WO2022264653A1 - Sheet for application to body - Google Patents
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- WO2022264653A1 WO2022264653A1 PCT/JP2022/016558 JP2022016558W WO2022264653A1 WO 2022264653 A1 WO2022264653 A1 WO 2022264653A1 JP 2022016558 W JP2022016558 W JP 2022016558W WO 2022264653 A1 WO2022264653 A1 WO 2022264653A1
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Classifications
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-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/16—Emollients or protectives, e.g. against radiation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
Definitions
- 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.
- 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 ⁇ -glucan.
- 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.
- 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.
- a body patch sheet having a 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.
- 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
- FIG. 2 is a graph showing viscoelastic behavior (relationship between measurement frequency and loss tangent (tan ⁇ )) of the gel layers of the body patch sheets obtained in Example 1 and Comparative Example 4.
- FIG. 2 is a graph showing viscoelastic behavior (relationship between measurement frequency and loss tangent (tan ⁇ )) of the gel layers of the body patch sheets obtained in Example 1 and Comparative Example 4.
- 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.
- 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.
- 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.
- adhesion 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).
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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).
- 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.
- 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.
- 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.
- 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.
- 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.
- the viscous property and elastic property of the gel layer can be evaluated using the value of loss tangent (tan ⁇ ) as an index.
- a gel layer with a large loss tangent value means a higher viscous property.
- 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.
- it is preferably 0.70 or less, more preferably 0.60.
- 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.
- the loss tangent of the gel layer can be measured by the method described in Examples.
- 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.
- a sheet with high tack strength exhibits high adhesion immediately after application to the skin.
- 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.
- 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
- component (A) water
- purified water such as deionized water, distilled water, highly pure water, and ultrapure water
- 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.
- 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).
- 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.
- component (B) 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.
- 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.
- 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.
- 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)
- 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.
- 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.
- 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.
- 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.
- 800 or less 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).
- component (D) polyvinyl alcohol
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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 %.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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,
- 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.
- 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.
- the blending amount of component (B) relative to the blending amount of component (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.
- 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.
- 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.
- 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.
- 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.
- 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. .
- 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.
- 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.;
- 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. .
- 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.
- 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.
- 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.
- 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
- 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) 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.
- 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.
- 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.
- 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) 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.
- a body patch sheet having a 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,
- 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.
- 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.
- 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.
- 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 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>.
- 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 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 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 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.
- 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 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.
- 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.
- 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 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 >.
- a body patch sheet having a gel layer comprising 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).
- component (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.
- 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.
- 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.
- the amount of component (B) blended with respect to the blended amount of component (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>.
- 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
- 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
- ⁇ 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.
- 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.
- surface is the active-ingredient amount (mass %) of each component.
- a polymer having cross-linking ability by aluminum ions and not belonging to component (B) is indicated as "component (B')".
- 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.
- 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 ⁇ )> The loss tangent (tan ⁇ ) 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 ⁇ ) was calculated from these values.
- 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.
- ⁇ 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%.
- 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.
- 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.
- 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.
- ⁇ 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
- 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.
- 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.
- 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.
- 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.
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Abstract
Description
例えば特開2005-314290号公報(特許文献1)には、支持体と、当該支持体の少なくとも一方の面上に配置された粘着剤層と、を備える貼付剤であって、前記粘着剤層がβ-グルカンを含む粘着基剤から形成されることを特徴とする貼付剤が、使用感に優れ、かつ、充分な粘着力を有することが開示されている。
特開2013-79198号公報(特許文献2)には、少なくともゲル基体層、支持体層、及び粘着層を有し、かつこの順で積層された層構造を有する、ゲル基体層の他の層が接していない側の表面の一部又は全部と冷却対象部位が、直接触れるように装着して使用する衣料装着用冷却シートであって、ゲル基体層がポリビニルアルコールを含む冷却用組成物から形成され、ポリビニルアルコールを所定量含む衣料装着用冷却シートが、人体の皮膚等の冷却対象部位に触れても、べたつかず、冷却及び保冷効果に優れることが開示されている。 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.
国際公開第2018/155310号(特許文献4)には、ゼラチン、ポリビニルアルコール、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合体、及びL-メンチルグリセリルエーテルをそれぞれ所定量含有する貼付剤用基剤が、清涼化剤としてL-メンチルグリセリルエーテルを用いた場合であっても、基剤の粘着力を保持しつつ、不快な臭いの発生が抑制された貼付剤用基剤及びそれを用いた貼付剤を提供できることが開示されている。 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.
[1]ゲル層を有する身体貼付用シートであって、
該ゲル層は、次の成分(A)~(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C)アルミニウム原子
(D)ポリビニルアルコール
を含有し、
該ゲル層中の成分(A)の含有量が50質量%以上85質量%以下であり、
該ゲル層中の成分(D)の含有量が8質量%以上であり、
質量比[(B)/(C)]が70以上800以下である、身体貼付用シート。
[2]下記工程(I)~工程(III)をこの順で含む、ゲル層を有する身体貼付用シートの製造方法。
工程(I) 次の成分(A)、(B)、(C1)及び(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C1)アルミニウム含有化合物
(D)ポリビニルアルコール
を配合してなり、
成分(A)の配合量が50質量%以上85質量%以下であり、
成分(D)の配合量が8質量%以上であり、
質量比[(B)/(C1)]が25以上140以下であるゲル形成用組成物を調製する工程
工程(II) 基材と剥離フィルムとの間に前記ゲル形成用組成物を充填し、基材、ゲル形成用組成物層、及び剥離フィルムを順に有する積層シートを作製する工程
工程(III) 前記積層シートを包装体内に密封し、次いで該包装体内で前記ゲル形成用組成物層を架橋させる工程 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
しかし、従来の身体貼付用シートでは、身体貼付用シートを皮膚に貼付する際にシートの粘着面の指へのべたつきを感じたり、剥離フィルムを剥がした後にシートの粘着面同士が貼り付いた際、元の状態に戻しにくい等、取り扱い性の問題も生じ得る。すなわち、密着性を高めようとすると取り扱い性に問題が生じ、また、取り扱い性を高めようとすると密着性が劣る結果となる。以上の点で、従来の身体貼付用シートにおいては改善の余地があった。 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.
以下の記載において、「(身体貼付用シートの)皮膚への密着性が良好である」とは、少なくとも、皮膚への貼付直後の密着性、及び、負荷条件下での密着性がともに良好であることをいう。「貼付直後の密着性」とは、関節以外の部分(例えばふくらはぎ)に身体貼付用シートを貼付した直後に日常動作を行った場合の密着性を意味する。また「負荷条件下での密着性」とは、曲率の高い部分(例えばひざ等の関節部分)に身体貼付用シートを貼付した直後に、貼付部分に動きを加えた場合の密着性を意味する。皮膚への貼付直後の密着性、及び、負荷条件下での密着性は、実施例に記載の方法により評価できる。
さらに、本発明の身体貼付用シートは長時間貼付時の剥がれにくさ、油分の存在する皮膚への密着性、並びに再貼付性も良好である。
本発明において、「(身体貼付用シートの)貼付時の取り扱い性に優れる」とは、少なくとも、身体貼付用シートを皮膚に貼付しやすいことを意味する。シートの皮膚への貼付しやすさは、実施例に記載の方法により評価できる。
さらに、本発明の身体貼付用シートは、シートの粘着面の指へのべたつきが抑制されること、貼付時にシートの粘着面同士が貼り付いた際に、粘着面同士を離しやすい(元の状態に戻しやすい)ことにも優れる。
なお、本発明の身体貼付用シートの粘着面とは、該シートのゲル層面を意味する。また、以下の記載において「貼付時にシートの粘着面同士が貼り付いた際に、粘着面同士を離しやすい(元の状態に戻しやすい)こと」を「粘着面同士が一旦貼り付いても元の状態に戻しやすい」ともいう。 [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.
本発明の身体貼付用シート(以下、単に「本発明のシート」ともいう)は、ゲル層を有する身体貼付用シートであって、該ゲル層は、次の成分(A)~(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C)アルミニウム原子
(D)ポリビニルアルコール
を含有し、
該ゲル層中の成分(A)の含有量が50質量%以上85質量%以下であり、
該ゲル層中の成分(D)の含有量が8質量%以上であり、
質量比[(B)/(C)]が70以上800以下である。
本発明の身体貼付用シートは上記構成を有することにより、皮膚への密着性に優れるとともに、貼付時の取り扱い性に優れるものとなる。 [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.
成分(B)はカルボキシ基を有するポリマーであり、成分(C)のイオン化物である3価のアルミニウムイオンとのイオン間相互作用により架橋構造を形成し得る。すなわち該アルミニウムイオンは成分(B)の架橋剤として作用し得る。よって本発明のシートを構成するゲル層中で、成分(B)は成分(C)により架橋された架橋構造を有していると考えられる。
一方、成分(D)はアルミニウムイオンによる架橋形成能を有さないポリマーであり、ゲル層中では、成分(B)と成分(C)とから構成される架橋マトリックス内に成分(D)の高分子鎖が流動可能な状態で存在していると考えられる。
そして本発明のシートを構成するゲル層は、成分(B)と成分(C)とを特定の比率で含有し、且つ成分(D)を所定量含有させることで、従来のゲル層よりも広い周波数領域で粘性的性質を示すものとなる。さらに該ゲル層は、低周波数領域では粘性的性質が強く、高周波数領域に移行するにつれて粘性的性質がより強くなるという特徴的な粘弾性挙動を示した。そして、このような粘弾性挙動を示すゲル層は、皮膚への高い密着性を発現し、貼付時の貼り付け性に優れるだけでなく、貼付時のべたつきが抑えられ、粘着面(すなわちゲル層)同士が一旦貼り付いても元の状態に戻しやすいことが見出された。このような粘着物性が発現した作用機構としては、ゲル層における質量比[(B)/(C)]を所定値以下とし、且つ成分(D)の存在割合を増加させることにより、架橋点が少なく変形しやすいゲル構造が形成されるため、シートの皮膚への密着性が向上したと考えられる。またゲル層において、成分(D)の存在割合を増加させるとゲル層のタック力向上により皮膚への密着性も向上するが、質量比[(B)/(C)]を所定値以上とすることで過度なタック力の向上を抑え、貼付時の取り扱い性を良好に保つことができたと考えられる。 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.
本発明の身体貼付用シートは、次の成分(A)~(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C)アルミニウム原子
(D)ポリビニルアルコール
を含有し、成分(A)の含有量が50質量%以上85質量%以下であり、成分(D)の含有量が8質量%以上であり、質量比[(B)/(C)]が70以上800以下であるゲル層を有する。
該ゲル層中で、成分(B)は成分(C)により架橋された架橋構造を有している。該ゲル層を有する本発明のシートは皮膚への密着性に優れるとともに、貼付時の取り扱い性に優れるものとなる。 <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.
本発明において、ゲル層の粘性的性質及び弾性的性質は、損失正接(tanδ)の値を指標として評価することができる。損失正接の値が大きいゲル層は、より粘性的性質が高いことを意味する。 (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.
ゲル層の損失正接は、具体的には実施例に記載の方法により測定できる。 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.
ボールタック試験は、具体的には実施例に記載の方法により行うことができる。 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.
本発明のシートを構成するゲル層は水を含有することで、薬効成分、冷感成分等の有効成分を皮膚に効果的に浸透させることができる。
成分(A)としては例えば、脱イオン水、蒸留水、高純水、超純水等の精製水を用いることができる。
ゲル層中の成分(A)の含有量は、有効成分を皮膚に効果的に浸透させる観点から、50質量%以上であり、好ましくは55質量%以上、より好ましくは60質量%以上、さらに好ましくは65質量%以上である。また、皮膚への密着性を向上させる及びゲル層の密着性及び安定性を確保する観点からは、85質量%以下であり、好ましくは80質量%以下、より好ましくは78質量%以下、さらに好ましくは77質量%以下である。そして、ゲル層中の成分(A)の含有量は、50質量%以上85質量%以下であり、好ましくは55質量%以上80質量%以下、より好ましくは60質量%以上78質量%以下、さらに好ましくは65質量%以上77質量%以下である。 (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.
本発明のシートを構成するゲル層は、成分(B)としてカルボキシメチルセルロース又はその塩を含有する。成分(B)は、成分(B)はカルボキシ基を有するポリマーであり、成分(C)のイオン化物である3価のアルミニウムイオンとのイオン間相互作用により架橋構造を形成し得る。
カルボキシメチルセルロースの塩としては、ナトリウム塩、カリウム塩等のアルカリ金属塩、アンモニウム塩等が挙げられる。入手容易性等の観点から、カルボキシメチルセルロースの塩としてはカルボキシメチルセルロースのアルカリ金属塩が好ましく、カルボキシメチルセルロースのナトリウム塩(カルボキシメチルセルロースナトリウム)がより好ましい。 (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).
なお、成分(B)のエーテル化度とは、成分(B)のグルコース単位あたりのカルボキシメチル基の置換度をいう。成分(B)がカルボキシメチルセルロースナトリウムである場合、そのエーテル化度は、例えばCMC工業会分析法(灰化法)に従い、以下の方法により測定できる。
〔カルボキシメチルセルロースナトリウムのエーテル化度の測定〕
カルボキシメチルセルロースナトリウム1gを精秤し、磁性ルツボに入れて600℃で灰化し、灰化によって生成した酸化ナトリウムをN/10硫酸でフェノールフタレインを指示薬として滴定し、カルボキシメチルセルロースナトリウム1gあたりの滴定量YmLを次式に入れて計算し、求めたエーテル化度を示すことができる。
エーテル化度=(162×Y)/(10,000-80×Y) 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)
なお成分(B)がカルボキシメチルセルロースの塩である場合、ゲル層中の成分(B)の含有量とは、塩としての含有量を意味する。 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.
本発明のシートを構成するゲル層は、成分(C)としてアルミニウム原子を含有する。成分(C)のイオン化物である3価のアルミニウムイオンは成分(B)の架橋剤として作用し得、ゲル層中では、成分(B)とのイオン間相互作用により架橋構造を形成していると考えられる。
成分(C)であるアルミニウム原子の供給源は、アルミニウム含有化合物(以下「成分(C1)」ともいう)である限り特に制限されないが、成分(B)を架橋し得るアルミニウムイオンとしての供給しやすさの観点、及び水溶性であることから、好ましくはアルミニウムを含有する無機金属塩である。 (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.
上記の中でも、アルミニウムイオンの供給しやすさの観点、及び水溶性であるという観点から、成分(C1)としては水酸化アルミニウム及び(メタ)ケイ酸アルミン酸マグネシウムからなる群から選ばれる1種以上が好ましい。また、ゲル層の保存安定性を向上させる観点から、成分(C1)は2種以上のアルミニウム含有化合物を含むことが好ましく、少なくとも(メタ)ケイ酸アルミン酸マグネシウムを含むことがより好ましく、水酸化アルミニウム及び(メタ)ケイ酸アルミン酸マグネシウムであることがさらに好ましい。 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.
なお、ゲル層中の成分(C)の含有量は、日本薬局方 一般試験法 誘導結合プラズマ発光分光分析法及び誘導結合プラズマ質量分析法に従って測定することができる。 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.
本発明のシートを構成するゲル層は、成分(D)としてポリビニルアルコールを含有する。前記成分(B)及び成分(C)に加えて成分(D)を含有させることにより、ゲル層のタック力及び低周波数領域の粘性的性質が向上し、これにより皮膚への密着性を向上させることができる。 (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.
成分(D)の重量平均分子量が好ましくは150,000以下、より好ましくは110,000以下、さらに好ましくは100,000以下であると、ゲル層中での成分(D)の高分子鎖の絡み合いが少なく、より変形しやすいゲル構造を形成できると考えられる。この効果によりゲル層のタック力がより向上し、皮膚への密着性も向上すると考えられる。
成分(D)の粉末原料の重量平均分子量は、下記条件で、粉末原料を水に溶解させた水溶液をサイズ排除クロマトグラフィー(SEC)で測定することで得られる。なお「成分(D)の粉末原料」とは、ゲル層又は後述するゲル形成用組成物に配合する前の、粉末状態の成分(D)を意味する。また、ゲル層中の成分(D)の重量平均分子量は、下記条件で、ゲル層の抽出液をSECで測定することで得られる。
<SEC測定条件>
測定装置:東ソー(株)製「SEC-8320」
溶離液:0.2mol/Lリン酸バッファー/アセトニトリル=9/1(V/V%)
ガードカラム:東ソー(株)製「PWXL(6mm×4cm)」
分析カラム:東ソー(株)製「G4000PWxL+G2500PWxL(7.8mm×30cm)
流量:1mL/min
カラム温度:40℃
注入量:100μL
サンプルサイズ:1mg/mL
分子量換算標準:東ソー(株)製PEO(SE-150(97.7万)、SE-70(58万)、SE-30(39.4万)、SE-15(14.3万)、SE-8(10.1万)、SE-2(2.1万))
検出器:RI 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
成分(D)のケン化度は、JIS K6726:1994に従って測定することができる。 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.
但し成分(D)としては、アルミニウムイオンとのイオン間相互作用により架橋構造を形成し得る官能基の含有量が少ないことが好ましい。成分(B)の架橋構造の形成を阻害させないためである。例えば成分(D)中のカルボキシ基の含有量は、好ましくは0.1モル%以下、より好ましくは0.01モル%以下であり、さらに好ましくは0モル%である。 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 %.
ゲル層中の成分(D)の含有量は、下記条件で、ゲル層の抽出液を1H-NMRで測定することで得られる。
<1H-NMR測定条件>
測定装置:JEOL製「MR-400」
観測核:1H
周波数:300MHz以上
パルス遅延時間:25秒
積算回数:32回
モード:Presaturation
溶媒:D2O
内部標準:0.1%トリメチルプロピオン酸Na
サンプルサイズ:10mg/mL 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
ゲル層は、本発明の目的を損なわない範囲で前記成分(A)~(D)以外の成分を適宜含有してもよい。その他の成分としては、例えば、化粧品、香粧品、医薬品、医薬部外品等に一般的に使用される成分等が挙げられる。
これらの製品に一般的に使用される成分としては、例えば、成分(B)及び成分(D)以外の水溶性ポリマー、保湿剤、美白剤、血行促進剤、消炎剤、殺菌剤、紫外線吸收剤、着色剤、防腐剤、抗酸化剤、香料、油剤、pH調整剤、キレート剤、保水剤、薬剤、冷感剤、温感剤、アルコール類等が挙げられる。 (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.
本発明のシートを構成する上記ゲル層は、次の成分(A)~(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C)アルミニウム原子
(D)ポリビニルアルコール
を含有し、成分(A)の含有量が50質量%以上85質量%以下であり、成分(D)の含有量が8質量%以上であり、質量比[(B)/(C)]が70以上800以下であるゲル形成用組成物を用いて形成することができる。なお本発明においては、ゲル層中の各成分の含有量は、該ゲル層の形成に用いたゲル形成用組成物中の各成分の含有量又は配合量と同じであるとみなすことができる。 <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.
(A)水
(B)カルボキシメチルセルロース又はその塩
(C1)アルミニウム含有化合物
(D)ポリビニルアルコール
を配合してなり、
成分(A)の配合量が50質量%以上85質量%以下であり、
成分(D)の配合量が8質量%以上であり、
質量比[(B)/(C1)]が25以上140以下であるゲル形成用組成物を用いて形成することが好ましい。
ゲル形成用組成物に配合される成分(A)、(B)、(C1)及び(D)、その他の成分、並びにこれらの好適態様については、特に断りのない限り、前記ゲル層において記載した内容と同じである。 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.
本発明の身体貼付用シートの構成は、前記ゲル層を有する限り特に制限されないが、シートの取り扱い性及び強度の観点から、該ゲル層と、基材とを有することが好ましい。すなわち本発明の身体貼付用シートは、前記ゲル層と基材とを積層した2層構成とすることができる。また、ゲル層において基材が積層されていない面には、剥離フィルムを積層してもよい。剥離フィルムは、ゲル層を保護するために用いられ、シートの貼付時にはゲル層から剥離されるフィルムであり、例えば無軸延伸ポリプロピレンフィルム、二軸延伸ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム等を用いることができる。これらの中でも、優れた剥離性を付与する観点から、エンボス加工が施されているものが好ましく、エンボス加工が施された無軸延伸ポリプロピレンフィルムがより好ましい。
シートの取り扱い性の観点から、本発明の身体貼付用シートは基材、ゲル層、及び剥離フィルムをこの順で有する3層構成であることが好ましい。 <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.
本発明のシートを構成する基材としては、織布、不織布、偏布、合成樹脂フィルム、耐水紙等のシート状の基材を用いることができる。また、これらのシート状基材が複数積層されてなる積層基材を使用することもできる。
具体的には、ナイロン、ポリプロピレン、ポリエステル、ポリエチレン、ポリスチレン、ポリウレタン、ポリオレフィン等からなる合成繊維の織布又は不織布;絹、綿、麻、レーヨン、コラーゲン等からなる天然繊維の織布又は不織布;ナイロン、ポリプロピレン、ポリエステル、ポリエチレン、ポリウレタン等の合成樹脂からなるフィルム;プルラン、デンプン等からなるシート状基材;又は、これらが複数積層されてなる積層基材等が挙げられる。
上記の中でも、シートの取り扱い性、ゲル層の積層しやすさ、追従性の観点から、基材としては、好ましくは不織布であり、より好ましくはナイロン、ポリプロピレン、ポリエステル、又はポリエチレンからなる不織布である。 (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. .
基材の坪量は特に制限されないが、シートの取り扱い性、ゲル層の積層しやすさの観点から、好ましくは10g/m2以上であり、また、追従性を向上させる観点から、好ましくは200g/m2以下、より好ましくは150g/m2以下、さらに好ましくは120g/m2以下である。 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.
本発明は、下記工程(I)~工程(III)をこの順で含む、ゲル層を有する身体貼付用シートの製造方法を提供する。該製造方法により、本発明の身体貼付用シートを効率よく製造することができる。
工程(I) 次の成分(A)、(B)、(C1)及び(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C1)アルミニウム含有化合物
(D)ポリビニルアルコール
を配合してなり、
成分(A)の配合量が50質量%以上85質量%以下であり、
成分(D)の配合量が8質量%以上であり、
質量比[(B)/(C1)]が25以上140以下であるゲル形成用組成物を調製する工程
工程(II) 基材と剥離フィルムとの間に前記ゲル形成用組成物を充填し、基材、ゲル形成用組成物層、及び剥離フィルムを順に有する積層シートを作製する工程
工程(III) 前記積層シートを包装体内に密封し、次いで該包装体内で前記ゲル形成用組成物層を架橋させる工程 [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
工程(I)では、次の成分(A)、(B)、(C1)及び(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C1)アルミニウム含有化合物
(D)ポリビニルアルコール
を配合してなり、
成分(A)の配合量が50質量%以上85質量%以下であり、
成分(D)の配合量が8質量%以上であり、
質量比[(B)/(C1)]が25以上140以下であるゲル形成用組成物を調製する。ゲル形成用組成物及びその調製方法、並びにその好適態様については前記の通りである。 <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.
工程(II)では、基材と剥離フィルムとの間に前記ゲル形成用組成物を充填し、基材、ゲル形成用組成物層、及び剥離フィルムを順に有する積層シートを作製する。基材及び剥離フィルムについては前記の通りである。
基材と剥離フィルムとの間にゲル形成用組成物を充填し、積層する方法としては、例えば、基材と剥離フィルムとの間にゲル形成用組成物を挟み込み、次いで、ベーカー式アプリケーター等を用いて所望の厚さに展延する方法;剥離フィルム上にゲル形成用組成物を所望の厚さとなるように塗工し、次いで基材を積層する方法;等が挙げられる。あるいは、基材と剥離フィルムとを対面させてそれぞれ搬送ロールにて走行させ、基材と剥離フィルムとの間にゲル形成用組成物を充填し、ロールで押圧しながら送り出して積層シート化することもできる。この際、2つのロール間距離を調整することにより、ゲル形成用組成物層を所望の厚さに調整できる。
工程(II)で得られた積層シートは、必要に応じ、所望の大きさに切断してから工程(III)に供する。 <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).
工程(III)では、工程(II)で得られた積層シートを包装体内に密封し、次いで該包装体内で前記ゲル形成用組成物層を架橋させる。これにより、架橋構造を有するゲル層を形成できる。 <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.
<1>
ゲル層を有する身体貼付用シートであって、
該ゲル層は、次の成分(A)~(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C)アルミニウム原子
(D)ポリビニルアルコール
を含有し、
該ゲル層中の成分(A)の含有量が50質量%以上85質量%以下であり、
該ゲル層中の成分(D)の含有量が8質量%以上であり、
質量比[(B)/(C)]が70以上800以下である、身体貼付用シート。
<2>
前記ゲル層中の成分(A)の含有量が、好ましくは55質量%以上、より好ましくは60質量%以上、さらに好ましくは65質量%以上であり、好ましくは80質量%以下、より好ましくは78質量%以下、さらに好ましくは77質量%以下である、<1>の身体貼付用シート。
<3>
前記ゲル層中の成分(B)の含有量が、好ましくは1.0質量%以上、より好ましくは1.5質量%以上、さらに好ましくは2.0質量%以上、よりさらに好ましくは2.3質量%以上、よりさらに好ましくは2.5質量%以上であり、好ましくは5.0質量%以下、より好ましくは4.0質量%以下、さらに好ましくは3.8質量%以下、よりさらに好ましくは3.4質量%以下である、<1>又は<2>の身体貼付用シート。
<4>
前記ゲル層中の成分(C)の含有量が、好ましくは0.002質量%以上、より好ましくは0.003質量%以上、さらに好ましくは0.005質量%以上、よりさらに好ましくは0.0062質量%以上、よりさらに好ましくは0.008質量%以上であり、好ましくは0.05質量%以下、より好ましくは0.04質量%以下、さらに好ましくは0.035質量%以下、よりさらに好ましくは0.02質量%以下である、<1>~<3>のいずれか1の身体貼付用シート。
<5>
前記質量比[(B)/(C)]が、好ましくは85以上、より好ましくは100以上であり、好ましくは600以下、より好ましくは550以下、さらに好ましくは500以下である、<1>~<4>のいずれか1の身体貼付用シート。
<6>
前記成分(D)の重量平均分子量が、好ましくは30,000以上、より好ましくは50,000以上、さらに好ましくは70,000以上であり、好ましくは150,000以下、より好ましくは120,000以下、さらに好ましくは100,000以下である、<1>~<5>のいずれか1の身体貼付用シート。
<7>
前記成分(D)のケン化度が、好ましくは75モル%以上、より好ましくは82モル%以上、さらに好ましくは85モル%以上であり、好ましくは98モル%以下、より好ましくは96モル%以下である、<1>~<6>のいずれか1の身体貼付用シート。
<8>
前記ゲル層中の成分(D)の含有量が、好ましくは8.3質量%以上、より好ましくは8.5質量%以上であり、好ましくは18質量%以下、より好ましくは14質量%以下、さらに好ましくは12質量%以下である、<1>~<7>のいずれか1の身体貼付用シート。
<9>
前記ゲル層中の質量比[(D)/(B)]が、好ましくは2以上、より好ましくは2.4以上、さらに好ましくは2.8以上、よりさらに好ましくは3以上であり、好ましくは8以下、より好ましくは6以下、さらに好ましくは5以下、よりさらに好ましくは4.5以下、よりさらに好ましくは4以下である、<1>~<8>のいずれか1の身体貼付用シート。
<10>
前記ゲル層中の前記成分(A)~(D)の合計含有量が、好ましくは70質量%以上、より好ましくは80質量%以上、さらに好ましくは85質量%以上であり、また、100質量%以下である、<1>~<9>のいずれか1の身体貼付用シート。 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.
前記ゲル層中のポリアクリル酸又はその塩の含有量が、好ましくは4質量%未満であり、より好ましくは3質量%未満、さらに好ましくは2質量%以下であり、よりさらに好ましくは1質量%以下であり、よりさらに好ましくは0質量%である、<1>~<10>のいずれか1の身体貼付用シート。
<12>
前記ゲル層中で、前記成分(B)が前記成分(C)により架橋された架橋構造を有する、<1>~<11>のいずれか1の身体貼付用シート。
<13>
前記ゲル層の、JIS Z0237:2009に従って傾斜板の角度30°、温度23℃、50%R.H.の条件下で行われるボールタック試験におけるボールナンバーが好ましくは15以上、より好ましくは18以上、さらに好ましくは19以上、よりさらに好ましくは20以上であり、好ましくは32以下、より好ましくは30以下、さらに好ましくは28以下、よりさらに好ましくは26以下である、<1>~<12>のいずれか1の身体貼付用シート。
<14>
前記ゲル層の、温度25℃、周波数0.1Hzでの動的粘弾性測定における損失正接が好ましくは0.18以上、より好ましくは0.20以上、さらに好ましくは0.22以上、よりさらに好ましくは0.25以上、よりさらに好ましくは0.28以上であり、好ましくは0.60以下、より好ましくは0.58以下、さらに好ましくは0.50以下である、<1>~<13>のいずれか1の身体貼付用シート。
<15>
前記ゲル層の厚さが、好ましくは0.1mm以上、より好ましくは0.3mm以上、さらに好ましくは0.5mm以上であり、好ましくは5mm以下、より好ましくは3mm以下、さらに好ましくは2mm以下である、<1>~<14>のいずれか1の身体貼付用シート。
<16>
前記身体貼付用シートが、前記ゲル層と基材とを積層した2層構成、又は、基材、前記ゲル層、及び剥離フィルムをこの順で有する3層構成である、<1>~<15>のいずれか1の身体貼付用シート。
<17>
前記基材が、好ましくは不織布、より好ましくはナイロン、ポリプロピレン、ポリエステル、又はポリエチレンからなる不織布である、<16>の身体貼付用シート。
<18>
ゲル層を有する身体貼付用シートであって、
該ゲル層は、次の成分(A)、(B)、(C1)及び(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C1)アルミニウム含有化合物
(D)ポリビニルアルコール
を配合してなるゲル形成用組成物であって、成分(A)の配合量が50質量%以上85質量%以下であり、成分(D)の配合量が8質量%以上であり、質量比(B)/(C1)が25以上140以下であるゲル形成用組成物を用いて形成され、
成分(B)が成分(C1)により架橋されてなる、身体貼付用シート。
<19>
次の成分(A)~(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C)アルミニウム原子
(D)ポリビニルアルコール
を含有し、成分(A)の含有量が50質量%以上85質量%以下であり、成分(D)の含有量が8質量%以上であり、質量比[(B)/(C)]が60以上800以下である、ゲル形成用組成物。
<20>
次の成分(A)、(B)、(C1)及び(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C1)アルミニウム含有化合物
(D)ポリビニルアルコール
を配合してなり、
成分(A)の配合量が50質量%以上85質量%以下であり、
成分(D)の配合量が8質量%以上であり、
質量比[(B)/(C1)]が25以上140以下である、ゲル形成用組成物。
<21>
前記ゲル形成用組成物に配合される成分(C1)の量が、好ましくは0.005質量%以上、より好ましくは0.01質量%以上、さらに好ましくは0.02質量%以上であり、好ましくは0.2質量%以下、より好ましくは0.1質量%以下、さらに好ましくは0.06質量%以下、よりさらに好ましくは0.04質量%以下である、<18>の身体貼付用シート又は<20>のゲル形成用組成物。
<22>
前記成分(C1)の配合量に対する成分(B)の配合量(質量比[(B)/(C1)])が、より好ましくは50以上、さらに好ましくは60以上であり、より好ましくは130以下、さらに好ましくは120以下、よりさらに好ましくは100以下、よりさらに好ましくは95以下である、<18>の身体貼付用シート、<20>又は<21>のゲル形成用組成物。
<23>
前記成分(C1)が、好ましくは水酸化アルミニウム、水酸化アルミニウムマグネシウム、アルミン酸ナトリウム、硫酸アルミニウム、硫酸アルミニウムカリウム、硫酸アルミニウムアンモニウム、炭酸アルミニウム、硝酸アルミニウム、塩化アルミニウム、(メタ)ケイ酸アルミン酸マグネシウム、酢酸アルミニウム、乳酸アルミニウム、ステアリン酸アルミニウム、ミリスチン酸アルミニウム、アルミニウムグリシネート、安息香酸アルミニウム、アラントインクロルヒドロキシアルミニウムからなる群から選ばれる1種以上、より好ましくは水酸化アルミニウム及び(メタ)ケイ酸アルミン酸マグネシウムからなる群から選ばれる1種以上、さらに好ましくは(メタ)ケイ酸アルミン酸マグネシウムを含み、よりさらに好ましくは水酸化アルミニウム及び(メタ)ケイ酸アルミン酸マグネシウムである、<18>の身体貼付用シート、<20>~<22>のいずれか1のゲル形成用組成物。 <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>.
下記工程(I)~工程(III)をこの順で含む、ゲル層を有する身体貼付用シートの製造方法。
工程(I) 次の成分(A)、(B)、(C1)及び(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C1)アルミニウム含有化合物
(D)ポリビニルアルコール
を配合してなり、
成分(A)の配合量が50質量%以上85質量%以下であり、
成分(D)の配合量が8質量%以上であり、
質量比[(B)/(C1)]が25以上140以下であるゲル形成用組成物を調製する工程
工程(II) 基材と剥離フィルムとの間に前記ゲル形成用組成物を充填し、基材、ゲル形成用組成物層、及び剥離フィルムを順に有する積層シートを作製する工程
工程(III) 前記積層シートを包装体内に密封し、次いで該包装体内で前記ゲル形成用組成物層を架橋させる工程 <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
成分(B)の1質量%水溶液の粘度は、25℃において、B型粘度計(東機産業(株)製「TVB-10」)を用いて測定した。 <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.).
成分(D)の粉末原料の重量平均分子量は、下記条件で、粉末原料を水に溶解させた水溶液をサイズ排除クロマトグラフィー(SEC)で測定することにより求めた。またゲル層中の成分(D)の重量平均分子量は、下記条件で、ゲル層の抽出液をサイズ排除クロマトグラフィー(SEC)で測定することにより求めた。表中に記載の成分(D)の重量平均分子量は、粉末原料及びゲル層中の成分(D)の重量平均分子量である。
<SEC測定条件>
測定装置:東ソー(株)製「SEC-8320」
溶離液:0.2mol/Lリン酸バッファー/アセトニトリル=9/1(V/V%)
ガードカラム:東ソー(株)製「PWXL(6mm×4cm)」
分析カラム:東ソー(株)製「G4000PWxL+G2500PWxL(7.8mm×30cm)」
流量:1mL/min
カラム温度:40℃
注入量:100μL
サンプルサイズ:1mg/mL
分子量換算標準:東ソー(株)製PEO(SE-150(97.7万)、SE-70(58万)、SE-30(39.4万)、SE-15(14.3万)、SE-8(10.1万)、SE-2(2.1万))
検出器:RI <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
(ゲル形成用組成物の調製)
表に示す処方に従ってゲル形成用組成物を調製した。具体的には、プロピレングリコールにパラオキシ安息香酸メチル及びメントールを加温溶解させた溶液と、ポリビニルアルコール及びpH調整剤を含有した水溶液とを予め調製した。ポリビニルアルコール及びpH調整剤を含有した水溶液を混練機に投入し、次いでその他の全成分を添加して混合し、ゲル形成用組成物を調製した。なお、表に記載した配合量は、各成分の有効成分量(質量%)である。また表中、アルミニウムイオンによる架橋形成能を有し且つ成分(B)に属さないポリマーを「成分(B’)」と表記した。 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')".
上記ゲル形成用組成物を、基材であるポリエステル不織布(厚さ0.7mm)と、ポリプロピレン剥離フィルムとの間に挟み込み、ベーカー式アプリケーターによってゲル形成用組成物層の厚さを1.5mmに調整して展延することで、不織布、ゲル形成用組成物層、及び剥離フィルムが順に積層されたシートを得た。該シートを12.5cm×8.5cmにカットしアルミピロー(120mm×170mm、アズワン製)に密封した後、表に記載の条件下にて熟成し、ゲル形成用組成物層の架橋反応を進行させて、不織布、ゲル層、及び剥離フィルムをこの順で有する3層構成の身体貼付用シートを製造した。
得られた身体貼付用シートを用いて、以下の方法で評価を行った。結果を表1~5に示す。 (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.
各例の身体貼付用シートのゲル層のボールタック試験は、JIS Z0237:2009に準拠して、傾斜板の角度30°、温度23℃、50%R.H.の条件下で行った。各例の身体貼付用シートをアルミピローから取り出し、剥離フィルムを剥がした後に速やかにボールタック試験機に設置してボールタック試験を実施し、ゲル層の粘着領域で5秒以上停止する最大のボールナンバーを表に示した。 <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.
各例の身体貼付用シートのゲル層の損失正接(tanδ)は、レオメータ(アントンパール(株)製「Physica MCR301」)を用いて測定した。各例の身体貼付用シートを直径25mmの円に切り出し、不織布側を両面テープでレオメータの試料部(直径25mmの平行平板)に固定した。次いで剥離フィルムをはがして、以下の条件でゲル層の損失弾性率及び貯蔵弾性率を測定し、これらの値から損失正接(tanδ)を算出した。測定は複数回(3回以上)行い、その平均値を採用した。
〔測定条件〕
・ノーマルフォース:1N
・ギャップ間隔:1~2mm
・ゲル層の質量:0.5~1.0g
・測定周波数:0.1Hz
・歪:2%
・温度:25℃ <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℃
貼付直後の密着性
各例の身体貼付用シートをアルミピローから取り出し、剥離フィルムを剥がした直後に、専門パネラーのふくらはぎに、シート長辺がふくらはぎの周方向に対し垂直となるよう貼付した。貼付から10秒経過後に、専門パネラーが足首の底背屈運動を10回行い、身体貼付用シートがふくらはぎから浮いている部分、すなわち該ふくらはぎから剥がれている部分の面積を測定した。身体貼付用シート全体の面積に対する、該シートが剥がれている部分の面積の割合(%)を求め、下記基準にしたがって評価した。評価の数値が高いほど、貼付直後の密着性が優れていることを表している。
なお、本実施例の専門パネラーによる評価は、いずれも3名のパネラーにより行われ、表に示した評価の数値は3名のパネラーの平均値である。
〔評価基準〕
7:シートが剥がれている部分の面積の割合が5%以下。
6:シートが剥がれている部分の面積の割合が5%超10%以下。
5:シートが剥がれている部分の面積の割合が10%超20%以下。
4:シートが剥がれている部分の面積の割合が20%超30%以下。
3:シートが剥がれている部分の面積の割合が30%超40%以下。
2:シートが剥がれている部分の面積の割合が40%超50%以下。
1:シートが剥がれている部分の面積の割合が50%超。 <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%.
各例の身体貼付用シートを前記と同様に専門パネラーのふくらはぎに貼付し、貼付から10秒経過後に剥離した。同試行を再度実施した後、専門パネラーのもう片方のふくらはぎに、剥離した身体貼付用シートを前記と同様に再度貼付し、10秒経過後に足首の底背屈運動を10回行った。前記と同様の方法で身体貼付用シートがふくらはぎから剥がれている部分の面積を測定し、前記基準にしたがって評価した。評価の数値が高いほど、貼り直し後の密着性が優れていることを表している。 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.
市販のボディクリーム(油剤:11%、乳化剤:2.5%、ポリオール:12%、水:72%、その他:2.5%)を専門パネラーのふくらはぎに塗布した。次いで前記と同様に、各例の身体貼付用シートを専門パネラーのふくらはぎに貼付し、貼付から10秒後に、専門パネラーが足首の底背屈運動を10回行った。前記と同様の方法で身体貼付用シートがふくらはぎから剥がれている部分の面積を測定し、前記基準にしたがって評価した。評価の数値が高いほど、ボディクリーム塗布後の密着性が優れていることを表している。 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.
各例の身体貼付用シートを前記と同様に専門パネラーのふくらはぎに貼付した。3時間貼付した後の剥がれにくさを5段階(5点:非常に剥がれにくい、4点:剥がれにくい、3点:やや剥がれにくい、2点:やや剥がれやすい、1点:剥がれやすい)で評価した。評価の数値が高いほど、長時間貼付後の密着性が優れていることを表している。 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.
負荷条件下の密着性
負荷条件を課した状態での密着性を評価した。この負荷条件は、曲率の高い部分へ身体貼付用シートを貼付し、且つ、貼付した部分に動きを加えるものであり、曲率の高い部位への貼付直後の密着性及び追従性を評価できる。
各例の身体貼付用シートをアルミピローから取り出し、剥離フィルムを剥がした直後に、専門パネラーのひざに、シート長辺が膝の周方向に対し並行となるよう貼付した。貼付から10秒経過後に、専門パネラーがひざの曲げ伸ばし(90°~180°)運動を10回行い、身体貼付用シートがひざから浮いている部分、すなわちひざから剥がれている部分の面積を測定した。身体貼付用シート全体の面積に対する、該シートが剥がれている部分の面積の割合(%)を求めた。評価基準はふくらはぎへの粘着性と同じである。評価の数値が高いほど、負荷条件下の密着性が優れていることを表している。 <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.
(貼付しやすさ)
各例の身体貼付用シートをアルミピローから取り出し、剥離フィルムを剥がした直後に、専門パネラーのふくらはぎに、シート長辺がふくらはぎの周方向に対し垂直となるように貼付した。その際の貼付しやすさを5段階(5点:非常に貼付しやすい、4点:貼付しやすい、3点:やや貼付しやすい、2点:やや貼付しにくい、1点:貼付しにくい)で評価した。評価の数値が高いほど、容易かつきれいに身体貼付用シートを貼付しやすいことを表しており、数値が低いほど皺等が生じて身体貼付用シートをきれいに貼付しにくいことを表している。 <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.
各例の身体貼付用シートを上記と同様に貼付した際の粘着面(ゲル層)の指へのべたつきを5段階(5点:べたつかない、4点:あまりべたつかない、3点:ややべたつく、2点:べたつく、1点:非常にべたつく)で評価した。評価の数値が高いほど、指へのべたつきの度合いが低いことを表している。 (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.
各例の身体貼付用シートをアルミピローから取り出し、剥離フィルムを剥がしてシートを二つ折りにして、粘着面同士を接着させた。次いで、粘着面を離すときの離しやすさを5段階(5点:離しやすい、4点:やや離しやすい、3点:やや離しにくい、2点:離しにくい、1点:非常に離しにくい)で評価した。評価の数値が高いほど、粘着面同士が一旦貼り付いても離しやすく(元の状態に戻しやすく)、取り扱い性が良好であることを表している。 (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.
各例の身体貼付用シートを、アルミピローに封入した状態で50℃の恒温槽で1か月保管した後、25℃に戻した。アルミピローから身体貼付用シートを取り出し、外観及びゲル性状の保存安定性を下記基準で5段階評価した。評価の数値が高いほど、保存安定性が高いことを表している。
(外観)
5:保存前の状態と同等
4:ゲルの変色、不織布への染みだしが若干みられる
3:ゲルの変色、不織布への染みだしがややみられる
2:ゲルの変色、不織布への染みだしがみられる
1:シートとして使用困難
(ゲル性状)
各例の身体貼付用シートをアルミピローから取り出し、専門パネラーの前腕部に30分貼付後に剥離した際の肌へのゲル残りを5段階で評価した。
5:保存前の状態と同等(ゲルが肌に残らない)
4:ゲルがわずかに肌に残る
3:ゲルがやや肌に残る
2:ゲルが脆く、多量のゲルが肌に残る
1:シートとして使用困難 <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
Claims (7)
- ゲル層を有する身体貼付用シートであって、
該ゲル層は、次の成分(A)~(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C)アルミニウム原子
(D)ポリビニルアルコール
を含有し、
該ゲル層中の成分(A)の含有量が50質量%以上85質量%以下であり、
該ゲル層中の成分(D)の含有量が8質量%以上であり、
質量比[(B)/(C)]が70以上800以下である、身体貼付用シート。 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. - 前記ゲル層中で、前記成分(B)が前記成分(C)により架橋された架橋構造を有する、請求項1に記載の身体貼付用シート。 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).
- 前記成分(D)の重量平均分子量が150,000以下である、請求項1又は2に記載の身体貼付用シート。 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.
- 前記成分(D)のケン化度が75モル%以上である、請求項1~3のいずれか1項に記載の身体貼付用シート。 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.
- 前記ゲル層の、JIS Z0237:2009に従って傾斜板の角度30°、温度23℃、50%R.H.の条件下で行われるボールタック試験におけるボールナンバーが15以上30以下である、請求項1~4のいずれかに記載の身体貼付用シート。 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 .
- 前記ゲル層の、温度25℃、周波数0.1Hzでの動的粘弾性測定における損失正接が0.20以上である、請求項1~5のいずれかに記載の身体貼付用シート。 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.
- 下記工程(I)~工程(III)をこの順で含む、ゲル層を有する身体貼付用シートの製造方法。
工程(I) 次の成分(A)、(B)、(C1)及び(D):
(A)水
(B)カルボキシメチルセルロース又はその塩
(C1)アルミニウム含有化合物
(D)ポリビニルアルコール
を配合してなり、
成分(A)の配合量が50質量%以上85質量%以下であり、
成分(D)の配合量が8質量%以上であり、
質量比[(B)/(C1)]が25以上140以下であるゲル形成用組成物を調製する工程
工程(II) 基材と剥離フィルムとの間に前記ゲル形成用組成物を充填し、基材、ゲル形成用組成物層、及び剥離フィルムを順に有する積層シートを作製する工程
工程(III) 前記積層シートを包装体内に密封し、次いで該包装体内で前記ゲル形成用組成物層を架橋させる工程 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
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280041823.1A CN117479959A (en) | 2021-06-15 | 2022-03-31 | Sheet for body attachment |
KR1020237037628A KR20240021754A (en) | 2021-06-15 | 2022-03-31 | body attachment sheet |
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JP2021-099341 | 2021-06-15 | ||
JP2021099341 | 2021-06-15 |
Publications (1)
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WO2022264653A1 true WO2022264653A1 (en) | 2022-12-22 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2022/016558 WO2022264653A1 (en) | 2021-06-15 | 2022-03-31 | Sheet for application to body |
Country Status (5)
Country | Link |
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JP (1) | JP7301190B2 (en) |
KR (1) | KR20240021754A (en) |
CN (1) | CN117479959A (en) |
TW (1) | TW202306595A (en) |
WO (1) | WO2022264653A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024127896A1 (en) * | 2022-12-14 | 2024-06-20 | 花王株式会社 | Sheet for application to body |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5517347A (en) * | 1978-07-24 | 1980-02-06 | Kobayashi Koji | Production of poultice with high water content |
JP2001064161A (en) * | 1999-08-30 | 2001-03-13 | Lion Corp | Cataplasm |
JP2016124870A (en) * | 2014-12-26 | 2016-07-11 | 花王株式会社 | Water-containing gel composition |
JP2020059697A (en) * | 2018-10-05 | 2020-04-16 | 花王株式会社 | Adhesive sheet for affixation to body housed in container |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5517347B2 (en) | 2009-05-07 | 2014-06-11 | 株式会社中尾製作所 | Door stopper device |
-
2022
- 2022-03-31 JP JP2022059579A patent/JP7301190B2/en active Active
- 2022-03-31 CN CN202280041823.1A patent/CN117479959A/en active Pending
- 2022-03-31 KR KR1020237037628A patent/KR20240021754A/en unknown
- 2022-03-31 WO PCT/JP2022/016558 patent/WO2022264653A1/en active Application Filing
- 2022-04-07 TW TW111113172A patent/TW202306595A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5517347A (en) * | 1978-07-24 | 1980-02-06 | Kobayashi Koji | Production of poultice with high water content |
JP2001064161A (en) * | 1999-08-30 | 2001-03-13 | Lion Corp | Cataplasm |
JP2016124870A (en) * | 2014-12-26 | 2016-07-11 | 花王株式会社 | Water-containing gel composition |
JP2020059697A (en) * | 2018-10-05 | 2020-04-16 | 花王株式会社 | Adhesive sheet for affixation to body housed in container |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024127896A1 (en) * | 2022-12-14 | 2024-06-20 | 花王株式会社 | Sheet for application to body |
Also Published As
Publication number | Publication date |
---|---|
JP7301190B2 (en) | 2023-06-30 |
TW202306595A (en) | 2023-02-16 |
JP2022191154A (en) | 2022-12-27 |
CN117479959A (en) | 2024-01-30 |
KR20240021754A (en) | 2024-02-19 |
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