesion Sheet)
The gel-forming composition is sandwiched between a polyester non-woven fabric (thickness of 0.7 mm) as a substrate and a polypropylene release film, and the thickness of the gel-forming composition layer is reduced to 1.5 mm with a baker applicator. By adjusting and spreading, a sheet was obtained in which the nonwoven fabric, the gel-forming composition layer, and the release film were laminated in this order. After the sheet was cut into 12.5 cm x 8.5 cm and sealed in an aluminum pillow (120 mm x 170 mm, manufactured by AS ONE), it was aged under the conditions shown in the table to promote the cross-linking reaction of the gel-forming composition layer. A body patch sheet having a three-layer structure having a nonwoven fabric, a gel layer, and a release film in this order was produced.
Using the obtained body patch sheet, evaluation was performed by the following methods. The results are shown in Tables 1-5.

<Ball tack test>
The ball tack test of the gel layer of the body patch sheet of each example was carried out according to JIS Z0237:2009 with an inclined plate angle of 30°, a temperature of 23°C, and a R.E. H. was performed under the conditions of Remove the sheet for body application of each example from the aluminum pillow, peel off the release film, and immediately place it in a ball tack tester to perform a ball tack test. The numbers are shown in the table.

<Loss tangent (tan δ)>
The loss tangent (tan δ) of the gel layer of the body patch sheet of each example was measured using a rheometer (“Physica MCR301” manufactured by Anton Paar Ltd.). A circle with a diameter of 25 mm was cut out from each example of the sheet to be attached to the body, and the nonwoven fabric side was fixed to the sample section (parallel flat plate with a diameter of 25 mm) of the rheometer with double-sided tape. Then, the release film was peeled off, 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 times or more), and the average value was adopted.
〔Measurement condition〕
・Normal force: 1N
・Gap distance: 1 to 2 mm
・Gel layer mass: 0.5 to 1.0 g
・Measurement frequency: 0.1Hz
・Strain: 2%
・Temperature: 25℃

<Adhesion (calf)>
Adhesiveness immediately after application The body application sheet of each example was removed from the aluminum pillow, and immediately after peeling off the release film, was applied to the calf of the expert panelist so that the long side of the sheet was perpendicular to the circumferential direction of the calf. After 10 seconds from application, a specialist panelist performed plantar dorsiflexion of the ankle 10 times, and measured the area of the part where the body application sheet was lifted from the calf, that is, the area of the part peeled off from the calf. The ratio (%) of the area where the sheet was peeled off relative to the total area of the body patch sheet was determined and evaluated according to the following criteria. The higher the evaluation value, the better the adhesion immediately after application.
In addition, the evaluation by the expert panelists in this example was conducted by three panelists, and the evaluation values shown in the table are the average values of the three panelists.
〔Evaluation criteria〕
7: The ratio of the area of the portion where the sheet is peeled is 5% or less.
6: The ratio of the area of the portion where the sheet is peeled is more than 5% and 10% or less.
5: The ratio of the area of the portion where the sheet is peeled is more than 10% and 20% or less.
4: The percentage of the area where the sheet is peeled off is more than 20% and 30% or less.
3: The ratio of the area of the portion where the sheet is peeled off is more than 30% and 40% or less.
2: The percentage of the area where the sheet is peeled off is more than 40% and 50% or less.
1: The ratio of the area of the portion where the sheet is peeled is more than 50%.

Re-adherability The body application sheet of each example was applied to the calf of the expert panelist in the same manner as described above, and 10 seconds after application, the sheet was removed. After the same trial was repeated, the peeled body adhesive sheet was again applied to the other calf of the expert panelist in the same manner as described above, and after 10 seconds, the ankle plantar dorsiflexion exercise was performed 10 times. The area of the part 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-sticking.

Adhesion after Application of Cream Commercially available body cream (oil agent: 11%, emulsifier: 2.5%, polyol: 12%, water: 72%, others: 2.5%) was applied to the calves of professional panelists. Next, in the same manner as described above, the sheet for body application of each example was applied to the calf of the expert panelist, and 10 seconds after application, the expert panelist performed ankle plantar dorsiflexion exercise 10 times. The area of the part 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 application of the body cream.

Long-term Adhesion The body application sheet of each example was applied to the calf of a specialist panelist in the same manner as described above. The difficulty of peeling after sticking for 3 hours was evaluated in 5 stages (5 points: very difficult to peel, 4 points: difficult to peel, 3 points: slightly difficult to peel, 2 points: slightly easy to peel, 1 point: easy to peel). . The higher the evaluation value, the better the adhesion after long-term application.

<Adhesion (knee)>
Adhesion under Load Conditions Adhesion was evaluated under load conditions. Under this load condition, the body application sheet is attached to a highly curved portion and motion is added to the attached portion, so that the adhesion and followability immediately after being attached to the highly curved portion can be evaluated.
The body application sheet of each example was taken out from the aluminum pillow, and immediately after peeling off the release film, the sheet was applied to the knee of the expert panelist so that the long side of the sheet was parallel to the circumferential direction of the knee. 10 seconds after application, a specialist panelist performs 10 knee bending and stretching exercises (90° to 180°), and measures the area of the part where the body application sheet is lifted from the knee, that is, the part peeled off from the knee. did. The ratio (%) of the area of the part where the sheet was peeled off relative to the area of the entire body patch sheet was determined. Evaluation criteria are the same as for calf adhesion. A higher evaluation value indicates better adhesion under load conditions.

<Handleability>
(Ease of application)
The body application sheet of each example was taken out from the aluminum pillow, and immediately after peeling off the release film, it was applied to the calf of the expert panelist so that the long side of the sheet was perpendicular to the circumferential direction of the calf. Five levels of ease of application (5 points: very easy to apply, 4 points: easy to apply, 3 points: slightly easy to apply, 2 points: slightly difficult to apply, 1 point: difficult to apply) evaluated with A higher evaluation value indicates that the body patch sheet can be easily and cleanly applied, and a lower value indicates that wrinkles or the like are generated and it is difficult to cleanly apply the body patch sheet.

(Stickiness on fingers)
The stickiness of the adhesive surface (gel layer) to the finger when the sheet for body application of each example is applied in the same manner as described above is evaluated in 5 levels (5 points: not sticky, 4 points: not very sticky, 3 points: slightly sticky, 2 points: sticky, 1 point: very sticky). A higher evaluation value indicates a lower degree of stickiness to fingers.

(Ease of releasing adhesive surfaces)
The body patch sheet of each example was taken out from the aluminum pillow, the release film was peeled off, the sheet was folded in two, and the adhesive surfaces were adhered to each other. Next, the ease of release when releasing the adhesive surface was rated in 5 levels (5 points: easy to release, 4 points: slightly easy to release, 3 points: slightly difficult to release, 2 points: difficult to release, 1 point: very difficult to release). evaluated. The higher the evaluation value, the easier it is to separate the adhesive surfaces once they are stuck together (the easier it is to return to the original state), indicating that the handleability is good.

<Storage stability>
The body patch sheet of each example was stored in a constant temperature bath at 50°C for one month in a state of being enclosed in an aluminum pillow, and then returned to 25°C. The sheet for body application was taken out from the aluminum pillow, and the appearance and the storage stability of the gel property were evaluated in 5 grades according to the following criteria. A higher evaluation value indicates higher storage stability.
(exterior)
5: Equivalent to the state before storage 4: Discoloration of the gel, bleeding into the nonwoven fabric is slightly observed 3: Discoloration of the gel, bleeding into the nonwoven fabric is slightly observed 2: Discoloration of the gel, bleeding into the nonwoven fabric 1: Difficult to use as a sheet (gel property)
The body application sheet of each example was taken out from the aluminum pillow, applied to the forearm of the expert panelist for 30 minutes, and then peeled off.
5: Equivalent to the state before storage (gel does not remain on the skin)
4: Gel slightly remains on skin 3: Gel slightly remains on skin 2: Gel is fragile and a large amount of gel remains on skin 1: Difficult to use as a sheet

From Tables 1 to 5, it can be seen that the body patch sheet of this example has good adhesion immediately after application to the skin and good adhesion under load conditions, is difficult to peel off when applied for a long period of time, and has good adhesion to skin with oily skin. Adhesion to the surface and re-adherability are also good. In addition, the gel layer is excellent in handleability at the time of application, and the gel layer is less likely to deteriorate over time and has good storage stability. On the other hand, the body patch sheet of this comparative example could not satisfy all of the adhesiveness immediately after application to the skin, the adhesiveness under load conditions, and the ease of application to the skin.

FIG. 1 is a graph showing the viscoelastic behavior (relationship between measurement frequency and loss tangent (tan δ)) of the gel layers of the body patch sheets obtained in Example 1 and Comparative Example 4. As shown in FIG. 1, the gel layer of Example 1 has a loss tangent of 0.20 or more in a wider frequency range than that of Comparative Example 4, indicating that it has viscous properties.

Claims

A body patch sheet having a gel layer,
The gel layer comprises the following components (A)-(D):
(A) water (B) carboxymethyl cellulose or a salt thereof (C) an aluminum atom (D) containing 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 body patch sheet having a mass ratio [(B)/(C)] of 70 or more and 800 or less.
The body patch sheet according to claim 1, wherein the gel layer has a crosslinked structure in which the component (B) is crosslinked by the component (C).
The body patch sheet according to claim 1 or 2, wherein the component (D) has a weight average molecular weight of 150,000 or less.
The body patch sheet according to any one of claims 1 to 3, wherein the component (D) has a degree of saponification of 75 mol% or more.
The gel layer was subjected to JIS Z0237: 2009 with an inclined plate angle of 30°, a temperature of 23°C, and a R.E. H. 5. The body patch sheet according to any one of claims 1 to 4, which has a ball number of 15 or more and 30 or less in a ball tack test conducted under the conditions of .
The body adhesive sheet according to any one of claims 1 to 5, 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 body adhesive sheet having a gel layer, comprising the following steps (I) to (III) in this order.
Step (I) The following components (A), (B), (C1) and (D):
(A) water (B) carboxymethyl cellulose or its salt (C1) an aluminum-containing compound (D) polyvinyl alcohol,
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,
Step (II) of preparing a gel-forming composition having a mass ratio [(B)/(C1)] of 25 or more and 140 or less Filling the gel-forming composition between the substrate and the release film, Step (III): The laminated sheet is sealed in a package, and then the gel-forming composition layer is crosslinked in the package. the process of causing